research papers
True molecular conformation and
by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applicationsaCenter for Material Interfaces, Electron Crystallography, Instituto Italiano di Tecnologia, Pontedera 56025, Italy, bSchool of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom, cDepartment of Earth Sciences, University of Pisa, Pisa 56126, Italy, dPAH Research, Igling-Holzhausen, D-86859, Germany, and eDepartment of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA
*Correspondence e-mail: mauro.gemmi@iit.it
The true molecular conformation and the e]dinaphtho[2,3-a;1′,2′,3′,4′-ghi]fluoranthene, 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene were determined ab initio by 3D electron diffraction. All three molecules are remarkable polycyclic aromatic hydrocarbons. The molecular conformation of two of these compounds could not be determined via classical spectroscopic methods due to the large size of the molecule and the occurrence of multiple and reciprocally connected aromatic rings. The molecular structure of the third molecule was previously considered provisional. These compounds were isolated as by-products in the synthesis of similar products and were at the same time nanocrystalline and available only in very limited amounts. 3D electron diffraction data, taken from submicrometric single crystals, allowed for direct ab initio structure solution and the unbiased determination of the internal molecular conformation. Detailed synthetic routes and spectroscopic analyses are also discussed. Based on many-body perturbation theory simulations, benzo[e]dinaphtho[2,3-a;1′,2′,3′,4′-ghi]fluoranthene may be a promising candidate for triplet–triplet annihilation and 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene may be a promising candidate for intermolecular singlet fission in the solid state.
of benzo[1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are organic molecules containing a series of conjugated carbon rings. The term `PAH' is generally restricted to compounds consisting of only C and H atoms, and comprising two or more aromatic rings bonded in various arrangements (Lawal, 2017). Early syntheses of PAHs (Anschütz, 1886; Scholl et al., 1910; Scholl & Meyer, 1932) attracted considerable interest due to their optoelectronic properties, which led to the creation of a number of functionalized compounds based on PAH backbones (Buchlovič et al., 2013; Ko et al., 2018; Castro et al., 2019). In particular, in the mid-1900s, Clar and co-workers synthesized and identified a number of PAHs and related compounds with unique physical and chemical properties (Clar et al., 1964, 1981; Clar & Schmidt, 1975).
In most cases, the identity of the newly synthesized organic compounds can be determined from combustion analysis and by a combination of NMR, IR, UV and i.e. compounds with different shapes but identical UV band positions (Clar & Schmidt, 1976, 1979; Clar et al., 1981).
In particular, a comparison of the UV and photoelectron (PE) spectral data provides information about the purity and helps to distinguish `isotopic PAHs',It is often impossible to characterize PAHs by single-crystal X-ray diffraction (XRD) because of the difficulty in obtaining suitable sufficiently large crystals. Therefore, the final confirmation is generally attained by powder XRD analysis. However, when there are many possible molecular structures that can match a particular stoichiometry, it may be difficult to determine the exact conformation based on spectroscopic data alone. Furthermore, PXRD is intrinsically limited to one-dimensional data and hampered by the overlap of independent reflections, which may become rather severe for unit-cell parameters longer than 20 Å. As a consequence of this unsatisfactory state of affairs, the conformation of several large PAHs mentioned in the literature is uncertain or unknown, and many more are considered suspect (Clar et al., 1981; Fetzer, 2000, 2007; Wilkes, 2010).
In recent years, electron diffraction (ED) has become a routine option for et al., 2007; Wan et al., 2013; Gemmi et al., 2019; Nannenga & Gonen, 2019). The 3D ED method has been used for the of hundreds of previously unknown structures, including inorganic materials (Kaiukov et al., 2020; Krysiak et al., 2021; Kapaca et al., 2021), small-molecule organics (Andrusenko et al., 2019; Jones et al., 2019; Brázda et al., 2019; Cui et al., 2020; Levine et al., 2020; Bruhn et al., 2021; Hall et al., 2021; Andrusenko et al., 2021; Papi et al., 2021), and macromolecules (Sawaya et al., 2016; Krotee et al., 2018; Lanza et al., 2019; Xu et al., 2019; Warmack et al., 2019). It is noteworthy that ab initio determination does not require information about the molecular conformation, but only a rough estimation of the atomic content of the In this article, we report the true molecular conformation and the determined by the 3D ED method for three PAHs belonging to two different systems.
determination when crystals sufficiently large for single-crystal XRD cannot be grown. The key development was the establishment of procedures for collecting and recombining 3D electron diffraction (3D ED) data (KolbFluoranthenes are one of the most studied classes of PAHs (Haritash & Kaushik, 2009). They are also known as `non-alternant PAHs' because they contain six-membered benzene rings fused with an additional five-membered ring (Gupte et al., 2016). Fluoranthene-based PAHs serve as a basic unit in preparing chromophores for organic light-emitting diodes (OLEDS) and field-effect transistors (Saranya et al., 2011). Benzo[e]dinaphtho[2,3-a;1′,2′,3′,4′-ghi]fluoranthene (I) is formed by together with two other hydrocarbons, namely, benzo[a]phenanthro[9′,10′-c]tetracene (II) and dibenzo[a,k]naphtho[1,2,3,4-ghi]perylene (III). Fig. 1 illustrates a stepwise model of the corresponding synthetic route described by Clar and co-workers (Clar et al., 1964). The molecular conformation of II is supported by several spectroscopic data, its reactive behaviour and, most conclusively, by an alternative synthesis with Zn dust that produces II exclusively (Fig. S1). Conversely, the molecular conformations of I and III were only reported as tentative (Clar et al., 1964). Spectroscopic data for II and III are presented and discussed in the supporting information.
The second system studied in this article involves both bisanthene and helianthrene compounds. Initially, 4,11-diphenylbisanthene (IV) was synthesized by Sauvage, who only determined the maximum positions of the longwave absorption bands (Sauvage, 1947a,b). Renewed interest in this compound was sparked in the 1970s, as it was shown to be one of the few molecules to fluoresce at IR wavelengths (Maulding, 1970; Rauhut et al., 1975). Following the procedure of Sauvage's synthesis (Sauvage, 1947a,b), we attempted to synthesize new IR emitters with a high fluorescent starting from helianthrone. Fig. 2 illustrates a stepwise model of the corresponding synthetic route. During this reaction, in addition to 4,11-diphenylbisanthene (IV), a number of by-products occur, among which only 7,16-diphenylhelianthrene (V) was identified previously (Arabei & Pavich, 2004). This compound appears in a greater yield when N2 is bubbled through the system during the reaction (Fort, 2010). Two additional by-products of the reaction, VI and VII, were not identified via spectroscopic data, but appear to form via a Diels–Alder condensation reaction. The molecular structures of by-products VI and VII have hitherto remained unknown, due to the large size of the molecules and the occurrence of multiple and reciprocally connected aromatic rings.
Here, we present the ab initio of compounds I, VI and VII, obtained through 3D ED data. This method also allowed for the confirmation of the predicted molecular conformation for compound I and for the true molecular identification of compounds VI and VII. Moreover, detailed synthetic routes and spectroscopic analyses of all the synthetic products are reported. Having solved the structures of these compounds, we eventually use many-body perturbation theory calculations within the GW approximation and the Bethe–Salpeter equation (BSE) (Golze et al., 2019; Blase et al., 2020) to assess their potential usefulness in photovoltaics.
2. Methods
2.1. Synthesis
Samples I, II and III were obtained starting from a Friedel–Crafts reaction (Friedel & Crafts, 1877) between dibenzo[g,p]chrysene (10 g) and o-toluyl chloride, with AlCl3 as catalyst. The two reactants were connected by a ketone group, either 2- or 3-(o-toluyl)dibenzo[g,p]chrysene (12 g). The 1- and 4-positions are excluded on steric grounds. After Elbs (15 g, 420–430 °C, 10 min under CO2), fractional crystallization and showed that three products had formed (Fig. 1): I (0.46 g, violet–red needles, m.p. 348–350 °C), II (1.5 g, thick orange–yellow needles, m.p. 258–259 °C) and III (0.1 g, fibrous orange–yellow needles, m.p. 282°C).
Multiple syntheses of samples IV, V, VI and VII (Fig. 2 and Fig. S2) started from adding phenyl–Li to helianthrone, which can be prepared on a 100 g basis (Scholl & Mansfeld, 1910). The resulting diol was pyrolyzed with ten times the quantity of Cu powder for 45 min at 360 °C under N2. Gradient gave an excellent yield of compound V and a smaller yield of IV, both not free of each other. There were also two major by-products: VI (m.p. >427 °C) and VII (m.p. 426–427 °C). Repeated gradient and gave four pure (>99%) products. Besides VI and VII, we eventually identified at least four other by-products, but these were not obtained free of each other.
2.2. Spectroscopy
UV spectroscopic analyses were conducted using an Agilent Cary 300 spectrophotometer. UV spectra were collected at room temperature using benzene (above 275 nm) or cyclohexane (above 200 nm) solvents (Fig. 3, Figs. S4–S7 and Tables S1–S3). Over 150 UV spectra had to be recorded to ensure the identity and of the various fractions. Fractional was obtained using a Heraeus tube oven ROK 3/30 with a Kelvitron REK 19-20 controller and a melting-point correction. Fluorescence (FL) spectroscopic analyses were carried out with an Aminco–Bowman SPF-500 spectrofluorometer (Table S4). Compound I was insufficiently soluble in cyclohexane solvent, so for the determination of reliable extinction coefficients, only benzene was used as solvent. Compound VI is well soluble in benzene and less soluble in cyclohexane. Compound VII is well soluble in both solvents. The gas-phase PE spectrum for compound I was obtained using a PerkinElmer PS-18 spectrometer with a Helectros Developments photon source (Fig. 3(b)). Samples were also analysed by positive ion mode Matrix-assisted laser desorption/ionization on a Bruker Daltonics ultrafleXtreme II using Colloidal Graphite as the matrix (Figs. S8–S10).
2.3. TEM microscopy and 3D electron diffraction
High-angle annular dark-field 6 thermionic source. 3D ED was performed in STEM mode after defocusing the beam. Therefore, the beam for the 3D ED experiments was almost parallel when crossing the sample (Köhler illumination). The TEM was set in STEM mode, but the beam, which is normally very convergent in this configuration, was purposely defocused (Benner & Probst, 1994). The actual beam convergence was 60 µrad. ED patterns were collected with a beam size of about 150 nm in diameter, obtained using a 5 µm C2 condenser aperture. Data were recorded by a single-electron ASI MEDIPIX detector (Nederlof et al., 2013). An extremely low dose illumination, corresponding to 0.01 e− Å−2 s−1, was used in order to avoid beam damage. The total dose during data collection depends on many experimental parameters, such as the number of frames, the exposure time and the image tracking mode, and is therefore different for each data collection. A rough estimation of the total dose during a stepwise data collection is in a range of about 1–5 e− Å−2. When working with such low doses, the availability of a hybrid-pixel single-electron detector is crucial for acquiring a diffraction pattern with a satisfactory signal-to-noise ratio.
(HAADF–STEM) imaging and ED data were recorded with a Zeiss Libra 120 TEM operating at 120 kV and equipped with a LaB3D ED acquisitions were performed rotating the sample around the TEM goniometer axis in steps of 1°, in total tilt ranges up to 120° (Figs. 4–6). The exposure time per frame was 1 s. The camera length was 180 mm, allowing a resolution in real space of up to 0.7 Å. During the experiment, the beam was precessed around the optical axis by an angle of 1°. Precession was obtained using a Nanomegas Digistar P1000 device. After each tilt, the crystal position was tracked by STEM imaging and a diffraction pattern was acquired. All data acquisitions were performed at room temperature.
3D ED data were analysed using the software PETS2.0 (Palatinus et al., 2019) and ADT3D (Kolb et al., 2011). was carried out by standard (SDM) as implemented in the software SIR2014 (Burla et al., 2015), using a fully kinematical approximation (Ihkl proportional to |Fhkl|2). Kinematical least-squares structure was performed with the software SHELXL (Sheldrick, 2015) using electron atomic scattering factors. Structures were finally refined considering dynamical effects (Palatinus et al., 2013, 2015) using the software JANA2006 (Petrícek et al., 2014) and assuming a simple platelet shape.
2.4. Computational details
Geometry relaxations of the crystal structures of compounds I, VI and VII, and of the single-molecule structure of compound I, were conducted using density functional theory (DFT) with the FHI-aims code (Blum et al., 2009). The Perdew–Burke–Ernzerhof (PBE) (Perdew et al., 1996, 1997) generalized gradient approximation was combined with the Tkatchenko–Scheffler (TS) (Tkatchenko & Scheffler, 2009) pairwise dispersion method. Tight numerical settings and tier 2 basis sets were used. Full unit-cell relaxation was performed until no force component on any atom exceeded 0.01 eV Å−1.
GW+BSE calculations for the crystal structures of compounds I, VI and VII were performed using the BerkeleyGW code (Deslippe et al., 2012). Quantum ESPRESSO (Giannozzi, 2009) was used to compute the mean-field eigenvectors and eigenvalues, and to generate the mean-field coarse-grid and fine-grid wave functions with the PBE exchange-correlation functional. For compound I, we used a coarse k-grid of 8 × 2 × 1 and a fine k-grid of 8 × 4 × 2. For compound VI, we used a coarse k-grid of 4 × 1 × 1 and a fine k-grid of 8 × 2 × 2. For compound VII, we used a coarse k-grid of 2 × 2 × 2 and a fine k-grid of 4 × 4 × 4. Troullier–Martins norm-conserving pseudopotentials (Troullier & Martins, 1991) were used and the cut-off was set at 50 Ry. About 550 unoccupied bands were included in the GW calculation. The static remainder correction was applied to accelerate the convergence with respect to the number of unoccupied states (Deslippe et al., 2013). The polarizability, inverse dielectric matrix and GW self-energy operator were constructed based on the mean-field eigenvalues and eigenfunctions using the coarse k-point settings. Optical properties, including excitation energies, wave functions and absorption spectra were calculated by solving the BSE within the Tamm–Dancoff approximation (TDA). 24 valence bands and 24 conduction bands were included in the BSE calculation (Figs. S11–S16). Taking the full dielectric matrix as input to screen the attraction between the electron (e) and hole (h), the e–h interaction kernel was constructed on the coarse k-point grid. To construct the Bethe–Salpeter Hamiltonian, the GW quasiparticle energies and e–h interaction kernel calculated with coarse k-point settings were interpolated onto the fine k-point grid. The subsequent diagonalization yielded the excitation energies and wave functions. The wave functions of compounds I and VI were converged using supercells of 8 × 4 × 2 and 8 × 2 × 2, respectively, based on the criterion proposed in Liu et al. (2020c). The degree of singlet charge-transfer character (%CT) was calculated by double-Bader analysis (DBA) (Wang et al., 2018; Liu et al., 2020c). The results for rubrene and pentacene are from Wang et al. (2016), the results for quaterrylene, perylene and tetracene are from Wang et al. (2018), the results for anthracene are from Liu et al. (2020c), and the results for terrylene are from Hall et al. (2021).
GW+BSE calculations for the single molecule of compound I were conducted using the FHI-aims code, using augmented tier-2 basis sets (Liu et al., 2020a). PBE was used as the DFT starting point. A detailed account of the GW implementation in FHI-aims is provided in Ren et al. (2012) and Caruso et al. (2013). Briefly, the self-energy is first calculated on the imaginary frequency axis and then analytically continued to the real frequency axis. A 16-parameter Pade approximation was used in the analytical continuation (Ren et al., 2012; Van Setten et al., 2015). Using the GW quasiparticle energies, BSE calculations were performed to obtain the singlet and triplet excitation energies (Liu et al., 2020c). Results for the known TTA chromophores, which we compare to compound I here, are from Wang et al. (2020), in which the same methodology was used. For GW calculations of the gas-phase PE spectra of I, VI and VII, we used the PBE-based hybrid functional (PBE0) (Adamo & Barone, 1999) as the mean-field starting point, with tight numerical settings and tier 4 basis sets. This method was benchmarked in Marom et al. (2012) and Knight et al. (2016), and shown to yield spectra in good agreement with experiments for a variety of organic compounds. For compounds VI and VII, only calculated GW@PBE0 spectra are presented, in the absence of experimental data.
3. Results and discussion
3.1. Benzo[e]dinaphtho[2,3-a;1′,2′,3′,4′-ghi]fluoranthene
The molecular conformation of compound I was reported as provisional (Clar et al., 1964). New absorption measurements (Fig. S3) match well with those reported by Clar et al. (1964), apart from the spurious long-wavelength band at 584 nm. The alleged composition from was C34H18 (Fig. S8), also consistent with the related UV spectrum (Fig. 3(a) and Table S1). The occurrence of cyclodehydrogenation, with the formation of a five-membered ring, is accompanied by a of the first UV band by 74.5 nm. In particular, the sharp band at about 440 nm is often found in fluoranthene-type PAHs, and never in alternant cata- or peri-condensed PAHs. The strongest argument in favour of Clar's assignment comes from the PE spectrum, which fits the calculated one (Clar et al., 1981). Also, our GW@PBE0 calculation, based on the by 3D ED data, is in excellent agreement with experimental PE data (Fig. 3(b)). We note that the computed ionization energies are vertical values. We do not consider the relaxation of the atomic positions in response to the electronic excitation, vibrational effects, scattering effects, detector resolution and other sources of noise in the experiment, which may affect the peak breadth and intensity. The comparison to experiment is focused on peak positions, with the dashed lines at the experimental peak maxima serving as a guide to the eye. Additionally, this spectrum shows an impurity band at 6.95 eV. This peak is not related to the presence of III, which should instead give a band at about 6.67 eV (Clar et al., 1981).
3D ED data were recorded from three flat crystal fragments of I, with sizes less than 1 µm (Fig. 4(a)). All data sets were consistent with a primitive orthorhombic with parameters a = 5.1 (1), b = 17.7 (4) and c = 23.2 (5) Å (Figs. 4(b)–(d)). Such a cell would likely contain four molecules. Upon inspection of the reconstruction, the extinction rules 0k0: k = 2n and 00l: l = 2n were observed. All 3D ED acquisitions miss information about h00, because this direction is always parallel to the main surface of the platelet and, standing vertical, cannot be sampled inside the TEM goniometer range. The possible space groups for compound I were therefore P22121 (No. 18) or P212121 (No. 19), both with multiplicity 4.
Structure solution was performed by SDM using the 3D ED data set with the highest angular range and the greatest resolution. The solution eventually converged in the P212121. All but one of the 34 non-H atoms of the molecule were located ab initio. The missing C and all H atoms were generated during least-squares against 3D ED data imposing constraints on the aromatic rings. More details about and are reported in Table S5.
The et al., 1964). Molecules of I are flat and arranged in four columns per which extend along a. Inside each column, molecules form a herringbone stack, parallel to one of the four planes of the {3,10,6} family (Figs. 7(a) and 7(b)). The intermolecular distance is about 3.5 Å, similar to that observed in terrylene, another PAH recently solved by the 3D ED method and potentially promising for electronic applications (Hall et al., 2021).
of compound I allowed for unequivocal confirmation of the molecular model inferred from spectroscopic data, which was previously considered provisional (Clar3.2. 7,14-Diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene
The two side products VI and VII obtained during the synthesis of IV were separated by repeated gradient 46H24. The molecular conformation could not be deduced by spectroscopic data alone and no crystal produced was sufficiently large for single-crystal XRD analysis. In the absence of experimental PE data, we present here the computed GW@PBE0 spectra of compounds VI and VII (Figs. 3(d) and 3(f)).
Compound VI appears as dark-green crystals that do not melt up to 427 °C and shows a deep-red colour in concentrated benzene solution or a carmine colour in While exposed to UV light, it appears violet–blue and has an intense orange–red fluorescence in daylight. Based on (Fig. S9) and combustion data, VI has the composition C3D ED data collected on three VI micrometric crystals (Fig. 5(a)) consistently indicated a primitive orthorhombic cell with parameters a = 9.9 (2), b = 26.5 (5) and c = 20.7 (4) Å (Figs. 5(b)–(d)). Such a cell would likely contain eight VI molecules. Upon inspection of the reconstruction, the extinction rules uniquely indicated the Pbca (No. 61), with multiplicity 8. Despite the remarkable complexity of the molecule, its structure solution was obtained ab initio by SDM on the basis of 3D ED data. All 46 non-H atoms of the molecule were located automatically in the first Fourier map, eventually revealing the molecular conformation that could not be obtained by spectroscopic data (Fig. 7(c)). More details about the and are reported in Table S5.
Molecules of VI are flat and pack as a sandwich herringbone structure parallel to the (102) and (10) planes (Fig. 7(d)). The phenyl groups act as nonplanar satellites of the molecule, forming with it an angle of about 66°. The intermolecular distance is about 3.5 Å.
Apparently, during the synthesis, phenyl–Li acts as a masked benzyne and connects to the reactive diene positions. A literature search supports the 3D ED result. In fact, the dimesityl analogue of VI was synthesized in an unequivocal manner by benzyne addition to 7,14-bis(mesityl)bisanthene (Konishi et al., 2013), when benzyne was liberated in situ from o-anthranilic acid and isoamyl nitrite. Due to severe twisting about the formal single bond, the phenyl and mesityl groups show little difference; hence, the UV spectra reported by Konishi et al. (2013) agrees with that obtained for compound VI (Fig. 3(c)). Compared to IV, lateral annelation shifts the first UV band by 79 nm to the blue (from 684.5 to 613 nm), due to the gain of one Clar sextet. There is a good mirror relationship between the absorption and fluorescence emission, and the is 6 nm.
Compound VII results in ochre crystals with a melting point of 426–427 °C and shows a permanganate colour in solution with benzene or cyclohexane. Under UV light it emits a green fluorescence and is moderately stable in daylight. This feature contrasts with the extreme sensitivity of helianthrene, whose fluorescence fades in daylight within seconds (Seip & Brauer, 1992). The combustion and (Fig. S10) analysis pointed to a composition of C46H26. As for compound VI, the molecular conformation could not be deduced by spectroscopic data and no crystal was sufficiently large for single-crystal XRD analysis.
3D ED data were recorded from six crystal fragments with a size of less than 1 µm (Fig. 6(a)). All of them delivered a triclinic with parameters a = 10.5 (2), b = 11.6 (3), c = 12.8 (3) Å, α = 85.3 (5), β = 76.1 (5) and γ = 84.9 (5)° (Figs. 6(b)–(d)). No possibility of cell centring was envisaged, and no extinction rule pointing to higher symmetry was recognised. Such a cell would conveniently host only two VII molecules. Structure solution of this compound was indeed obtained ab initio by SDM in the P (No. 2). All 46 non-H atoms of the molecule were automatically spotted in the first Fourier map, allowing also, in this case, the molecular conformation to be established, which could not be obtained by spectroscopic data (Fig. 7(e)). More details about the and are reported in Table S5.
The two terminal phenyl rings in VII act again as nonplanar satellites, forming an angle of about 65° with the main part of the molecule. Their presence partially breaks the aromaticity of the helianthrene group. The nonplanarity of VII allows for both C—H⋯π and π–π interactions, leading to the reduction of symmetry down to triclinic. No herringbone motif is present (Fig. 7(f)).
In the corresponding UV spectrum, a first sharp band was observed at 501 nm (Fig. 3(e)). Consistent with the 3D ED results, in going from V to VII, there is a blue shift by 79 nm due to the gain of one Clar sextet in the molecule. The is 16.5 nm (Fig. S7, Tables S2 and S3).
3.3. Electronic properties
Having definitively resolved the molecular and crystal structures of compounds I, VI and VII by 3D ED, we are now able to use computer simulations to assess their potential usefulness for photovoltaic applications. In particular, we are interested in discovering new materials capable of undergoing singlet fission (SF), the down-conversion of one singlet , 2013; Monahan & Zhu, 2015; Michl, 2019), and its reverse process, triplet–triplet annihilation (TTA), the up-conversion of two triplet excitons into one singlet (Baldo et al., 2000; Schmidt & Castellano, 2014; Schulze & Schmidt, 2015). Both of these processes can be harnessed to reduce losses and thus increase the conversion efficiency of solar cells. In a typical solar cell, the absorption of one photon produces one charge carrier. The absorption of a high-energy photon generates a highly excited singlet which subsequently thermalizes to the lowest such that the excess photon energy is lost to heat. SF can be potentially utilized to convert that excess photon energy into an additional charge carrier by generating two triplet excitons from one high-energy singlet Another source of losses in solar cells is that photons with energies below the gap of the absorber cannot be absorbed and their energy is lost. TTA can be utilized to convert two low-energy photons into an additional charge carrier. Hence, supplementing the traditional absorber with SF and TTA materials can significantly enhance the efficiency of solar cells by reducing losses at both the high end and the low end of the solar photon energy spectrum. SF and TTA materials are rare because few chromophores meet the stringent requirements for the excited-state energetics, as detailed below. Most of the known and predicted SF and TTA chromophores are PAHs, mainly acene and perylene derivatives. Therefore, we evaluate the PAHs studied here for these purposes.
into two triplet excitons (Smith & Michl, 2010To assess the potential of molecular crystals to undergo SF in the solid state, we consider a two-dimensional descriptor (Wang et al., 2018; Liu et al., 2020b,c), as shown in Fig. 8. The primary descriptor, displayed on the x axis, is the thermodynamic driving force for SF, which is the difference between the singlet energy and twice the triplet energy (Es − 2Et). A high driving force indicates that a material is likely to undergo SF with a high rate. However, an overly high driving force would lead to losses in solar energy conversion. Therefore, it has been suggested that materials with Es ≃ 2Et may be preferable (Wu et al., 2014). Owing to the approximations used in GW+BSE calculations, the values of Es − 2Et are systematically underestimated. Hence, we restrict the discussion to qualitative comparisons between materials.
The secondary descriptor, displayed on the y axis, is the degree of charge-transfer character (%CT) of the singlet wave function. wave functions have two spatial variables corresponding to the electron and hole probability distributions. If the hole is located on one molecule, the degree of charge-transfer character corresponds to the probability of finding the electron on other molecules. This descriptor is motivated by the growing body of experimental evidence for the involvement of an intermediate charge-transfer state in the SF process (Monahan & Zhu, 2015; Chan et al., 2013; Kim et al., 2019; Miyata et al., 2019; Margulies et al., 2017). A singlet with a high degree of charge-transfer character is thought to be favourable for SF (Monahan & Zhu, 2015; Sharifzadeh et al., 2013, 2015; Broch et al., 2018; Hart et al., 2018). To evaluate %CT, we use double-Bader analysis (DBA), an extension of the Bader charge-partitioning scheme, to wave functions with two spatial variables. The %CT is calculated by performing nested sums over the electron distributions obtained for different hole positions within a molecule. The error bars correspond to the range of %CT values obtained for different hole positions within the double-Bader analysis (Wang et al., 2018; Liu et al., 2020c).
In Fig. 8, compounds I and VI are compared to perylenes and with respect to these two descriptors. Pentacene has the highest SF driving force of the materials shown here and is known to undergo fast SF with a high triplet yield (Chan et al., 2011; Wilson et al., 2011). SF in tetracene is experimentally known to be slightly endoergic (Tomkiewicz et al., 1971; Grumstrup et al., 2010; Burdett et al., 2010; Chan et al., 2012; Burdett & Bardeen, 2012, 2013; Arias et al., 2016). Compound VI has a somewhat higher SF driving force, as well as a higher singlet CT character than tetracene. Based on this, it may be a promising candidate for intermolecular SF in the solid state. Compound I has a lower SF driving force than anthracene and perylene, whose derivatives are known to undergo TTA (Renaud et al., 2013; Jiang et al., 2013; Eaton et al., 2013; Mirjani et al., 2014; Renaud & Grozema, 2015; Le et al., 2016; Würthner et al., 2016). Therefore, it may be able to undergo TTA. The computed singlet and triplet excitation energies of compound VII are 2.90 and 2.00 eV, respectively. It is thus not a likely candidate for either SF or TTA; therefore, it is not shown in Figs. 8 and 9.
To further assess the potential of compound I to undergo TTA, we compare its excited-state energetics as an isolated molecule to several chromophores experimentally known to undergo TTA (Fig. 9). The comparison is based on the criteria proposed in Wang et al. (2020). The primary criterion for a chromophore to undergo TTA is that the energy release in the singlet pathway, = 2T1 − S1, plotted on the x axis, should be positive to provide thermodynamic driving force, but not overly large to avoid significant energy losses. As discussed in detail in Wang et al. (2020), GW+BSE@PBE systematically underestimates . Therefore, we assess new chromophores based on a comparison with known TTA chromophores, similar to our procedure for assessing SF candidates. In rubrene, TTA is experimentally known to be approximately isoergic (Cheng et al., 2010). Therefore, we consider the of rubrene as the lower limit for the singlet pathway to be open. Molecules with a smaller than rubrene may be more likely to undergo SF than TTA. This is indicated by the left dashed vertical line in Fig. 9. Of the experimentally known TTA chromophores calculated in Wang et al. (2020), pyrene has the highest . We then consider pyrene as the upper limit, above which the energy loss is too high for efficient TTA. This is indicated by the right vertical dashed line in Fig. 9.
The main process competing with TTA is the combination of two triplet excitons into a higher-energy T2, which decays nonradiatively. Hence, a secondary criterion for the of TTA to be as high as possible is for the energy release in the triplet pathway, = 2T1 − T2, to be as small as possible compared to . In Wang et al. (2020), we have found that most of the experimentally known TTA chromophores fall into the range between = and = + 0.32 eV. This is indicated by the two diagonal lines in Fig. 9. Compound I (highlighted in red) is well within this range, between perylene and an anthracene derivative. Therefore, based on energetic considerations, compound I may be a promising candidate for TTA. We note, however, that favourable energetics are a necessary but not sufficient condition for good TTA chromophores (Wang et al., 2020).
4. Conclusions
Organic syntheses typically yield several side products, which are generally discarded even if their quantity amounts to 20–50% of the total. Such side products are often unwanted. Moreover, the assessment of their potential use is complicated by the difficulty of their characterization. Spectroscopic data may be insufficient to unambiguously determine the molecular conformation, especially when molecules are complex or the presence of more than one species is suspected. Powder X-ray diffraction requires a sufficient amount of material and may suffer from peak overlap, in particular when the phase of interest cannot be properly purified, its unit-cell parameters are long and/or small crystal size causes severe peak broadening. In these cases, 3D electron diffraction emerges as a promising technique for conclusive determination of the molecular conformation and e]dinaphtho[2,3-a;1′,2′,3′,4′-ghi]fluoranthene (compound I), 7,14-diphenyl-naphtho[1,2,3,4-cde]bisanthene (compound VI) and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene (compound VII).
as we have demonstrated here for benzo[Once the structure is determined, computer simulations may be used to predict the electronic and optical properties of side products, in particular when the amount of material initially produced is insufficient for detailed experimental characterization. This can help to assess the potential usefulness of side products for various applications. In some cases, unintended side products may turn out to be as useful as the main reaction products. For example, the second system analysed here comprises four related molecules. Of these, IV exhibits exceptional optical properties (Gorelenko et al., 1977) and V found practical application as a pigment for visible-light-sensitive actinometers (Brauer et al., 1983). Based on the many-body perturbation theory simulations presented here, compounds I and VI may be useful for photovoltaic applications. Compound I may exhibit triplet–triplet annihilation, which may enable harvesting photons with energies below the gap of the absorber in a solar cell. Compound VI may exhibit intermolecular singlet fission in the solid state, which may enable the harvesting of two charge carriers from one high-energy photon in a solar cell. Compound VII is a wide-gap insulator.
We hope that the results reported in this article will inspire others to pursue further characterization of organic side products by 3D ED and computer simulations. This may lead to the discovery of potentially useful compounds for various applications. Thus, 3D ED is a promising new avenue for enriching our knowledge of organic synthetic routes and exploiting side products that would otherwise be discarded.
Supporting information
https://doi.org/10.1107/S205225252201154X/ur5001sup1.cif
contains datablocks I, VI, VII. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205225252201154X/ur5001Isup2.hkl
Structure factors: contains datablock VI. DOI: https://doi.org/10.1107/S205225252201154X/ur5001VIsup3.hkl
Structure factors: contains datablock VII. DOI: https://doi.org/10.1107/S205225252201154X/ur5001VIIsup4.hkl
Supporting information. DOI: https://doi.org/10.1107/S205225252201154X/ur5001sup5.pdf
For all structures, program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: JANA2006 (Petricek et al., 2014) (Palatinus et al., 2015); molecular graphics: VESTA Momma & Izumi, 2011); software used to prepare material for publication: JANA2006 (Petricek et al., 2014).
C34H18 | Z = 4 |
Mr = 426.5 | F(000) = 888 |
Orthorhombic, P212121 | Dx = 1.344 Mg m−3 |
Hall symbol: P 2xab;2ybc;2zac | Electron radiation, λ = 0.0335 Å |
a = 5.14 (10) Å | µ = 0 mm−1 |
b = 17.7 (4) Å | T = 293 K |
c = 23.2 (5) Å | Nanocrystal, dark orange |
V = 2110 (80) Å3 | 0.001 × 0.0003 × 0.0001 mm |
Zeiss Libra 120 diffractometer | θmax = 1.2°, θmin = 0.1° |
data have been collected by precession–assisted 3D electron diffration scans | h = −6→6 |
71669 measured reflections | k = −19→20 |
8927 independent reflections | l = −28→28 |
1138 reflections with I > 3σ(I) |
Refinement on F | 105 constraints |
R[F > 3σ(F)] = 0.172 | H-atom parameters constrained |
wR(F) = 0.201 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 1.82 | (Δ/σ)max = 0.045 |
8927 reflections | Δρmax = 0.77 e Å−3 |
181 parameters | Δρmin = −1.24 e Å−3 |
78 restraints | Absolute structure: 2000 of Friedel pairs used in the refinement |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0194 (11) | 0.2845 (5) | 0.5772 (4) | 0.0290 (7)* | |
H1 | 0.881851 | 0.245779 | 0.569831 | 0.0349* | |
C2 | 1.0787 (13) | 0.3383 (5) | 0.5346 (3) | 0.0290 (7)* | |
H2 | 0.983346 | 0.337812 | 0.496972 | 0.0349* | |
C3 | 1.2717 (15) | 0.3927 (5) | 0.5449 (3) | 0.0290 (7)* | |
H3 | 1.314004 | 0.430955 | 0.514626 | 0.0349* | |
C4 | 1.4055 (12) | 0.3934 (5) | 0.5978 (4) | 0.0290 (7)* | |
H4 | 1.54292 | 0.432133 | 0.605152 | 0.0349* | |
C5 | 1.3463 (14) | 0.3396 (6) | 0.6403 (3) | 0.0290 (7)* | |
C6 | 1.1533 (15) | 0.2852 (5) | 0.6300 (3) | 0.0290 (7)* | |
C7 | 1.0625 (9) | 0.2219 (3) | 0.67166 (19) | 0.0290 (7)* | |
C8 | 1.2304 (8) | 0.2393 (3) | 0.71765 (19) | 0.0290 (7)* | |
C9 | 1.4301 (11) | 0.2924 (5) | 0.7321 (4) | 0.0290 (7)* | |
C10 | 1.5055 (15) | 0.3487 (6) | 0.6929 (3) | 0.0290 (7)* | |
C11 | 1.7016 (16) | 0.4002 (5) | 0.7080 (3) | 0.0290 (7)* | |
H11 | 1.755371 | 0.44037 | 0.680049 | 0.0349* | |
C12 | 1.8223 (12) | 0.3955 (5) | 0.7622 (4) | 0.0290 (7)* | |
H12 | 1.96199 | 0.43215 | 0.772971 | 0.0349* | |
C13 | 1.7468 (15) | 0.3391 (6) | 0.8014 (2) | 0.0290 (7)* | |
H13 | 1.832696 | 0.335733 | 0.840113 | 0.0349* | |
C14 | 1.5507 (16) | 0.2876 (5) | 0.7864 (3) | 0.0290 (7)* | |
C15 | 0.8811 (8) | 0.1179 (3) | 0.72719 (18) | 0.0290 (7)* | |
C16 | 0.7066 (8) | 0.0573 (4) | 0.7319 (2) | 0.0290 (7)* | |
H16 | 0.701965 | 0.026436 | 0.768081 | 0.0349* | |
C17 | 0.5387 (10) | 0.0400 (4) | 0.6860 (2) | 0.0290 (7)* | |
H17 | 0.414347 | −0.00316 | 0.689373 | 0.0349* | |
C176 | 0.5453 (11) | 0.0834 (4) | 0.6352 (2) | 0.0290 (7)* | |
H176 | 0.425659 | 0.071042 | 0.602512 | 0.0349* | |
C18 | 0.7199 (10) | 0.1440 (4) | 0.6305 (2) | 0.0290 (7)* | |
H18 | 0.724619 | 0.174829 | 0.594341 | 0.0349* | |
C19 | 0.8879 (9) | 0.1613 (4) | 0.67644 (19) | 0.0290 (7)* | |
C20 | 1.2238 (7) | 0.1960 (3) | 0.76839 (17) | 0.0290 (7)* | |
C21 | 1.3920 (7) | 0.2133 (3) | 0.81444 (17) | 0.0290 (7)* | |
C22 | 1.3854 (6) | 0.1699 (3) | 0.86530 (16) | 0.0290 (7)* | |
C23 | 1.2105 (6) | 0.1092 (3) | 0.87009 (15) | 0.0290 (7)* | |
C24 | 1.0424 (6) | 0.0918 (3) | 0.82404 (16) | 0.0290 (7)* | |
H24 | 0.918038 | 0.048659 | 0.827447 | 0.0349* | |
C25 | 1.0491 (7) | 0.1353 (3) | 0.77317 (16) | 0.0290 (7)* | |
C26 | 1.2039 (7) | 0.0658 (3) | 0.92096 (17) | 0.0290 (7)* | |
H26 | 1.079533 | 0.022623 | 0.924374 | 0.0349* | |
C27 | 1.5537 (7) | 0.1873 (3) | 0.91136 (18) | 0.0290 (7)* | |
H27 | 1.678101 | 0.230442 | 0.907945 | 0.0349* | |
C28 | 1.5470 (8) | 0.1439 (4) | 0.96223 (19) | 0.0290 (7)* | |
C29 | 1.7153 (9) | 0.1613 (4) | 1.0083 (2) | 0.0290 (7)* | |
H29 | 1.839666 | 0.204425 | 1.004844 | 0.0349* | |
C30 | 1.7086 (10) | 0.1179 (5) | 1.0591 (2) | 0.0290 (7)* | |
H30 | 1.828189 | 0.130232 | 1.091868 | 0.0349* | |
C31 | 1.5337 (10) | 0.0571 (5) | 1.0639 (2) | 0.0290 (7)* | |
H31 | 1.529099 | 0.026269 | 1.100066 | 0.0349* | |
C32 | 1.3654 (9) | 0.0398 (4) | 1.0179 (2) | 0.0290 (7)* | |
H32 | 1.240975 | −0.003354 | 1.021328 | 0.0349* | |
C33 | 1.3722 (8) | 0.0832 (4) | 0.96702 (18) | 0.0290 (7)* |
C1—H1 | 1 | C17—H17 | 1 |
C1—C2 | 1.40 (4) | C17—C176 | 1.40 (5) |
C1—C6 | 1.40 (5) | C176—H176 | 1 |
C2—H2 | 1 | C176—C18 | 1.40 (4) |
C2—C3 | 1.40 (4) | C18—H18 | 1 |
C3—H3 | 1 | C18—C19 | 1.40 (4) |
C3—C4 | 1.40 (5) | C20—C21 | 1.41 (4) |
C4—H4 | 1 | C20—C25 | 1.41 (4) |
C4—C5 | 1.40 (4) | C21—C22 | 1.41 (5) |
C5—C6 | 1.40 (4) | C22—C23 | 1.41 (4) |
C5—C10 | 1.48 (5) | C22—C27 | 1.41 (4) |
C6—C7 | 1.55 (5) | C23—C24 | 1.41 (4) |
C7—C8 | 1.40 (4) | C23—C26 | 1.41 (5) |
C7—C19 | 1.40 (4) | C24—H24 | 1 |
C8—C9 | 1.43 (4) | C24—C25 | 1.41 (5) |
C8—C20 | 1.40 (5) | C26—H26 | 1 |
C9—C10 | 1.40 (4) | C26—C33 | 1.41 (4) |
C9—C14 | 1.40 (5) | C27—H27 | 1 |
C10—C11 | 1.40 (4) | C27—C28 | 1.41 (5) |
C11—H11 | 1 | C28—C29 | 1.41 (4) |
C11—C12 | 1.40 (5) | C28—C33 | 1.41 (4) |
C12—H12 | 1 | C29—H29 | 1 |
C12—C13 | 1.40 (4) | C29—C30 | 1.41 (5) |
C13—H13 | 1 | C30—H30 | 1 |
C13—C14 | 1.40 (4) | C30—C31 | 1.41 (4) |
C15—C16 | 1.40 (4) | C31—H31 | 1 |
C15—C19 | 1.40 (5) | C31—C32 | 1.41 (4) |
C15—C25 | 1.40 (4) | C32—H32 | 1 |
C16—H16 | 1 | C32—C33 | 1.41 (5) |
C16—C17 | 1.40 (4) | ||
H1—C1—C2 | 120 | C17—C176—H176 | 120 |
H1—C1—C6 | 120 | C17—C176—C18 | 120.0 (9) |
C2—C1—C6 | 120.0 (12) | H176—C176—C18 | 120 |
C1—C2—H2 | 120 | C176—C18—H18 | 120 |
C1—C2—C3 | 120.0 (12) | C176—C18—C19 | 120.0 (9) |
H2—C2—C3 | 120 | H18—C18—C19 | 120 |
C2—C3—H3 | 120 | C7—C19—C15 | 120.0 (8) |
C2—C3—C4 | 120.0 (9) | C7—C19—C18 | 120.0 (9) |
H3—C3—C4 | 120 | C15—C19—C18 | 120.0 (12) |
C3—C4—H4 | 120 | C8—C20—C21 | 120.0 (12) |
C3—C4—C5 | 120.0 (13) | C8—C20—C25 | 120.0 (8) |
H4—C4—C5 | 120 | C21—C20—C25 | 120.0 (9) |
C4—C5—C6 | 120.0 (12) | C20—C21—C22 | 120.0 (12) |
C4—C5—C10 | 112.6 (14) | C21—C22—C23 | 120.0 (8) |
C6—C5—C10 | 127.4 (9) | C21—C22—C27 | 120.0 (12) |
C1—C6—C5 | 120.0 (9) | C23—C22—C27 | 120.0 (9) |
C1—C6—C7 | 112.9 (12) | C22—C23—C24 | 120.0 (9) |
C5—C6—C7 | 127.1 (11) | C22—C23—C26 | 120.0 (8) |
C6—C7—C8 | 97.4 (13) | C24—C23—C26 | 120.0 (12) |
C6—C7—C19 | 142.6 (8) | C23—C24—H24 | 120 |
C8—C7—C19 | 120.0 (9) | C23—C24—C25 | 120.0 (12) |
C7—C8—C9 | 139.5 (7) | H24—C24—C25 | 120 |
C7—C8—C20 | 120.0 (12) | C15—C25—C20 | 120.0 (9) |
C9—C8—C20 | 100.5 (11) | C15—C25—C24 | 120.0 (12) |
C8—C9—C10 | 121.0 (13) | C20—C25—C24 | 120.0 (8) |
C8—C9—C14 | 119.0 (9) | C23—C26—H26 | 120 |
C10—C9—C14 | 120.0 (12) | C23—C26—C33 | 120.0 (12) |
C5—C10—C9 | 107.6 (14) | H26—C26—C33 | 120 |
C5—C10—C11 | 132.4 (9) | C22—C27—H27 | 120 |
C9—C10—C11 | 120.0 (12) | C22—C27—C28 | 120.0 (12) |
C10—C11—H11 | 120 | H27—C27—C28 | 120 |
C10—C11—C12 | 120.0 (9) | C27—C28—C29 | 120.0 (12) |
H11—C11—C12 | 120 | C27—C28—C33 | 120.0 (8) |
C11—C12—H12 | 120 | C29—C28—C33 | 120.0 (9) |
C11—C12—C13 | 120.0 (12) | C28—C29—H29 | 120 |
H12—C12—C13 | 120 | C28—C29—C30 | 120.0 (13) |
C12—C13—H13 | 120 | H29—C29—C30 | 120 |
C12—C13—C14 | 120.0 (12) | C29—C30—H30 | 120 |
H13—C13—C14 | 120 | C29—C30—C31 | 120.0 (9) |
C9—C14—C13 | 120.0 (9) | H30—C30—C31 | 120 |
C16—C15—C19 | 120.0 (8) | C30—C31—H31 | 120 |
C16—C15—C25 | 120.0 (9) | C30—C31—C32 | 120.0 (10) |
C19—C15—C25 | 120.0 (12) | H31—C31—C32 | 120 |
C15—C16—H16 | 120 | C31—C32—H32 | 120 |
C15—C16—C17 | 120.0 (9) | C31—C32—C33 | 120.0 (13) |
H16—C16—C17 | 120 | H32—C32—C33 | 120 |
C16—C17—H17 | 120 | C26—C33—C28 | 120.0 (9) |
C16—C17—C176 | 120.0 (13) | C26—C33—C32 | 120.0 (12) |
H17—C17—C176 | 120 | C28—C33—C32 | 120.0 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···C18 | ** | 2.43 | 3.18 (10) | 130.76 |
C16—H16···C24 | 1.00 | 2.47 | 2.81 (8) | 99.51 |
C17—H17···C12i | 1.00 | 2.44 | 3.38 (10) | 156.54 |
C18—H18···C1 | 1.00 | 2.50 | 3.18 (10) | 125.03 |
C24—H24···C16 | 1.00 | 2.47 | 2.81 (8) | 99.37 |
Symmetry code: (i) −x+2, y−1/2, −z+3/2. |
C46H24 | Z = 8 |
Mr = 576.7 | F(000) = 2400 |
Orthorhombic, Pbca | Dx = 1.402 Mg m−3 |
Hall symbol: -P -2xab;-2ybc;-2zac | Electron radiation, λ = 0.0335 Å |
a = 9.9 (2) Å | µ = 0 mm−1 |
b = 26.5 (5) Å | T = 293 K |
c = 20.7 (4) Å | Nanocrystal, blue |
V = 5460 (180) Å3 | 0.001 × 0.001 × 0.0001 mm |
Zeiss Libra 120 diffractometer | θmax = 1.2°, θmin = 0.1° |
data have been collected by precession–assisted 3D electron diffration scans | h = −11→11 |
132615 measured reflections | k = −33→33 |
9870 independent reflections | l = −25→25 |
1463 reflections with I > 3σ(I) |
Refinement on F | 141 constraints |
R[F > 3σ(F)] = 0.249 | H-atom parameters constrained |
wR(F) = 0.284 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 2.11 | (Δ/σ)max = 1.056 |
9870 reflections | Δρmax = 0.27 e Å−3 |
208 parameters | Δρmin = −0.32 e Å−3 |
120 restraints |
x | y | z | Uiso*/Ueq | ||
C1 | −0.431 (3) | 0.2203 (3) | −0.1858 (4) | 0.0016 (8)* | |
H1 | −0.413136 | 0.197668 | −0.223426 | 0.0019* | |
C2 | −0.437 (3) | 0.2730 (3) | −0.1946 (4) | 0.0016 (8)* | |
H2 | −0.430941 | 0.28765 | −0.238973 | 0.0019* | |
C3 | −0.451 (3) | 0.3051 (3) | −0.1407 (4) | 0.0016 (8)* | |
H3 | −0.447945 | 0.342505 | −0.14655 | 0.0019* | |
C4 | −0.468 (2) | 0.2843 (3) | −0.0787 (4) | 0.0016 (8)* | |
H4 | −0.482469 | 0.307048 | −0.040826 | 0.0019* | |
C5 | −0.466 (2) | 0.2316 (3) | −0.0702 (4) | 0.0016 (8)* | |
H5 | −0.475327 | 0.216951 | −0.025955 | 0.0019* | |
C6 | −0.451 (3) | 0.1996 (2) | −0.1239 (4) | 0.0016 (8)* | |
C7 | −0.0556 (8) | 0.06042 (18) | 0.0768 (2) | 0.0016 (8)* | |
H7 | −0.052168 | 0.098081 | 0.074594 | 0.0019* | |
C8 | 0.0321 (8) | 0.0341 (2) | 0.1184 (3) | 0.0016 (8)* | |
H8 | 0.097686 | 0.053117 | 0.145695 | 0.0019* | |
C9 | 0.0272 (8) | −0.0190 (2) | 0.1215 (3) | 0.0016 (8)* | |
H9 | 0.089408 | −0.037666 | 0.150939 | 0.0019* | |
C10 | −0.0653 (7) | −0.04586 (18) | 0.0829 (2) | 0.0016 (8)* | |
H10 | −0.068808 | −0.083521 | 0.085114 | 0.0019* | |
C11 | −0.1530 (7) | −0.01955 (14) | 0.04131 (19) | 0.0016 (8)* | |
C12 | −0.1482 (7) | 0.03359 (14) | 0.03824 (19) | 0.0016 (8)* | |
C13 | −0.2359 (6) | 0.05990 (13) | −0.00337 (18) | 0.0016 (8)* | |
C14 | −0.2310 (7) | 0.11302 (15) | −0.0065 (2) | 0.0016 (8)* | |
H14 | −0.165347 | 0.132033 | 0.020832 | 0.0019* | |
C15 | −0.3187 (7) | 0.13932 (14) | −0.0480 (2) | 0.0016 (8)* | |
H15 | −0.315223 | 0.176985 | −0.050193 | 0.0019* | |
C16 | −0.4112 (7) | 0.11251 (12) | −0.0865 (2) | 0.0016 (8)* | |
C17 | −0.4160 (6) | 0.05938 (10) | −0.08346 (16) | 0.0016 (8)* | |
C18 | −0.3284 (6) | 0.03308 (10) | −0.04188 (15) | 0.0016 (8)* | |
C19 | −0.3332 (6) | −0.02008 (10) | −0.03881 (15) | 0.0016 (8)* | |
C20 | −0.2456 (6) | −0.04638 (12) | 0.00277 (18) | 0.0016 (8)* | |
C21 | −0.2504 (7) | −0.09951 (14) | 0.0058 (2) | 0.0016 (8)* | |
H21 | −0.188296 | −0.118156 | 0.035322 | 0.0019* | |
C22 | −0.3430 (7) | −0.12633 (14) | −0.0327 (2) | 0.0016 (8)* | |
H22 | −0.346383 | −0.163992 | −0.030521 | 0.0019* | |
C23 | −0.4306 (6) | −0.10003 (12) | −0.0743 (2) | 0.0016 (8)* | |
C24 | −0.4257 (6) | −0.04689 (10) | −0.07732 (16) | 0.0016 (8)* | |
C25 | −0.5231 (7) | −0.12684 (14) | −0.1128 (2) | 0.0016 (8)* | |
C26 | −0.5134 (6) | −0.02059 (9) | −0.11891 (15) | 0.0016 (8)* | |
C27 | −0.5085 (6) | 0.03256 (9) | −0.12197 (15) | 0.0016 (8)* | |
C28 | −0.4988 (7) | 0.13881 (13) | −0.1281 (2) | 0.0016 (8)* | |
C29 | −0.5913 (7) | 0.11199 (13) | −0.1666 (2) | 0.0016 (8)* | |
C30 | −0.6789 (8) | 0.13829 (16) | −0.2082 (3) | 0.0016 (8)* | |
H30 | −0.675503 | 0.175956 | −0.210364 | 0.0019* | |
C31 | −0.7715 (9) | 0.11148 (17) | −0.2467 (3) | 0.0016 (8)* | |
H31 | −0.833618 | 0.130131 | −0.27618 | 0.0019* | |
C32 | −0.7763 (8) | 0.05835 (15) | −0.2436 (2) | 0.0016 (8)* | |
H32 | −0.841903 | 0.03934 | −0.270952 | 0.0019* | |
C33 | −0.6886 (7) | 0.03205 (12) | −0.20207 (19) | 0.0016 (8)* | |
C34 | −0.5962 (6) | 0.05886 (11) | −0.16355 (18) | 0.0016 (8)* | |
C35 | −0.6059 (6) | −0.04740 (11) | −0.15742 (18) | 0.0016 (8)* | |
C36 | −0.6935 (7) | −0.02110 (13) | −0.19900 (19) | 0.0016 (8)* | |
C37 | −0.7860 (8) | −0.04791 (16) | −0.2375 (2) | 0.0016 (8)* | |
H37 | −0.848196 | −0.02926 | −0.266989 | 0.0019* | |
C38 | −0.7909 (8) | −0.10103 (18) | −0.2344 (3) | 0.0016 (8)* | |
H38 | −0.856508 | −0.120047 | −0.26175 | 0.0019* | |
C39 | −0.7032 (8) | −0.12734 (17) | −0.1929 (3) | 0.0016 (8)* | |
H39 | −0.706663 | −0.165009 | −0.190707 | 0.0019* | |
C40 | −0.6107 (7) | −0.10053 (13) | −0.1544 (2) | 0.0016 (8)* | |
C41 | −0.6202 (15) | −0.2719 (4) | −0.1014 (6) | 0.0016 (8)* | |
H41 | −0.700471 | −0.293382 | −0.09199 | 0.0019* | |
C42 | −0.6257 (15) | −0.2195 (4) | −0.0903 (6) | 0.0016 (8)* | |
H42 | −0.70776 | −0.204093 | −0.070543 | 0.0019* | |
C43 | −0.5156 (17) | −0.1887 (3) | −0.1072 (7) | 0.0016 (8)* | |
C44 | −0.3974 (15) | −0.2107 (4) | −0.1321 (5) | 0.0016 (8)* | |
H44 | −0.318653 | −0.188954 | −0.143416 | 0.0019* | |
C45 | −0.3903 (15) | −0.2633 (4) | −0.1412 (5) | 0.0016 (8)* | |
H45 | −0.306309 | −0.278973 | −0.158618 | 0.0019* | |
C46 | −0.5017 (17) | −0.2939 (3) | −0.1256 (7) | 0.0016 (8)* | |
H46 | −0.496516 | −0.331292 | −0.13185 | 0.0019* |
C1—H1 | 1 | C22—C23 | 1.41 (3) |
C1—C2 | 1.41 (5) | C23—C24 | 1.41 (5) |
C1—C6 | 1.41 (5) | C23—C25 | 1.41 (3) |
C2—H2 | 1 | C24—C26 | 1.41 (3) |
C2—C3 | 1.41 (4) | C25—C40 | 1.41 (3) |
C3—H3 | 1 | C26—C27 | 1.41 (5) |
C3—C4 | 1.41 (5) | C26—C35 | 1.41 (3) |
C4—H4 | 1 | C27—C34 | 1.41 (3) |
C4—C5 | 1.41 (5) | C28—C29 | 1.41 (3) |
C5—H5 | 1 | C29—C30 | 1.41 (3) |
C5—C6 | 1.41 (4) | C29—C34 | 1.41 (5) |
C7—H7 | 1 | C30—H30 | 1 |
C7—C8 | 1.41 (3) | C30—C31 | 1.41 (3) |
C7—C12 | 1.41 (3) | C31—H31 | 1 |
C8—H8 | 1 | C31—C32 | 1.41 (5) |
C8—C9 | 1.41 (5) | C32—H32 | 1 |
C9—H9 | 1 | C32—C33 | 1.41 (3) |
C9—C10 | 1.41 (3) | C33—C34 | 1.41 (3) |
C10—H10 | 1 | C33—C36 | 1.41 (5) |
C10—C11 | 1.41 (3) | C35—C36 | 1.41 (3) |
C11—C12 | 1.41 (5) | C35—C40 | 1.41 (5) |
C11—C20 | 1.41 (3) | C36—C37 | 1.41 (3) |
C12—C13 | 1.41 (3) | C37—H37 | 1 |
C13—C14 | 1.41 (5) | C37—C38 | 1.41 (5) |
C13—C18 | 1.41 (3) | C38—H38 | 1 |
C14—H14 | 1 | C38—C39 | 1.41 (3) |
C14—C15 | 1.41 (3) | C39—H39 | 1 |
C15—H15 | 1 | C39—C40 | 1.41 (3) |
C15—C16 | 1.41 (3) | C41—H41 | 1 |
C16—C17 | 1.41 (5) | C41—C42 | 1.41 (5) |
C16—C28 | 1.41 (3) | C41—C46 | 1.41 (5) |
C17—C18 | 1.41 (3) | C42—H42 | 1 |
C17—C27 | 1.41 (3) | C42—C43 | 1.41 (4) |
C18—C19 | 1.41 (5) | C43—C44 | 1.41 (5) |
C19—C20 | 1.41 (3) | C44—H44 | 1 |
C19—C24 | 1.41 (3) | C44—C45 | 1.41 (5) |
C20—C21 | 1.41 (5) | C45—H45 | 1 |
C21—H21 | 1 | C45—C46 | 1.41 (4) |
C21—C22 | 1.41 (3) | C46—H46 | 1 |
C22—H22 | 1 | ||
H1—C1—C2 | 120.06 | C22—C23—C25 | 120.0 (12) |
H1—C1—C6 | 120.06 | C24—C23—C25 | 120.0 (7) |
C2—C1—C6 | 119.9 (9) | C19—C24—C23 | 120.0 (7) |
C1—C2—H2 | 120.05 | C19—C24—C26 | 120.0 (12) |
C1—C2—C3 | 119.9 (12) | C23—C24—C26 | 120.0 (7) |
H2—C2—C3 | 120.04 | C23—C25—C40 | 120.0 (12) |
C2—C3—H3 | 120 | C24—C26—C27 | 120.0 (7) |
C2—C3—C4 | 120.0 (14) | C24—C26—C35 | 120.0 (12) |
H3—C3—C4 | 120 | C27—C26—C35 | 120.0 (7) |
C3—C4—H4 | 120 | C17—C27—C26 | 120.0 (7) |
C3—C4—C5 | 120.0 (8) | C17—C27—C34 | 120.0 (12) |
H4—C4—C5 | 120 | C26—C27—C34 | 120.0 (7) |
C4—C5—H5 | 120 | C16—C28—C29 | 120.0 (12) |
C4—C5—C6 | 120.0 (12) | C28—C29—C30 | 120.0 (12) |
H5—C5—C6 | 120 | C28—C29—C34 | 120.0 (8) |
C1—C6—C5 | 120.0 (14) | C30—C29—C34 | 120.0 (8) |
H7—C7—C8 | 120 | C29—C30—H30 | 120 |
H7—C7—C12 | 120 | C29—C30—C31 | 120.0 (12) |
C8—C7—C12 | 120.0 (12) | H30—C30—C31 | 120 |
C7—C8—H8 | 120 | C30—C31—H31 | 120 |
C7—C8—C9 | 120.0 (8) | C30—C31—C32 | 120.0 (8) |
H8—C8—C9 | 120 | H31—C31—C32 | 120 |
C8—C9—H9 | 120 | C31—C32—H32 | 120 |
C8—C9—C10 | 120.0 (8) | C31—C32—C33 | 120.0 (8) |
H9—C9—C10 | 120 | H32—C32—C33 | 120 |
C9—C10—H10 | 120 | C32—C33—C34 | 120.0 (12) |
C9—C10—C11 | 120.0 (12) | C32—C33—C36 | 120.0 (7) |
H10—C10—C11 | 120 | C34—C33—C36 | 120.0 (7) |
C10—C11—C12 | 120.0 (7) | C27—C34—C29 | 120.0 (7) |
C10—C11—C20 | 120.0 (12) | C27—C34—C33 | 120.0 (12) |
C12—C11—C20 | 120.0 (7) | C29—C34—C33 | 120.0 (7) |
C7—C12—C11 | 120.0 (8) | C26—C35—C36 | 120.0 (12) |
C7—C12—C13 | 120.0 (12) | C26—C35—C40 | 120.0 (7) |
C11—C12—C13 | 120.0 (7) | C36—C35—C40 | 120.0 (7) |
C12—C13—C14 | 120.0 (7) | C33—C36—C35 | 120.0 (7) |
C12—C13—C18 | 120.0 (12) | C33—C36—C37 | 120.0 (8) |
C14—C13—C18 | 120.0 (7) | C35—C36—C37 | 120.0 (12) |
C13—C14—H14 | 120 | C36—C37—H37 | 120 |
C13—C14—C15 | 120.0 (8) | C36—C37—C38 | 120.0 (8) |
H14—C14—C15 | 120 | H37—C37—C38 | 120 |
C14—C15—H15 | 120 | C37—C38—H38 | 120 |
C14—C15—C16 | 120.0 (12) | C37—C38—C39 | 120.0 (8) |
H15—C15—C16 | 120 | H38—C38—C39 | 120 |
C15—C16—C17 | 120.0 (7) | C38—C39—H39 | 120 |
C15—C16—C28 | 120.0 (12) | C38—C39—C40 | 120.0 (12) |
C17—C16—C28 | 120.0 (7) | H39—C39—C40 | 120 |
C16—C17—C18 | 120.0 (7) | C25—C40—C35 | 120.0 (8) |
C16—C17—C27 | 120.0 (7) | C25—C40—C39 | 120.0 (12) |
C18—C17—C27 | 120.0 (12) | C35—C40—C39 | 120.0 (8) |
C13—C18—C17 | 120.0 (12) | H41—C41—C42 | 120 |
C13—C18—C19 | 120.0 (7) | H41—C41—C46 | 120 |
C17—C18—C19 | 120.0 (7) | C42—C41—C46 | 120.0 (13) |
C18—C19—C20 | 120.0 (7) | C41—C42—H42 | 120 |
C18—C19—C24 | 120.0 (7) | C41—C42—C43 | 120.0 (14) |
C20—C19—C24 | 120.0 (12) | H42—C42—C43 | 120.01 |
C11—C20—C19 | 120.0 (12) | C42—C43—C44 | 120.0 (15) |
C11—C20—C21 | 120.0 (7) | C43—C44—H44 | 120.01 |
C19—C20—C21 | 120.0 (7) | C43—C44—C45 | 120.0 (12) |
C20—C21—H21 | 120 | H44—C44—C45 | 120.01 |
C20—C21—C22 | 120.0 (8) | C44—C45—H45 | 120.01 |
H21—C21—C22 | 120 | C44—C45—C46 | 120.0 (14) |
C21—C22—H22 | 120 | H45—C45—C46 | 120.01 |
C21—C22—C23 | 120.0 (12) | C41—C46—C45 | 120.0 (15) |
H22—C22—C23 | 120 | C41—C46—H46 | 120.01 |
C22—C23—C24 | 120.0 (7) | C45—C46—H46 | 120.01 |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···C14 | 1.00 | 2.48 | 2.82 (7) | 99.53 |
C10—H10···C21 | 1.00 | 2.48 | 2.82 (7) | 99.53 |
C14—H14···C7 | 1.00 | 2.48 | 2.82 (7) | 99.56 |
C15—H15···C5 | 1.00 | 2.13 | 2.89 (9) | 131.67 |
C15—H15···C6 | 1.00 | 2.12 | 2.60 (6) | 106.98 |
C21—H21···C10 | 1.00 | 2.48 | 2.82 (7) | 99.55 |
C22—H22···C43 | 1.00 | 2.41 | 2.84 (7) | 105.43 |
C22—H22···C44 | 1.00 | 2.50 | 3.09 (8) | 117.66 |
C32—H32···C37 | 1.00 | 2.48 | 2.82 (11) | 99.54 |
C37—H37···C32 | 1.00 | 2.48 | 2.82 (11) | 99.54 |
C45—H45···C1i | 1.00 | 2.43 | 3.36 (13) | 154.10 |
Symmetry code: (i) −x−1/2, y−1/2, z. |
C46H30 | V = 1500 (60) Å3 |
Mr = 582.7 | Z = 2 |
Triclinic, P1 | F(000) = 604 |
Hall symbol: -P 1 | Dx = 1.287 Mg m−3 |
a = 10.5 (2) Å | Electron radiation, λ = 0.0335 Å |
b = 11.6 (3) Å | µ = 0 mm−1 |
c = 12.8 (3) Å | T = 293 K |
α = 85.3 (5)° | Nanocrystal, yellow |
β = 76.1 (5)° | 0.001 × 0.0004 × 0.0001 mm |
γ = 84.9 (5)° |
Zeiss Libra 120 diffractometer | θmax = 1.2°, θmin = 0.1° |
data have been collected by precession–assisted 3D electron diffration scans | h = −12→12 |
51475 measured reflections | k = −14→14 |
8265 independent reflections | l = −15→15 |
1315 reflections with I > 3σ(I) |
Refinement on F | 149 constraints |
R[F > 3σ(F)] = 0.162 | H-atom parameters constrained |
wR(F) = 0.196 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 1.84 | (Δ/σ)max = 0.023 |
8265 reflections | Δρmax = 0.27 e Å−3 |
241 parameters | Δρmin = −0.44 e Å−3 |
93 restraints |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4415 (9) | 0.9191 (7) | 0.3132 (6) | 0.0174 (5)* | |
H1 | 0.534328 | 0.918917 | 0.269097 | 0.0209* | |
C2 | 0.3691 (11) | 1.0244 (6) | 0.3401 (6) | 0.0174 (5)* | |
H2 | 0.410318 | 1.099122 | 0.315146 | 0.0209* | |
C3 | 0.2388 (11) | 1.0247 (6) | 0.4019 (6) | 0.0174 (5)* | |
H3 | 0.187211 | 1.099662 | 0.421042 | 0.0209* | |
C4 | 0.1809 (10) | 0.9198 (7) | 0.4368 (6) | 0.0174 (5)* | |
H4 | 0.088076 | 0.920048 | 0.480871 | 0.0209* | |
C5 | 0.2533 (11) | 0.8146 (6) | 0.4100 (6) | 0.0174 (5)* | |
H5 | 0.212087 | 0.73988 | 0.434909 | 0.0209* | |
C6 | 0.3837 (11) | 0.8143 (6) | 0.3482 (5) | 0.0174 (5)* | |
C7 | 0.2089 (6) | 0.4264 (4) | 0.0166 (4) | 0.0174 (5)* | |
H7 | 0.161845 | 0.50474 | 0.027119 | 0.0209* | |
C8 | 0.1656 (7) | 0.3471 (4) | −0.0435 (5) | 0.0174 (5)* | |
H8 | 0.088009 | 0.369441 | −0.075477 | 0.0209* | |
C9 | 0.2319 (7) | 0.2365 (4) | −0.0584 (5) | 0.0174 (5)* | |
H9 | 0.201335 | 0.180573 | −0.100848 | 0.0209* | |
C10 | 0.3417 (6) | 0.2048 (4) | −0.0130 (4) | 0.0174 (5)* | |
H10 | 0.38862 | 0.126356 | −0.023431 | 0.0209* | |
C11 | 0.3850 (5) | 0.2839 (3) | 0.0468 (3) | 0.0174 (5)* | |
C12 | 0.3185 (5) | 0.3948 (3) | 0.0617 (3) | 0.0174 (5)* | |
C13 | 0.3618 (5) | 0.4741 (3) | 0.1217 (3) | 0.0174 (5)* | |
C14 | 0.2951 (6) | 0.5854 (3) | 0.1366 (4) | 0.0174 (5)* | |
H14 | 0.217584 | 0.607792 | 0.104612 | 0.0209* | |
C15 | 0.3385 (7) | 0.6649 (4) | 0.1969 (5) | 0.0174 (5)* | |
H15 | 0.291463 | 0.743256 | 0.207409 | 0.0209* | |
C16 | 0.4485 (7) | 0.6331 (4) | 0.2424 (4) | 0.0174 (5)* | |
C17 | 0.5153 (6) | 0.5219 (3) | 0.2275 (4) | 0.0174 (5)* | |
C18 | 0.4719 (5) | 0.4423 (3) | 0.1672 (3) | 0.0174 (5)* | |
C19 | 0.5383 (5) | 0.3315 (3) | 0.1524 (3) | 0.0174 (5)* | |
C20 | 0.4949 (5) | 0.2521 (3) | 0.0922 (3) | 0.0174 (5)* | |
C21 | 0.5616 (6) | 0.1408 (4) | 0.0773 (4) | 0.0174 (5)* | |
H21 | 0.531022 | 0.08485 | 0.034884 | 0.0209* | |
C22 | 0.6717 (7) | 0.1091 (4) | 0.1225 (5) | 0.0174 (5)* | |
H22 | 0.71875 | 0.030812 | 0.111916 | 0.0209* | |
C23 | 0.7150 (6) | 0.1885 (4) | 0.1827 (4) | 0.0174 (5)* | |
C24 | 0.6493 (9) | 0.3003 (5) | 0.1964 (8) | 0.0174 (5)* | |
C25 | 0.8280 (7) | 0.1545 (6) | 0.2284 (6) | 0.0174 (5)* | |
C26 | 0.6938 (7) | 0.3802 (6) | 0.2594 (4) | 0.0174 (5)* | |
C27 | 0.6275 (6) | 0.4932 (7) | 0.2754 (4) | 0.0174 (5)* | |
C28 | 0.4915 (9) | 0.7156 (6) | 0.3040 (5) | 0.0174 (5)* | |
C29 | 0.5472 (13) | 0.6595 (7) | 0.3904 (8) | 0.0174 (5)* | |
C30 | 0.5541 (14) | 0.7225 (6) | 0.4791 (8) | 0.0174 (5)* | |
H30 | 0.51413 | 0.803775 | 0.477049 | 0.0209* | |
C31 | 0.6299 (14) | 0.6753 (6) | 0.5527 (7) | 0.0174 (5)* | |
H31 | 0.634806 | 0.719693 | 0.615191 | 0.0209* | |
C32 | 0.6989 (13) | 0.5649 (7) | 0.5375 (8) | 0.0174 (5)* | |
H32 | 0.752389 | 0.531657 | 0.589262 | 0.0209* | |
C33 | 0.6921 (13) | 0.5019 (6) | 0.4487 (8) | 0.0174 (5)* | |
H33 | 0.740698 | 0.42419 | 0.437942 | 0.0209* | |
C34 | 0.6162 (13) | 0.5491 (7) | 0.3752 (7) | 0.0174 (5)* | |
C35 | 0.8323 (8) | 0.3632 (7) | 0.2613 (7) | 0.0174 (5)* | |
C36 | 0.9015 (10) | 0.4550 (5) | 0.2816 (6) | 0.0174 (5)* | |
H36 | 0.858471 | 0.53528 | 0.285997 | 0.0209* | |
C37 | 1.0317 (10) | 0.4331 (6) | 0.2956 (7) | 0.0174 (5)* | |
H37 | 1.080603 | 0.497889 | 0.309823 | 0.0209* | |
C38 | 1.0928 (8) | 0.3192 (7) | 0.2893 (7) | 0.0174 (5)* | |
H38 | 1.184711 | 0.303761 | 0.299242 | 0.0209* | |
C39 | 1.0236 (10) | 0.2274 (5) | 0.2691 (7) | 0.0174 (5)* | |
H39 | 1.066642 | 0.147158 | 0.264759 | 0.0209* | |
C40 | 0.8934 (10) | 0.2494 (6) | 0.2550 (7) | 0.0174 (5)* | |
C41 | 1.0589 (9) | −0.1197 (7) | 0.1467 (6) | 0.0174 (5)* | |
H41 | 1.13812 | −0.147224 | 0.091323 | 0.0209* | |
C42 | 1.0090 (9) | −0.0039 (6) | 0.1411 (6) | 0.0174 (5)* | |
H42 | 1.052548 | 0.051013 | 0.081674 | 0.0209* | |
C43 | 0.8978 (9) | 0.0347 (5) | 0.2189 (7) | 0.0174 (5)* | |
C44 | 0.8367 (9) | −0.0424 (7) | 0.3023 (6) | 0.0174 (5)* | |
H44 | 0.757472 | −0.014851 | 0.357728 | 0.0209* | |
C45 | 0.8866 (10) | −0.1581 (6) | 0.3080 (6) | 0.0174 (5)* | |
H45 | 0.843102 | −0.213073 | 0.367427 | 0.0209* | |
C46 | 0.9977 (10) | −0.1968 (6) | 0.2302 (6) | 0.0174 (5)* | |
H46 | 1.033299 | −0.279308 | 0.234149 | 0.0209* |
C1—H1 | 1 | C23—C24 | 1.42 (6) |
C1—C2 | 1.40 (6) | C23—C25 | 1.45 (4) |
C1—C6 | 1.40 (6) | C24—C26 | 1.45 (4) |
C2—H2 | 1 | C25—C40 | 1.45 (5) |
C2—C3 | 1.40 (6) | C25—C43 | 1.52 (7) |
C3—H3 | 1 | C26—C27 | 1.44 (6) |
C3—C4 | 1.40 (6) | C26—C35 | 1.45 (6) |
C4—H4 | 1 | C27—C34 | 1.45 (6) |
C4—C5 | 1.40 (6) | C28—C29 | 1.45 (5) |
C5—H5 | 1 | C29—C30 | 1.42 (5) |
C5—C6 | 1.40 (6) | C29—C34 | 1.42 (6) |
C7—H7 | 1 | C30—H30 | 1 |
C7—C8 | 1.42 (4) | C30—C31 | 1.42 (4) |
C7—C12 | 1.41 (4) | C31—H31 | 1 |
C8—H8 | 1 | C31—C32 | 1.42 (6) |
C8—C9 | 1.41 (6) | C32—H32 | 1 |
C9—H9 | 1 | C32—C33 | 1.42 (5) |
C9—C10 | 1.42 (4) | C33—H33 | 1 |
C10—H10 | 1 | C33—C34 | 1.42 (4) |
C10—C11 | 1.41 (4) | C35—C36 | 1.42 (5) |
C11—C12 | 1.42 (6) | C35—C40 | 1.42 (7) |
C11—C20 | 1.42 (4) | C36—H36 | 1 |
C12—C13 | 1.42 (4) | C36—C37 | 1.42 (5) |
C13—C14 | 1.42 (6) | C37—H37 | 1 |
C13—C18 | 1.42 (4) | C37—C38 | 1.42 (7) |
C14—H14 | 1 | C38—H38 | 1 |
C14—C15 | 1.42 (4) | C38—C39 | 1.42 (5) |
C15—H15 | 1 | C39—H39 | 1 |
C15—C16 | 1.42 (4) | C39—C40 | 1.42 (5) |
C16—C17 | 1.42 (6) | C41—H41 | 1 |
C16—C28 | 1.45 (4) | C41—C42 | 1.40 (7) |
C17—C18 | 1.42 (4) | C41—C46 | 1.40 (5) |
C17—C27 | 1.45 (4) | C42—H42 | 1 |
C18—C19 | 1.41 (6) | C42—C43 | 1.40 (5) |
C19—C20 | 1.42 (4) | C43—C44 | 1.40 (5) |
C19—C24 | 1.42 (4) | C44—H44 | 1 |
C20—C21 | 1.42 (6) | C44—C45 | 1.40 (7) |
C21—H21 | 1 | C45—H45 | 1 |
C21—C22 | 1.42 (4) | C45—C46 | 1.40 (5) |
C22—H22 | 1 | C46—H46 | 1 |
C22—C23 | 1.42 (4) | ||
H1—C1—C2 | 120 | C19—C24—C23 | 120.0 (10) |
H1—C1—C6 | 120 | C19—C24—C26 | 120.6 (12) |
C2—C1—C6 | 120.0 (19) | C23—C24—C26 | 119.4 (14) |
C1—C2—H2 | 120 | C23—C25—C40 | 115.3 (14) |
C1—C2—C3 | 120.0 (12) | C23—C25—C43 | 122.4 (9) |
H2—C2—C3 | 120 | C40—C25—C43 | 120.0 (17) |
C2—C3—H3 | 120 | C24—C26—C27 | 120.2 (13) |
C2—C3—C4 | 120.0 (12) | C24—C26—C35 | 115.2 (10) |
H3—C3—C4 | 120 | C27—C26—C35 | 119.1 (10) |
C3—C4—H4 | 120 | C17—C27—C26 | 117.3 (9) |
C3—C4—C5 | 120.0 (19) | C17—C27—C34 | 113.4 (12) |
H4—C4—C5 | 120 | C26—C27—C34 | 120.9 (10) |
C4—C5—H5 | 120 | C16—C28—C29 | 112.4 (17) |
C4—C5—C6 | 120.0 (12) | C28—C29—C30 | 120.1 (18) |
H5—C5—C6 | 120 | C28—C29—C34 | 118.8 (14) |
C1—C6—C5 | 120.0 (12) | C30—C29—C34 | 120.0 (14) |
H7—C7—C8 | 120 | C29—C30—H30 | 114.25 |
H7—C7—C12 | 120 | C29—C30—C31 | 120.0 (16) |
C8—C7—C12 | 120.0 (12) | H30—C30—C31 | 125.08 |
C7—C8—H8 | 120 | C30—C31—H31 | 120 |
C7—C8—C9 | 120.0 (14) | C30—C31—C32 | 120.0 (13) |
H8—C8—C9 | 120 | H31—C31—C32 | 120 |
C8—C9—H9 | 120 | C31—C32—H32 | 120 |
C8—C9—C10 | 120.0 (9) | C31—C32—C33 | 120.0 (14) |
H9—C9—C10 | 120 | H32—C32—C33 | 120 |
C9—C10—H10 | 120 | C32—C33—H33 | 120 |
C9—C10—C11 | 120.0 (12) | C32—C33—C34 | 120.0 (16) |
H10—C10—C11 | 120 | H33—C33—C34 | 120 |
C10—C11—C12 | 120.0 (13) | C27—C34—C29 | 119.9 (12) |
C10—C11—C20 | 120.0 (12) | C27—C34—C33 | 119.3 (16) |
C12—C11—C20 | 120.0 (8) | C29—C34—C33 | 120.0 (13) |
C7—C12—C11 | 120.0 (8) | C26—C35—C36 | 121.2 (13) |
C7—C12—C13 | 120.0 (12) | C26—C35—C40 | 118.4 (11) |
C11—C12—C13 | 120.0 (13) | C36—C35—C40 | 120.0 (17) |
C12—C13—C14 | 120.0 (13) | C35—C36—H36 | 120 |
C12—C13—C18 | 120.0 (12) | C35—C36—C37 | 120.0 (13) |
C14—C13—C18 | 120.0 (8) | H36—C36—C37 | 120 |
C13—C14—H14 | 120 | C36—C37—H37 | 120 |
C13—C14—C15 | 120.0 (13) | C36—C37—C38 | 120.0 (10) |
H14—C14—C15 | 120 | H37—C37—C38 | 120 |
C14—C15—H15 | 120 | C37—C38—H38 | 120 |
C14—C15—C16 | 120.0 (12) | C37—C38—C39 | 120.0 (17) |
H15—C15—C16 | 120 | H38—C38—C39 | 120 |
C15—C16—C17 | 120.0 (9) | C38—C39—H39 | 120 |
C15—C16—C28 | 119.2 (13) | C38—C39—C40 | 120.0 (13) |
C17—C16—C28 | 120.8 (14) | H39—C39—C40 | 120 |
C16—C17—C18 | 120.0 (13) | C25—C40—C35 | 121.4 (17) |
C16—C17—C27 | 118.1 (9) | C25—C40—C39 | 118.6 (13) |
C18—C17—C27 | 121.9 (12) | C35—C40—C39 | 120.0 (10) |
C13—C18—C17 | 120.0 (12) | H41—C41—C42 | 120 |
C13—C18—C19 | 120.0 (8) | H41—C41—C46 | 120 |
C17—C18—C19 | 120.0 (13) | C42—C41—C46 | 120.0 (15) |
C18—C19—C20 | 120.0 (13) | C41—C42—H42 | 120 |
C18—C19—C24 | 120.0 (8) | C41—C42—C43 | 120.0 (11) |
C20—C19—C24 | 120.0 (12) | H42—C42—C43 | 120 |
C11—C20—C19 | 120.0 (12) | C25—C43—C42 | 128.9 (10) |
C11—C20—C21 | 120.0 (8) | C25—C43—C44 | 111.1 (17) |
C19—C20—C21 | 120.0 (13) | C42—C43—C44 | 120.0 (17) |
C20—C21—H21 | 120 | C43—C44—H44 | 120 |
C20—C21—C22 | 120.0 (9) | C43—C44—C45 | 120.0 (15) |
H21—C21—C22 | 120 | H44—C44—C45 | 120 |
C21—C22—H22 | 120 | C44—C45—H45 | 120 |
C21—C22—C23 | 120.0 (12) | C44—C45—C46 | 120.0 (11) |
H22—C22—C23 | 120 | H45—C45—C46 | 120 |
C22—C23—C24 | 120.0 (14) | C41—C46—C45 | 120.0 (17) |
C22—C23—C25 | 119.3 (13) | C41—C46—H46 | 120 |
C24—C23—C25 | 120.7 (10) | C45—C46—H46 | 120 |
Acknowledgements
IA, EM and MG acknowledge the Regione Toscana for funding the purchase of the Timepix through the FELIX project. CH, JP and SRH acknowledge the Engineering and Physical Sciences Research Council UK, MagnaPharm, a collaborative research project funded by the European Union's Horizon 2020 Research and Innovation program and the Bristol Centre for Functional Nanomaterials, and the Centre for Doctoral Training in Condensed Matter Physics for project funding. Work at CMU was supported by the National Science Foundation (NSF) Division of Materials Research. This research used resources of the Argonne Leadership Computing Facility (ALCF), which is a DOE Office of Science User Facility, and of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy.
Funding information
Funding for this research was provided by: Engineering and Physical Sciences Research Council (grant Nos. EP/L016648/1 and EP/L015544/1); European Union's Horizon 2020 Research and Innovation (grant No. 736899); Regione Toscana (grant No. CREO FESR 2014-2020 action); National Science Foundation, Division of Materials Research (grant No. DMR-2021803); DOE Office of Science User Facility (contract No. DE-AC02-06CH11357 ); Office of Science of the U.S. Department of Energy (contract No. DE-AC02-05CH11231).
References
Adamo, C. & Barone, V. (1999). J. Chem. Phys. 110, 6158–6170. Web of Science CrossRef CAS Google Scholar
Andrusenko, I., Hamilton, V., Lanza, A. E., Hall, C. L., Mugnaioli, E., Potticary, J., Buanz, A., Gaisford, S., Piras, A. M., Zambito, Y., Hall, S. R. & Gemmi, M. (2021). Int. J. Pharm. 608, 121067. Web of Science CSD CrossRef PubMed Google Scholar
Andrusenko, I., Hamilton, V., Mugnaioli, E., Lanza, A., Hall, C., Potticary, J., Hall, S. R. & Gemmi, M. (2019). Angew. Chem. 131, 11035–11038. CrossRef Google Scholar
Anschütz, R. (1886). Justus Liebigs Ann. Chem. 235, 299–341. Google Scholar
Arabei, S. M. & Pavich, T. A. (2004). J. Appl. Spectrosc. 71, 187–193. CrossRef CAS Google Scholar
Arias, D. H., Ryerson, J. L., Cook, J. D., Damrauer, N. H. & Johnson, J. C. (2016). Chem. Sci. 7, 1185–1191. Web of Science CrossRef CAS PubMed Google Scholar
Baldo, M. A., Adachi, C. & Forrest, S. R. (2000). Phys. Rev. B, 62, 10967–10977. Web of Science CrossRef CAS Google Scholar
Benner, G. & Probst, W. (1994). J. Microsc. 174, 133–142. CrossRef Web of Science Google Scholar
Blase, X., Duchemin, I., Jacquemin, D. & Loos, P. F. (2020). J. Phys. Chem. Lett. 11, 7371–7382. Web of Science CrossRef CAS PubMed Google Scholar
Blum, V., Gehrke, R., Hanke, F., Havu, P., Havu, V., Ren, X., Reuter, K. & Scheffler, M. (2009). Comput. Phys. Commun. 180, 2175–2196. Web of Science CrossRef CAS Google Scholar
Brauer, H.-D., Schmidt, R., Gauglitz, G. & Hubig, S. (1983). Photochem. Photobiol. 37, 595–598. CrossRef CAS Web of Science Google Scholar
Brázda, P., Palatinus, L. & Babor, M. (2019). Science, 364, 667–669. Web of Science PubMed Google Scholar
Broch, K., Dieterle, J., Branchi, F., Hestand, N. J., Olivier, Y., Tamura, H., Cruz, C., Nichols, V. M., Hinderhofer, A., Beljonne, D., Spano, F. C., Cerullo, G., Bardeen, C. J. & Schreiber, F. (2018). Nat. Commun. 9, 954. Web of Science CrossRef PubMed Google Scholar
Bruhn, J. F., Scapin, G., Cheng, A., Mercado, B. Q., Waterman, D. G., Ganesh, T., Dallakyan, S., Read, B. N., Nieusma, T., Lucier, K. W., Mayer, M. L., Chiang, N. J., Poweleit, N., McGilvray, P. T., Wilson, T. S., Mashore, M., Hennessy, C., Thomson, S., Wang, B., Potter, C. S. & Carragher, B. (2021). Front. Mol. Biosci. 8, 648603. Web of Science CSD CrossRef PubMed Google Scholar
Buchlovič, M., Kříž, Z., Hofr, C. & Potáček, M. (2013). Bioorg. Med. Chem. 21, 1078–1081. Web of Science PubMed Google Scholar
Burdett, J. J. & Bardeen, C. J. (2012). J. Am. Chem. Soc. 134, 8597–8607. Web of Science CrossRef CAS PubMed Google Scholar
Burdett, J. J. & Bardeen, C. J. (2013). Acc. Chem. Res. 46, 1312–1320. Web of Science CrossRef CAS PubMed Google Scholar
Burdett, J. J., Müller, A. M., Gosztola, D. & Bardeen, C. J. (2010). J. Chem. Phys. 133, 144506. Web of Science CrossRef PubMed Google Scholar
Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). J. Appl. Cryst. 48, 306–309. Web of Science CrossRef CAS IUCr Journals Google Scholar
Caruso, F., Rinke, P., Ren, X., Rubio, A. & Scheffler, M. (2013). Phys. Rev. B, 88, 075105. Web of Science CrossRef Google Scholar
Castro, K. P., Bukovsky, E. V., Kuvychko, I. V., DeWeerd, N. J., Chen, Y.-S., Deng, S. H. M., Wang, X.-B., Popov, A. A., Strauss, S. H. & Boltalina, O. V. (2019). Chem. Eur. J. 25, 13547–13565. Web of Science CSD CrossRef CAS PubMed Google Scholar
Chan, W.-L., Berkelbach, T. C., Provorse, M. R., Monahan, N. R., Tritsch, J. R., Hybertsen, M. S., Reichman, D. R., Gao, J. & Zhu, X.-Y. (2013). Acc. Chem. Res. 46, 1321–1329. Web of Science CrossRef CAS PubMed Google Scholar
Chan, W.-L., Ligges, M., Jailaubekov, A., Kaake, L., Miaja-Avila, L. & Zhu, X.-Y. (2011). Science, 334, 1541–1545. Web of Science CrossRef CAS PubMed Google Scholar
Chan, W.-L., Ligges, M. & Zhu, X.-Y. (2012). Nat. Chem. 4, 840–845. Web of Science CrossRef CAS PubMed Google Scholar
Cheng, Y. Y., Fückel, B., Khoury, T., Clady, R. G. C. R., Tayebjee, M. J. Y., Ekins-Daukes, N. J., Crossley, M. J. & Schmidt, T. W. (2010). J. Phys. Chem. Lett. 1, 1795–1799. Web of Science CrossRef CAS Google Scholar
Clar, E., Guye-Vuillème, J. F. & Stephen, J. F. (1964). Tetrahedron, 20, 2107–2117. CrossRef CAS Web of Science Google Scholar
Clar, E., Robertson, J. M., Schloegl, R. & Schmidt, W. (1981). J. Am. Chem. Soc. 103, 1320–1328. CrossRef CAS Web of Science Google Scholar
Clar, E. & Schmidt, W. (1975). Tetrahedron, 31, 2263–2271. CrossRef CAS Web of Science Google Scholar
Clar, E. & Schmidt, W. (1976). Tetrahedron, 32, 2563–2566. CrossRef CAS Web of Science Google Scholar
Clar, E. & Schmidt, W. (1979). Tetrahedron, 35, 2673–2680. CrossRef CAS Web of Science Google Scholar
Cui, P., Svensson Grape, E., Spackman, P. R., Wu, Y., Clowes, R., Day, G. M., Inge, A. K., Little, M. A. & Cooper, A. I. (2020). J. Am. Chem. Soc. 142, 12743–12750. Web of Science CSD CrossRef CAS PubMed Google Scholar
Deslippe, J., Samsonidze, G., Jain, M., Cohen, M. L. & Louie, S. G. (2013). Phys. Rev. B, 87, 1–6. Web of Science CrossRef Google Scholar
Deslippe, J., Samsonidze, G., Strubbe, D. A., Jain, M., Cohen, M. L. & Louie, S. G. (2012). Comput. Phys. Commun. 183, 1269–1289. Web of Science CrossRef CAS Google Scholar
Eaton, S. W., Shoer, L. E., Karlen, S. D., Dyar, S. M., Margulies, E. A., Veldkamp, B. S., Ramanan, C., Hartzler, D. A., Savikhin, S., Marks, T. J. & Wasielewski, M. R. (2013). J. Am. Chem. Soc. 135, 14701–14712. Web of Science CSD CrossRef CAS PubMed Google Scholar
Fetzer, J. C. (2000). Chemical Analysis, A Series of Monographs on Analytical Chemistry and Its Applications, Vol. 158, Large (C> = 24) Polycyclic Aromatic Hydrocarbons: Chemistry and Analysis, series edited by J. D. Winefordner. New York: Wiley Interscience. Google Scholar
Fetzer, J. C. (2007). Polycycl. Aromat.. Compd. 27, 143–162. Web of Science CrossRef CAS Google Scholar
Fort, E. H. (2010). Doctoral dissertation, Boston College University, Newton, USA. Google Scholar
Friedel, C. & Crafts, J. M. (1877). Comptes Rendus, 84, 1392–1395. Google Scholar
Gemmi, M., Mugnaioli, E., Gorelik, T. E., Kolb, U., Palatinus, L., Boullay, P., Hovmöller, S. & Abrahams, J. P. (2019). ACS Cent. Sci. 5, 1315–1329. Web of Science CrossRef CAS PubMed Google Scholar
Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C., Ceresoli, D., Chiarotti, G. L., Cococcioni, M., Dabo, I., Dal Corso, A., de Gironcoli, S., Fabris, S., Fratesi, G., Gebauer, R., Gerstmann, U., Gougoussis, C., Kokalj, A., Lazzeri, M., Martin-Samos, L., Marzari, N., Mauri, F., Mazzarello, R., Paolini, S., Pasquarello, A., Paulatto, L., Sbraccia, C., Scandolo, S., Sclauzero, G., Seitsonen, A. P., Smogunov, A., Umari, P. & Wentzcovitch, R. M. (2009). J. Phys. Condens. Matter, 21, 395502. Web of Science CrossRef PubMed Google Scholar
Golze, D., Dvorak, M. & Rinke, P. (2019). Front. Chem. 7, 377. Web of Science CrossRef PubMed Google Scholar
Gorelenko, A. Ya., Tolkachev, V. A. & Khalimanovich, D. M. (1977). J. Appl. Spectrosc. 26, 710–712. CrossRef Google Scholar
Grumstrup, E. M., Johnson, J. C. & Damrauer, N. H. (2010). Phys. Rev. Lett. 105, 257403. Web of Science CrossRef PubMed Google Scholar
Gupte, A., Tripathi, A., Patel, H., Rudakiya, D. & Gupte, S. (2016). Open Biotechnol. J. 10, 363–378. CrossRef CAS Google Scholar
Hall, C. L., Andrusenko, I., Potticary, J., Gao, S., Liu, X., Schmidt, W., Marom, N., Mugnaioli, E., Gemmi, M. & Hall, S. R. (2021). ChemPhysChem, 22, 1631–1637. Web of Science CSD CrossRef CAS PubMed Google Scholar
Haritash, A. K. & Kaushik, C. P. (2009). J. Hazard. Mater. 169, 1–15. Web of Science CrossRef PubMed CAS Google Scholar
Hart, S. M., Silva, W. R. & Frontiera, R. R. (2018). Chem. Sci. 9, 1242–1250. Web of Science CrossRef CAS PubMed Google Scholar
Jiang, H., Zhang, K. K., Ye, J., Wei, F., Hu, P., Guo, J., Liang, C., Chen, X., Zhao, Y., McNeil, L. E., Hu, W. & Kloc, C. (2013). Small, 9, 990–995. Web of Science CrossRef CAS PubMed Google Scholar
Jones, C. G., Asay, M., Kim, L. J., Kleinsasser, J. F., Saha, A., Fulton, T. J., Berkley, K. R., Cascio, D., Malyutin, A. G., Conley, M. P., Stoltz, B. M., Lavallo, V., Rodríguez, J. A. & Nelson, H. M. (2019). ACS Cent. Sci. 5, 1507–1513. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kaiukov, R., Almeida, G., Marras, S., Dang, Z., Baranov, D., Petralanda, U., Infante, I., Mugnaioli, E., Griesi, A., De Trizio, L., Gemmi, M. & Manna, L. (2020). Inorg. Chem. 59, 548–554. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Kapaca, E., Jiang, J., Cho, J., Jordá, J. L., Díaz-Cabañas, M. J., Zou, X., Corma, A. & Willhammar, T. (2021). J. Am. Chem. Soc. 143, 8713–8719. Web of Science CrossRef CAS PubMed Google Scholar
Kim, V. O., Broch, K., Belova, V., Chen, Y. S., Gerlach, A., Schreiber, F., Tamura, H., Della Valle, R. G., D'Avino, G., Salzmann, I., Beljonne, D., Rao, A. & Friend, R. (2019). J. Chem. Phys. 151, 164706. Web of Science CrossRef PubMed Google Scholar
Knight, J. W., Wang, X., Gallandi, L., Dolgounitcheva, O., Ren, X., Ortiz, J. V., Rinke, P., Körzdörfer, T. & Marom, N. (2016). J. Chem. Theory Comput. 12, 615–626. Web of Science CrossRef CAS PubMed Google Scholar
Ko, S. H., Lee, T., Park, H., Ahn, D.-S., Kim, K., Kwon, Y., Cho, S. J. & Ryoo, R. (2018). J. Am. Chem. Soc. 140, 7101–7107. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kolb, U., Gorelik, T., Kübel, C., Otten, M. T. & Hubert, D. (2007). Ultramicroscopy, 107, 507–513. Web of Science CrossRef PubMed CAS Google Scholar
Kolb, U., Mugnaioli, E. & Gorelik, T. E. (2011). Cryst. Res. Technol. 46, 542–554. Web of Science CrossRef CAS Google Scholar
Konishi, A., Hirao, Y., Matsumoto, K., Kurata, H. & Kubo, T. (2013). Chem. Lett. 42, 592–594. Web of Science CSD CrossRef CAS Google Scholar
Krotee, P., Griner, S. L., Sawaya, M. R., Cascio, D., Rodriguez, J. A., Shi, D., Philipp, S., Murray, K., Saelices, L., Lee, J., Seidler, P., Glabe, C. G., Jiang, L., Gonen, T. & Eisenberg, D. S. (2018). J. Biol. Chem. 293, 2888–2902. Web of Science CrossRef CAS PubMed Google Scholar
Krysiak, Y., Maslyk, M., Silva, B. N., Plana-Ruiz, S., Moura, H. M., Munsignatti, E. O., Vaiss, V. S., Kolb, U., Tremel, W., Palatinus, L., Leitão, A. A., Marler, B. & Pastore, H. O. (2021). Chem. Mater. 33, 3207–3219. Web of Science CrossRef ICSD CAS Google Scholar
Lanza, A., Margheritis, E., Mugnaioli, E., Cappello, V., Garau, G. & Gemmi, M. (2019). IUCrJ, 6, 178–188. Web of Science CrossRef CAS PubMed IUCr Journals Google Scholar
Lawal, A. T. (2017). Cogent Environ. Sci. 3, 1339841. CrossRef Google Scholar
Le, A. K., Bender, J. A. & Roberts, S. T. (2016). J. Phys. Chem. Lett. 7, 4922–4928. Web of Science CrossRef CAS PubMed Google Scholar
Levine, A. M., Bu, G., Biswas, S., Tsai, E. H. R., Braunschweig, A. B. & Nannenga, B. L. (2020). Chem. Commun. 56, 4204–4207. Web of Science CSD CrossRef CAS Google Scholar
Liu, C., Kloppenburg, J., Yao, Y., Ren, X., Appel, H., Kanai, Y. & Blum, V. (2020a). J. Chem. Phys. 152, 044105. Web of Science CrossRef PubMed Google Scholar
Liu, X., Tom, R., Gao, S. & Marom, N. (2020b). J. Phys. Chem. C, 124, 26134–26143. Web of Science CrossRef CAS Google Scholar
Liu, X., Tom, R., Wang, X., Cook, C., Schatschneider, B. & Marom, N. (2020c). J. Phys. Condens. Matter, 32, 184001. Web of Science PubMed Google Scholar
Margulies, E. A., Logsdon, J. L., Miller, C. E., Ma, L., Simonoff, E., Young, R. M., Schatz, G. C. & Wasielewski, M. R. (2017). J. Am. Chem. Soc. 139, 663–671. Web of Science CSD CrossRef CAS PubMed Google Scholar
Marom, N., Caruso, F., Ren, X., Hofmann, O. T., Körzdörfer, T., Chelikowsky, J. R., Rubio, A., Scheffler, M. & Rinke, P. (2012). Phys. Rev. B, 86, 245127. Web of Science CrossRef Google Scholar
Maulding, D. (1970). J. Org. Chem. 35, 1221–1223. CrossRef CAS Web of Science Google Scholar
Michl, J. (2019). Mol. Front. J. 03, 84–91. CrossRef CAS Google Scholar
Mirjani, F., Renaud, N., Gorczak, N. & Grozema, F. C. (2014). J. Phys. Chem. C, 118, 14192–14199. Web of Science CrossRef CAS Google Scholar
Miyata, K., Conrad-Burton, F. S., Geyer, F. L. & Zhu, X.-Y. (2019). Chem. Rev. 119, 4261–4292. Web of Science CrossRef CAS PubMed Google Scholar
Monahan, N. & Zhu, X.-Y. (2015). Annu. Rev. Phys. Chem. 66, 601–618. Web of Science CrossRef CAS PubMed Google Scholar
Nannenga, B. L. & Gonen, T. (2019). Nat. Methods, 16, 369–379. Web of Science CrossRef CAS PubMed Google Scholar
Nederlof, I., van Genderen, E., Li, Y.-W. & Abrahams, J. P. (2013). Acta Cryst. D69, 1223–1230. Web of Science CrossRef CAS IUCr Journals Google Scholar
Palatinus, L., Brázda, P., Jelínek, M., Hrdá, J., Steciuk, G. & Klementová, M. (2019). Acta Cryst. B75, 512–522. Web of Science CrossRef IUCr Journals Google Scholar
Palatinus, L., Jacob, D., Cuvillier, P., Klementová, M., Sinkler, W. & Marks, L. D. (2013). Acta Cryst. A69, 171–188. Web of Science CrossRef CAS IUCr Journals Google Scholar
Palatinus, L., Petříček, V. & Corrêa, C. A. (2015). Acta Cryst. A71, 235–244. Web of Science CrossRef IUCr Journals Google Scholar
Papi, F., Potticary, J., Lanza, A. E., Hall, S. R. & Gemmi, M. (2021). Cryst. Growth Des. 21, 6341–6348. Web of Science CSD CrossRef CAS Google Scholar
Perdew, J. P., Burke, K. & Ernzerhof, M. (1996). Phys. Rev. Lett. 77, 3865–3868. CrossRef PubMed CAS Web of Science Google Scholar
Perdew, J. P., Burke, K. & Ernzerhof, M. (1997). Phys. Rev. Lett. 78, 1396. CrossRef Web of Science Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2014). Z. Kristallogr. Cryst. Mater. 229, 345–352. Google Scholar
Rauhut, M. M., Roberts, B. G., Maulding, D. R., Bergmark, W. & Coleman, R. (1975). J. Org. Chem. 40, 330–335. CrossRef CAS Web of Science Google Scholar
Ren, X., Rinke, P., Blum, V., Wieferink, J., Tkatchenko, A., Sanfilippo, A., Reuter, K. & Scheffler, M. (2012). New J. Phys. 14, 053020. Web of Science CrossRef Google Scholar
Renaud, N. & Grozema, C. (2015). J. Phys. Chem. Lett. 6, 360–365. Web of Science CrossRef CAS PubMed Google Scholar
Renaud, N., Sherratt, P. A. & Ratner, M. A. (2013). J. Phys. Chem. Lett. 4, 1065–1069. Web of Science CrossRef CAS PubMed Google Scholar
Saranya, G., Kolandaivel, P. & Senthilkumar, K. (2011). J. Phys. Chem. A, 115, 14647–14656. Web of Science CrossRef CAS PubMed Google Scholar
Sauvage, G. (1947a). Ann. Chim. 2, 844–873. CAS Google Scholar
Sauvage, G. (1947b). Comptes Rendus, 225, 247–249. CAS Google Scholar
Sawaya, M. R., Rodriquez, J., Cascio, D., Collazo, M. J., Shi, D., Reyes, F. E., Hattne, J., Gonen, T. & Eisenberg, D. S. (2016). PNAS, 113, 11232–11236. Web of Science CrossRef CAS PubMed Google Scholar
Schmidt, T. W. & Castellano, F. N. (2014). J. Phys. Chem. Lett. 5, 4062–4072. Web of Science CrossRef CAS PubMed Google Scholar
Scholl, R. & Mansfeld, J. (1910). EurJIC, 43, 1734–1746. CAS Google Scholar
Scholl, R. & Meyer, K. (1932). Ber. Dtsch Chem. Ges. A/B, 65, 902–915. CrossRef Google Scholar
Scholl, R., Seer, C. & Weitzenböck, R. (1910). Ber. Dtsch Chem. Ges. 43, 2202–2209. CrossRef CAS Google Scholar
Schulze, T. F. & Schmidt, T. W. (2015). Energy Environ. Sci. 8, 103–125. Web of Science CrossRef CAS Google Scholar
Seip, M. & Brauer, H.-D. (1992). J. Am. Chem. Soc. 114, 4486–4490. CrossRef CAS Web of Science Google Scholar
Setten, M. J. van, Caruso, F., Sharifzadeh, S., Ren, X., Scheffler, M., Liu, F., Lischner, J., Lin, L., Deslippe, J. R., Louie, S. G., Yang, C., Weigend, F., Neaton, J. B., Evers, F. & Rinke, P. (2015). J. Chem. Theory Comput. 11, 5665–5687. Web of Science PubMed Google Scholar
Sharifzadeh, S., Darancet, P., Kronik, L. & Neaton, J. B. (2013). J. Phys. Chem. Lett. 4, 2197–2201. Web of Science CrossRef CAS Google Scholar
Sharifzadeh, S., Wong, C. Y., Wu, H., Cotts, B. L., Kronik, L., Ginsberg, N. S. & Neaton, J. B. (2015). Adv. Funct. Mater. 25, 2038–2046. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, M. B. & Michl, J. (2010). Chem. Rev. 110, 6891–6936. Web of Science CrossRef CAS PubMed Google Scholar
Smith, M. B. & Michl, J. (2013). Annu. Rev. Phys. Chem. 64, 361–386. Web of Science CrossRef CAS PubMed Google Scholar
Tkatchenko, A. & Scheffler, M. (2009). Phys. Rev. Lett. 102, 073005. Web of Science CrossRef PubMed Google Scholar
Tomkiewicz, Y., Groff, R. P. & Avakian, P. (1971). J. Chem. Phys. 54, 4504–4507. CrossRef CAS Web of Science Google Scholar
Troullier, N. & Martins, J. L. (1991). Phys. Rev. B, 43, 1993–2006. CrossRef CAS Web of Science Google Scholar
Wan, W., Sun, J., Su, J., Hovmöller, S. & Zou, X. (2013). J. Appl. Cryst. 46, 1863–1873. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X., Garcia, T., Monaco, S., Schatschneider, B. & Marom, N. (2016). CrystEngComm, 18, 7353–7362. Web of Science CrossRef CAS Google Scholar
Wang, X., Liu, X., Cook, C., Schatschneider, B. & Marom, N. (2018). J. Chem. Phys. 148, 184101. Web of Science CrossRef PubMed Google Scholar
Wang, X., Tom, R., Liu, X., Congreve, D. N. & Marom, N. (2020). J. Mater. Chem. C, 8, 10816–10824. Web of Science CrossRef CAS Google Scholar
Warmack, R. A., Boyer, D. R., Zee, C.-T., Richards, L. S., Sawaya, M. R., Cascio, D., Gonen, T., Eisenberg, D. S. & Clarke, S. G. (2019). Nat. Commun. 10, 3357. Web of Science CrossRef PubMed Google Scholar
Wilkes, H. (2010). Methods of Hydrocarbon Analysis, in Handbook of Hydrocarbon and Lipid Microbiology, edited by K. N. Timmis. Berlin, Heidelberg: Springer. Google Scholar
Wilson, M. W. B., Rao, A., Clark, J., Kumar, R. S. S., Brida, D., Cerullo, G. & Friend, R. H. (2011). J. Am. Chem. Soc. 133, 11830–11833. Web of Science CrossRef CAS PubMed Google Scholar
Wu, T. C., Thompson, N. J., Congreve, D. N., Hontz, E., Yost, S. R., Van Voorhis, T. & Baldo, M. A. (2014). Appl. Phys. Lett. 104, 193901. Web of Science CrossRef Google Scholar
Würthner, F., Saha-Möller, C. R., Fimmel, B., Ogi, S., Leowanawat, P. & Schmidt, D. (2016). Chem. Rev. 116, 962–1052. Web of Science PubMed Google Scholar
Xu, H., Lebrette, H., Clabbers, M. T. B., Zhao, J., Griese, J. J., Zou, X. & Högbom, M. (2019). Sci. Adv. 5, eaax4621. Web of Science CrossRef PubMed Google Scholar
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