research papers
π–π-Induced aggregation and single-crystal fluorescence anisotropy of 5,6,10b-triazaacephenanthrylene
aFaculty of Chemistry, Jagiellonian University, Gronostajowa 2, Kraków, Małopolskie 30-387, Poland, and bIstituto di Scienze e Tecnologie Molecolari, CNR-ISTM and INSTM UdR di Milano, via C. Golgi, Milano, 20133, Italy
*Correspondence e-mail: ostrowsk@chemia.uj.edu.pl, gryl@chemia.uj.edu.pl
The structural origin of absorption and fluorescence anisotropy of the single crystal of the π-conjugated heterocyclic system 5,6,10b-triazaacephenanthrylene, TAAP, is presented in this study. X-ray analysis shows that the crystal framework in the P is formed by centrosymmetric dimers of face-to-face mutually oriented TAAP molecules joined by π–π non-covalent interactions. The conformation of the TAAP molecule is stabilized by intramolecular C—H⋯N(sp2), N(sp2)H⋯π(CN), and C—H⋯O(sp2) hydrogen bonds. The presence of weak π–π interactions is confirmed by quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) analysis. The analysis of the optical spectra of TAAP in solution and in the solid state does not allow the specification of the aggregation type. DFT calculations for the dimer in the gas phase indicate that the lowest singlet excitation is forbidden by symmetry, suggesting H-type aggregation, even though the overall is bathochromically shifted as for the J-type. The experimental determination of the permanent of a TAAP molecule in 1,4-dioxane solution indicates the presence of the monomer form. The calculated absorption and emission spectra of the crystal in a simple approximation are consistent with the experimentally determined orientation of the absorption and emission transition dipole moments in TAAP single crystals. The electrostatic interaction between monomers with a permanent (ca 4 D each) could result in the unusual spectroscopic JH-aggregate behaviour of the TAAP dimer.
1. Introduction
Optical properties of π-conjugated crystalline materials depend on the packing arrangement in the (Varghese & Das, 2011; Varughese, 2014). The molecular self-assembly is guided by hydrogen-bonding, π–π stacking and C—H⋯π non-covalent interactions between planar π-conjugated systems (Loots & Barbour, 2012). There are three main geometries of aromatic π–π interactions in the dimer that are known, taking into account the relative position of the planar aromatic molecules: edge-to-face (T-shaped), eclipsed face-to-face (cofacial, sandwich-type) and offset face-to-face (slipped, head-to-tail) (Loots & Barbour, 2012; Janiak, 2000; Hunter et al., 2001). The strength of electronic transitions for π–π coupled conjugated systems depends on the vector sum of the transition dipole moments for monomers. There are two main types of aggregates, J-type (Würthner et al., 2011) and H-type (Nüesch & Grätzel, 1995; Spano, 2000; Xu et al., 2012), that are considered by Kasha's approach (Gierschner & Park, 2013; McRae & Kasha, 1958; Kasha et al., 1965). For J-type aggregates, the π-dimers consist of coplanar mutually shifted molecules with a head-to-tail orientation of the monomer transition dipole moments. In this case, the of the dimer splits into two states, a lower energy state and a higher energy state, which have parallel and antiparallel transition dipole moments, respectively. The absorption and emission transitions gain only the lower state with a non-zero total transition The absorption band for the dimer related to the S0→S1 transition is bathochromically shifted with respect to that of the monomer band. For H-type aggregates, the molecules are aligned face-to-face, with an antiparallel orientation of the molecular transition dipole moments. The excited π-dimer state splits into a higher state and a lower state, with a parallel and an antiparallel orientation of the transition dipole moments, respectively (Fig. 1). The absorption transitions to the higher state are not forbidden for H-type aggregates and, as a result, a hypsochromically shifted absorption band is usually observed. The emission proceeds from the lowest vibrational level of the lower-energy H-dimer to the weakly allowed higher vibrational states of the ground electronic state (Spano, 2010; Spano & Silva, 2014). As a result of fast non-radiative relaxation, the weak emission implies that H-type aggregates are considered as poor emitters (Fang et al., 2014).
The determination of the aggregation type relying only on blue or red spectral band shifts from the monomer in solution to the dimer in the solid state may be misleading for several reasons. Kasha's loosely-bonded dimers (Gierschner & Park, 2013; McRae & Kasha, 1958; Kasha et al., 1965). Molecules with permanent dipole moments may induce both intra- and intermolecular charge transfer, resulting in bathochromic spectral band shifts (Huang et al., 2011). Enhanced intrachain planarization, as in the case of poly(3-hexylthiophene) aggregates (Brown et al., 2003), may also lead to red shifts with the H-type geometry and nature. Crystals that revealed such unusual spectral characteristics are classified as HJ- or JH-type according to the new paradigm for organic electronic materials design (Yamagata et al., 2014). In this two-letter notation, the first refers to the Coulombic long-range coupling and the second to the charge transfer (CT) short-range coupling. These couplings compete with the π–π interactions between neighbouring molecules (Yamagata et al., 2014). Coulombic coupling induces H-type aggregation behaviour with the coupling parameter J0 > 0, whereas CT coupling promotes J-type with J0 < 0 (Spano & Silva, 2014; Yamagata et al., 2014).
theory explains the shifts of absorption bands forRecently, we have described the synthesis of the new π-conjugated heterocyclic system 5,6,10b-triazaacephenanthrylene (TAAP) (Ostrowska et al., 2016), which is structurally related to the naturally occurring such as aristolactams (Kumar et al., 2003; Michl et al., 2014). The π-conjugated TAAP planar chromophore exhibits a donor–acceptor architecture with a few different acceptor groups: carbonyl imide, nitrile, and two This specific electronic arrangement results in delocalization of the N5 and N10b lone electron pairs into the π system, leading to the formation of The possible resonance structures are shown in Fig. 2. In the B and C forms, the carbonyl O atom withdraws the electron lone pair from either the N5 or N10b atoms. In the D form, the electron lone pair from N5 is shifted to atom N6, whereas in the E and F forms, the electron lone pair of N10b is attracted by the imine N atom at C1 and the nitrile N atom at C2, respectively. It was shown that pyrazine-fused heterocyclic systems with two imine moieties can be used as electron-withdrawing units to construct conjugated organic materials for optoelectronic applications (Lu et al., 2014). In the TAAP heterocyclic system, the located at the p orbital of the N10b atom changes the character of the imine group from (typically observed for quinoxaline) to electron donor.
In the present study, we show the influence of face-to-face monomer π–π overlap in dimers on the aggregation type, single-crystal absorption and fluorescence anisotropy of the new heterocyclic system of TAAP. We have attempted to define the aggregation type of TAAP in order to understand its optical properties in solution and the crystalline state.
It should be noted that, until now, surprisingly little has been published on single-crystal fluorescence anisotropy, except for rubrene (El Helou et al., 2010; Ma et al., 2013), green fluorescent protein (GFP) (Inoué et al., 2002; Rosell & Boxer, 2003) and complexes of nickel with (Hara et al., 2011). However, it should be noted that recent publications concerning the usage of distinct fluorescence bands, based on intramolecular proton transfer, e.g. for alcohol vapour detection (Chen et al., 2016), as well as the multicolour fluorescence of hetero-Ln-MOF (where MOF denotes metal–organic framework), hierarchical single crystals, provide potential applications in miniaturized optoelectronic devices (Pan et al., 2017).
2. Experimental
2.1. General aspects
1H NMR and 13C NMR spectra were recorded using a Bruker Avance III 600 and a Bruker Avance II 300 at 300 K. The chemical shifts (δ) are reported in parts per million (ppm) on a δ scale downfield from TMS. The 1H NMR spectra were referenced internally to the residual proton resonance in CDCl3 (δ 7.26 ppm), CD2Cl2 (5.32 ppm), tetrachloroethane-d2 (6.00 ppm), THF-d8 (1.73, 3.58 ppm), dioxane-d8 (3.53 ppm), toluene-d8 (7.09, 7.00, 6.98, 2.09 ppm) and benzene-d6 (δ 7.15 ppm). The fluorescence measurements for crystalline TAAP were recorded at 298 K with an excitation slit width of 5 nm, an emission slit of 5 nm and a 700 V PMT voltage. Sample crystals were illuminated under a polarized microscope with an illuminator using 8 pieces UV (410 nm) LED (LEDs were distributed around the sample every 45°) and observed through an analyzer (linear polarization filter). The UV–Vis spectra for TAAP were recorded using a Hitachi U-3900 H spectrophotometer in 1 cm cells at 298 K after equilibrating for 20 min.
The fluorescence measurements for TAAP solution were performed using a Hitachi F-4500 spectrofluorometer. All spectra were recorded at 298 K with an excitation slit width of 5 nm, an emission slit of 5 nm and a 400 V or 600 V of the PMT voltage.
The fluorescence properties of a TAAP single crystal was analyzed with an Al–Si Nikon Inc. (Japan) confocal laser scanning system (LSCM) built onto a Nikon inverted Ti-E microscope using a Zeiss Plan-APOCHROMAT 100 ×/1.4na Oil DIC objective. Images were acquired at a resolution of 2048 × 2048. The Al–Si system was equipped with four-channel detection, as well as LSBF imaging by diascopic detection of forward scattered excitation laser light during confocal laser scanning. The excitation for confocal microscopy was provided by a
with an excitation wavelength at 405 nm. The fluorescence spectra were collected using a 32-channel spectral detector.2.2. Synthesis and growth of single crystals of TAAP
The synthesis of TAAP has been described previously (Ostrowska et al., 2016). The single crystals were isolated independently from highly concentrated solutions of TAAP in acetonitrile, acetonitrile–water, toluene, CDCl3, DMSO-d6, tetrachloroethane-d2, THF-d8 and dioxane-d8. Natural cooling and slow evaporation of solvents in each case gave single crystals with the same habit and crystal structure.
2.3. X-ray crystallography
The single-crystal X-ray diffraction experiments for TAAP_RT and TAAP_LT were carried out using monochromated Cu Kα radiation (λ = 1.54178 Å) and Mo Kα radiation (λ = 0.71073 Å), respectively. The experimental data were processed with CrysAlisPro. Crystallographic data and the details of data collection and are summarized in Table S1.1 (see supporting information). The structure was solved using with SIR92 (Altomare et al., 1994). A procedure by full-matrix least-squares methods based on F2 values against unique reflections, including all atomic fractional coordinates and anisotropic displacement parameters for non-H atoms, was performed using SHELXL2013 (Sheldrick, 2015). H atoms were found from difference Fourier maps and were included in the procedure in the riding model, assuming isotropic displacement parameters.
3. Results and discussion
3.1. X-ray determination of TAAP
Single-crystal X-ray 3, toluene, CH3CN, CH3CN–water mixture and tetrachloroethane-d2, as triclinic crystals, with a centrosymmetric in the P (Fig. 3 and Table S1.1). Selected geometrical parameters for TAAP_LT and TAAP_RT are summarized in Tables S1.2 and S1.3, respectively. The TAAP molecules form dimers arranged in a cofacial sandwich-like fashion, with an interlayer distance of 3.468 Å at 293 K (RT) and 3.413 Å at 130 K (LT).
revealed that TAAP crystallizes from most of the solvents such as THF, CHClThe imine atom N11 forms two intramolecular interactions, acting as a strong donor for the weak C≡N π-acceptor (Desiraju & Steiner, 2001; Kumar et al., 1998) [N11—H11⋯π(C≡N): 2.54 (2), 3.127 (2) Å, ∠DHA 124 (2)°] and strong acceptor for weak C—H donor [C10—H10⋯N11: 2.16, 2.795 (2) Å, ∠DHA 123°]. The nitrogen N11 atom is directly involved in the planarization of the antiaromatic heterocyclic system (Figs. 3 and S1.1–S1.3). The intramolecular hydrogen bond H10⋯N11 leads to the formation of an additional quasi-aromatic ring (Jezierska-Mazzarello et al., 2012; Krygowski et al., 2014) with the closed-coupled H11 proton and sp2 of the N10B atom. That is confirmed by the valence angle sum of 360° at N10B (C3A1—N10B—C10A = 116.9, C10A—N10B—C1 = 126.4 and C1—N10B—C3A1 = 116.7°). Extension of the π-conjugation onto the imine and nitrile groups shifts the centre of gravity of the monomer towards atom N10B (Fig. 3b). The two molecules of the dimer in the antiparallel configuration are shifted towards each other, with a centroid-to-centroid distance of 3.559 Å (the positions of centroids are defined for moieties without the imine and nitrile groups), resembling the π–π stacking interactions between adjacent sheets in graphite. The conformation of the TAAP molecule is additionally stabilized by the intramolecular hydrogen bond H56⋯O4 [C56—H56⋯O4: 2.56, 2.955 (2) Å, ∠DHA 105°] (Figs. S1.1 and S1.2, and Tables S1.4 and S1.5). The packing arrangement of the dimers is governed exclusively by very weak C—H⋯π and van der Waals interactions (Tables S1.4 and S1.5). It is important to note that the centrosymmetric dimers are translationally aligned approximately along [111] (shown in Fig. 3c), with the direction of the π–π interaction at about 15° with respect to [111] towards the ab plane, resembling the π–π β-motif (Loots & Barbour, 2012).
The crystallographic data clearly reveal that the monomer of TAAP belongs to the C1(1) symmetry group, whereas the dimer is centrosymmetric with the symmetry corresponding to the Ci, which allows us to categorize the symmetry of its states with two irreducible representations Ag and Au. According to the theory of Kasha (Gierschner & Park, 2013; McRae & Kasha, 1958; Kasha et al., 1965), the S1 in H aggregate splits into two energy levels: the lower belonging to the totally symmetric representation Ag and the higher assigned to the representation Au, that is antisymmetric with respect to the inversion. In the ground state, the resultant for a centrosymmetric dimer is zero. This is the result of the antiparallel orientation of identical monomer dipole moments. The polarization of the molecules may have an impact not only on the packing motifs in the single-crystal structure but also on the formation of the dimers in solution with the dipole moments of adjacent monomers in an antiparallel configuration.
3.2. QTAIM charge-density and NCI analyses
QTAIM charge-density analysis (Bader, 2003) was performed for the dimer of TAAP to confirm the existence of π–π interactions in the using AIMAll software (Keith, 2010). The wavefunction for calculations was obtained at the DFT/B3LYP 6-311G**(2d,2p) level using GAUSSIAN09 (Frisch et al., 2009), which uses experimental geometry with C—H distances fitted to neutron values (Allen & Bruno, 2010).
Molecular graphs with marked bond critical points (bcp, green), ring critical points (rcp, red), and cage critical points (ccp, blue) are presented in Figs. 4(a) and 4(b). The bcp analysis for the obtained intermolecular interactions is presented in Table S2.1. The existence of three weak intramolecular hydrogen bonds of C—H⋯O or C—H⋯N type (namely H10⋯N11A, H56A⋯O4A and H52A⋯N6A) was confirmed. These three interactions make the rigid. Additionally, between the two dimer components, there are five pairwise interactions of the N⋯N, C⋯C and N⋯C types, forming π–π interactions and stabilizing the dimer structure. All weak inter- and intramolecular interactions can be classified as closed-shell interactions – |V(r)|/G(r) > 1 and ∇2ρ(r) > 0, E(r)/ρ(r) > 0 (Table S6).
Counterpoise-corrected interaction energy has been calculated for the dimer of TAAP using the experimental geometry fitted to the neutron X—H distances (Allen & Bruno, 2010) and utilizing the DFT M052X/6–311+G(2df,2p) approach which has proven to be effective for the evaluation of weak interactions (Zhao & Truhlar, 2007). The basis set superposition error (BSSE) corrected energy is equal to −47.74 kJ mol−1. For comparison, the interaction energy using the same method and basis set is −40.08 kJ mol−1 in the adenine–tymine stack, −35.44 kJ mol−1 in the uracil dimer, and −21.30 kJ mol−1 in the water dimer. Aside from the identified π–π interactions, there is also one weak H⋯H bonding interaction (C56A—H56A⋯H10B—C10B) and one weak C8A⋯H36B interaction. NCI analysis was performed to confirm the QTAIM results and to visualize intermolecular interactions between the two dimer components. The NCI method uses the reduced gradient of electron density s(r) to visualize inter- and intramolecular interactions (Table S2.1). To classify these interactions as favourable or unfavourable, the electron density is multiplied by the sign of second Hessian eigenvalue (). Strong and attractive interactions are those with ρ(r) > 0 and 0, whereas for weak interactions ρ(r) ≃ 0 and and strong and repulsive interactions are with ρ(r) > 0 and 0. Non-covalent interactions can be visualized as isosurfaces, where small red and blue disc-shaped regions represent strong repulsive and attractive interactions, respectively, and broad green and usually irregular surfaces refer to weak interactions. The analysis was performed via NCIPLOT (Contreras-García et al., 2011) on the density obtained from the DFT calculations using DFT/B3LYP/6-311G**(2d,2p) with GAUSSIAN09 (Frisch et al., 2009) and the results are shown in Figs. 4(c) and 4(d). The NCI analysis confirmed the existence of geometrically predicted inter- and intramolecular interactions responsible for the formation of the stable dimer in the The broad green surface represents the π–π interactions between the π-conjugated heterocyclic rings of TAAP. From the overall shape of the surface, it is evident that dispersion is a major source of attractive forces between the two molecules forming a dimer. This is typical for non-directional π–π interactions and C—H⋯π interactions.
3.3. Anisotropy of optical properties
The optical properties of biaxial TAAP single crystals were characterized by means of polarized light microscopy. The polarized white-light beam travels perpendicular to the crystallographic (001) face of the crystal. The directions of the plane-polarized light against the crystallographic axes of TAAP are marked in Fig. 5(a). Single crystals of TAAP illuminated with linearly polarized light exhibit different colours depending on the polarization orientation of the incident light, which is known as phenomenon (Figs. 5b and 5c). Colours ranging from red to yellow are observed as complementary for the absorption of blue–green (at 485–505 nm) and indigo (at 415–445 nm) light, respectively. The approximate orientation of the absorption transition (TDM) against the and crystallographic axes is along the oscillation direction of the polarized light. The absorption transition dipole moments are located in the orthogonally oriented planes defined by Nicols (compare with Fig. 5).
We have also observed single-crystal fluorescence anisotropy when the crystal was illuminated by UV–LED diodes with monochromatic nonpolarized light at 410 nm and the emitted fluorescence was examined through a linear polarizing filter (Figs. 5d and 5e). Again the light beam travelled perpendicular to the crystallographic (001) face of the crystal. The excitation light with the electric field vector oriented parallel to the transition was absorbed. We observed the maximum intensity of emission when the analyzer was oriented along the emission transition (Fig. 5e) that is parallel to the direction of the absorption transition (compare with Fig. 5b).
Relative orientations of the a, b and c crystallographic directions with respect to the were determined using the CrysAlisPro software on a SuperNova diffractometer (Figs. 5a and 6a, and Table S1.1). The fluorescence experiment for the single crystals revealed that the emission transition similarly to that of the absorption transition is oriented in the plane defined by [110] and vector c* perpendicular to the (001) plane.
TAAP in the solid state exhibits a fluorescence emission influenced by restriction of the phenyl-group rotations, formation of intramolecular hydrogen bonds and π-overlapping molecular species (compare Figs. 5e and 6b). The fluorescence data for solid TAAP exhibit one band with high intensity at 584 nm. The fluorescence spectrum in the solid state was recorded by excitation at a wavelength of 350 nm, derived from the two-dimensional excitation–emission spectra of TAAP (Fig. S3.1).
3.4. Analysis of optical spectra in solution
The absorption spectra of TAAP were recordered in toluene, CHCl3, THF, CH3CN and DMSO solutions, as shown in Fig. 7(a). In toluene solution, the absorption maxima appear at 346, 358, 400, 447, 472 and 503 nm with molar absorption coefficients (∊) of 17480, 18130, 6200, 7060, 8200 and 5010 M−1cm−1, respectively. The maxima at 346, 358, 400, 447, 472 and 503 nm are attributed to π–π* transitions. TAAP exhibits fluorescence emission enhancement in toluene, CHCl3, THF, CH3CN and DMSO at 527 and 556 nm (Fig. 7b). The fluorescence of TAAP in acetonitrile (Φi = 0.021) was determined using fluorescein as a standard (see Figs. S3.2 and S3.3, and §S4 in the supporting information).
To investigate the possibility of aggregation of TAAP in toluene, CHCl3, THF, CH3CN and DMSO solutions, the effect of solute concentration on the spectral profiles of the absorption and fluorescence spectra was systematically examined by gradually diluting the respective stock solutions. The absorption spectra for the highest and lowest concentrations were normalized at their respective maxima, unveiling the same spectral characteristic for the bands and no unusual solution behaviour of TAAP in the studied solvents (Figs. S5.1–S5.4). Temperature-dependent optical absorption spectra of TAAP in toluene were recorded at temperatures of 296, 308, 318, 328, 338, 348, 358 and 368 K (Fig. S6.1). It is rather apparent that with temperature increase the aggregate size should decrease. Consequently, at elevated temperatures the relevant absorption and emission spectra should lose their characteristic features. The emission spectra obtained for different concentrations of TAAP in toluene (Figs. S5.5 and S5.6) only reveal the effect of reabsorption, which is especially manifested in the onset region of the fluorescence spectrum for more concentrated samples (see Fig. 7b). All the fluorescence spectra, corrected for reabsorption and normalized, exhibit a similar pattern (see §S7 in the supporting information). The shift and disappearance of the band may indicate the reabsorption phenomenon (El-Daly & Hirayama, 1997; Ghosh et al., 2013) but do not reflect the change of equilibrium between monomer and dimer in solution. Such an equilibrium should be manifested by the changes in the relative intensities of the monomer and dimer features located at wavelengths of 525 nm and 561 nm, respectively. The same effect can be observed in acetonitrile, chloroform and CDCl3 or benzene-d6 (see Figs. S5.5 and S5.6). The influence of the reabsorption on the emission band shapes and shifts is shown in §S7. The corrected fluorescence intensities were calculated for the secondary for TAAP at 100, 50, 10 and 5 µM in acetonitrile.
3.5. Theoretical calculations of optical properties of TAAP monomers and dimers
DFT calculations for the optical properties of the TAAP monomer and dimer were performed using Gaussian09 with B3LYP functional and 6-31G(d,p) basis set (Frisch et al., 2009) with the aim of revealing the spectral differences between the TAAP monomer and dimer, and to evaluate the possible aggregation type. The calculations were performed in the gas-phase (see §S8 in the supporting information). To simulate spectra in solution, the geometries of both monomer and dimer were fully relaxed, whereas to simulate the solid the geometry of the dimer was extracted from the The gas-phase geometry differs from the solid-state geometry only by small changes in the torsion angles of the two phenyl groups: Ph3 at C30 and Ph5 at N5. It has also been verified that the solvent effect (from the PCM model) has a marginal effect on the position of the absorption bands. Therefore, the crystal geometry was used in our calculations.
In order to obtain the optical absorption spectra of TAAP down to 250 nm, the lowest 50 singlet states for the monomer and 100 singlet states for the dimer were included. The optical spectra in the gas phase have been computed by smearing the transitions with a Gaussian broadening of 0.15 eV. To obtain the S1 state of the dimer was performed imposing Ci symmetry (see Fig. S8.1).
of the dimer, TD-DFT geometry optimization on theAt the B3LYP level, the calculated spectral bands for the monomer and dimer in the gas phase are blue shifted by ∼0.3 eV with respect to the experimental UV–Vis data of TAAP in toluene and other solvents (Fig. 8a). This is at odds with the generally good performance of TD-DFT/B3LYP in predicting the absorption spectra of organic molecules (typical blue shift 0.05–0.1 eV). However, it is known that TD-DFT cannot describe properly excitations in certain classes of molecules, characterized either by a multiconfigurational wavefunction or by a large differential correlation between the ground and excited states (Fabian, 2010). The existence of several resonance structures in TAAP (Fig. 2) in zwitterionic forms might be an indication of a multiconfigurational character.
In view of these results, a pragmatic approach was adopted and a shift of −0.33 eV to the excitation energies obtained by TD-DFT/B3LYP was applied. This was done in order to align the first . From our calculations, we assigned the experimental peak at 472 nm as the first vibronic level of the S0→S1 transition (the difference between the 0–0 and 0–1 vibronic levels is ∼1300 cm−1, which corresponds to the peak at 1295 cm−1 in the IR spectrum). The peak at 448 nm is of electronic origin (S0→S2). Note that the calculations reproduce the weak shoulder at 400 nm (S0→S3) and the rise of the strong at 370 nm and shorter wavelengths.
of the monomer to the lowest absorption peak of TAAP in solution. The resulting calculated absorption of the monomer is shown in Fig. 8In Table 1, the character of the transitions and the orientation of the transition dipole moments (TDM) of the TAAP monomer are reported. In Fig. S8.2, TD-DFT transition densities are shown. To rationalize the electronic transitions, the atoms of TAAP were grouped into three fragments: triazaacephenanthrylene (tap), the phenyl ring attached to atom N5 (Ph5) and the phenyl ring attached to atom C30 (Ph3). Thus, the S0→S1 transition is from the imine NH group to tap; S0→S2 is from Ph5 to tap, S0→S3 is from Ph3 to tap and S0→S4 is from (Ph3+Ph5) to tap. All these transitions are of π–π* character and their TDM are parallel to the plane of the molecule. Interestingly, the S0→S8 transition is the first one to have a component perpendicular to the plane of the molecule. This weak transition is of π–π* character, and the transition is from Ph5 to Ph3.
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To discuss aggregation, the (b). The of the dimer is red-shifted with respect to the monomer, thus suggesting J-type aggregation. If the interaction between the monomers in the dimer could be approximated by dipole–dipole interaction (Jablonsky diagram, Fig. 1), each (MO) of the monomer would give rise to a pair of MOs in the dimer, one even (gerade) and one odd (ungerade), with respect to inversion. As a consequence, each excitation in the dimer would be split into a pair of dark and bright singlets (Davydov splitting) (Basko et al., 2003; Davydov, 1971). The bright singlet should have a transition twice as large as the corresponding transition in the monomer. In the present case, the π–π interaction between the monomers perturbs this simple picture.
of the TAAP dimer was calculated and compared to that of the monomer, both in the gas phase. After applying a shift of −0.33 eV, the results are shown in Fig. 8The low lying excitations (S1 and S2) come in pairs (dark and bright) and mirror closely in character the first two excited states of the monomer. The TDM of the S0→S3 in the dimer at 466 nm (2.66 eV) has a non-negligible component perpendicular to the plane of the tap. This transition is similar in character to the S0→S8 transition in the monomer at 3.52 eV (352 nm) and shows the largest from the monomer to the dimer.
3.6. Orientation of transition dipole moments
With the 6-31G(d,p) basis set employed in the TD-DFT calculations, the permanent dipole of the monomer is 3.82 D and the angle α between the dipole vector and the line joining the gravity centres of two TAAP molecules α equals 74.7°. The calculated angle θ between the transition and the line joining the centres of gravity, and the calculated angle β between the permanent and the transition are both given in Table 2. According to Kasha's theory (Gierschner & Park, 2013; McRae & Kasha, 1958; Kasha et al., 1965), the nature of the excited states splitting depends on the θ angle. For the aggregate with θ < 54.7°, the electronic transition from the ground to the would lead to the of the absorption band relative to the monomer, while for aggregates with θ > 54.7°, the shift is hypsochromic.
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In the low-lying excited states of the dimer, the angle between the TDM and the line connecting the geometrical centres of the monomers is 54.22°, which is very close to the critical angle of 54.7°. The value of θ angle suggests that the aggregate and the isolated monomer should have absorption bands at almost the same wavelength. In this case, the determination of the aggregation type on the basis of absorption spectra is inconclusive.
To explain why H-type aggregation causes bathochromical shift, the ca 4 D) each lead to the unusual spectroscopic JH-aggregate behaviour of the TAAP dimer.
energy levels of the dimer were analysed (see Fig. S8.1). The low-lying excitations are dominated by one single transition, with only a minor admixture from other energy levels. We have found that the splitting of dimer HOMO and HOMO–1 is large (0.08 eV), while that of LUMO and LUMO+1 is negligible. The HOMO and HOMO–1 levels of the dimer are raised in energy with respect to monomer HOMO. As a result, the symmetry-permitted transitions of the dimer are lower in energy with respect to the HOMO–LUMO transition of the monomer. Since the lowest singlet excitation is not allowed by symmetry, this suggests H-type aggregation, even though the overall is bathochromically shifted, as for the J-type. This could suggest that electrostatic interactions between monomers with permanent dipole moments (3.7. 1H NMR data for TAAP in solution
To substantiate the formation of either monomer or dimer in solution, NMR experiments were performed. The 1H NMR spectra of TAAP were measured in CDCl3, CD2Cl2, benzene-d6, toluene-d8, THF-d8 and dioxane-d8, and display only one set of signals (Fig. 9a). The 1H NMR spectra of TAAP, detected at low and high concentrations in CDCl3 and benzene-d6, do not show any changes of chemical shifts and broadening of the signals (§S9, Figs. S9.1–S9.4). Temperature-dependent spectra in tetrachloroethane measured in the range 296–345 K indicated no equilibrium between the monomer and dimer. In addition, the 1H diffusion-ordered spectroscopy (DOSY) NMR (Avram & Frish, 2005) spectrum shows only one set of signals at logD = −8.38, indicating the presence of only one form in CDCl3 (Fig. 9b). The attempt to identify this form using nuclear Overhauser effect (NOE) spectroscopy was undertaken. Full assignment of the H and C atoms of TAAP was performed by two-dimensional COSY, HSQC and HMBC measurements in THF-d8 (see §S10). The through-space correlations were determined by ROESY spectra only with the monomer measured in THF-d8. No intermolecular cross coupling between H atoms of the two monomers in the dimer have been found. We obtained the same results performing the two-dimensional NMR measurements in dioxane-d8.
The only evidence of two different species was found in the DOSY spectra of TAAP at 345 K in tetrachloroethane-d2 [logD = −9.32 and logD = −9.28, Fig. 9(c)]. The set of signals at logD = −9.32 contained features that are characteristic of spin systems observed in one-dimensional 1H NMR spectra, detected in different solvents (Fig. 9a), whereas the set at logD = −9.28 indicated the downfield shift of the H-10 signal from 10.32 ppm to the aromatic region. The small difference between the logD values may indicate a similar hydrodynamic radius for both species.
In order to determine the equilibrium between the monomer and dimer species, a measurement of the permanent **(2d,2p), Fig. S2.1] and indicates that the equilibrium is shifted almost exclusively to the monomer form.
of TAAP in saturated 1,4-dioxane solution was performed (see §S11 in the supporting information). The experimentally obtained value of 4.24 D at 300 K is in good agreement with the calculated ground-state [3.82 D by TD-DFT/6-31G(d,p) basis set and 4.94 D by DFT/B3LYP/6-311GSingle crystals of TAAP were obtained from a cooled tetrachloroethane-d2 solution in an NMR cuvette. X-ray diffraction experiments confirmed that the was in fact the same P form found for TAAP crystallized from all other solvents.
3.8. Spectroscopic properties of single crystals of TAAP
The photophysical properties of TAAP single crystals were investigated using UV–vis absorption and and 7). The formation of the dimer by molecules with permanent dipole moments is manifested strongly in the 55 nm red-shift of the UV–vis absorption bands, attributed to the S0→S1 transition with respect to those recorded for TAAP in solution.
spectroscopy. UV–vis spectra were measured in order to determine the aggregation type on the basis of the band spectral shifts. The absorption spectra of TAAP crystals revealed three bathochromically shifted band maxima at 456, 482 and 509 nm (Figs. 6In order to explain the anisotropy of the optical properties, we analyzed the TDM of the monomer and the dimer, reporting them in the reference frame of the crystal, with the (001) plane parallel to plane of the paper. The calculated TDMs of the low-lying excitations are shown in Fig. 10. In the monomer, all but the S0→S8 transition have a TDM component approximately parallel to the [10] direction. The intermolecular interactions cause red-shifted S0→S8 transitions, which becomes the S0→S3 transition in the dimer and has a large component along the [110] direction. The closest crystallographic directions (with low Miller indices) are reported in the last column of Tables 1 and 2.
To simulate the effect of polarized light, the . The perceived RGB colour of TAAP was determined by subtracting the from the spectrum of visible light (Broadbent, 2004) as a function of the polarization direction. When the polarizer is rotated at −45° (roughly in the [10] direction), TAAP absorbs both in the blue and green regions, hence the perceived colour is orange–red. Conversely, when the polarized light is rotated at +45° (roughly in the [110] direction), TAAP absorbs mostly in the indigo–blue region, thus the perceived colour is yellow.
of the dimer was computed, by setting the dipole component perpendicular to the polarization plane of the light to zero. The result is shown in Fig. 11Finally, the spectra of solid TAAP were simulated from the absorption and emission spectra of the dimer, taking into account the effect of the solid environment, allowing for the influence of the electric field generated by the neighbouring molecules within the Clausius–Mossotti (CM) approximation (see §S12 in the supporting information):
where ε(ω) is the complex dielectric function, N is the of dimers in the crystal and α(ω) is the molecular polarizability calculated from TD-DFT. The CM approximation is valid in principle only for an isotropic and uniform medium and is equivalent to space-averaging the local field effects. Then, we calculated the absorbance η from the extinction coefficient κ:
where n is the refraction index, ω is the frequency and c is the speed of light.
The result is shown in Fig. 12 and compared to the experimental spectra. The calculated absorption is in fair agreement with the experimental spectrum. It is clear that in the crystal phase the small splitting of the LUMO in the dimer may lead to the additional electronic coupling in the Frenkel states and the resultant broadening of states.
The emission peak was calculated as the vertical energy difference between the S1 and S0 states, both in the geometry of S1 relaxed by TD-DFT/B3LYP. The calculated emission has been rescaled to match the normalized experimental spectrum and is slightly red-shifted (645 nm, 1.92 eV) with respect to the experiments. The main differences between the S0 and S1 geometry are the dihedral angles of the two phenyl groups. The Ph5 torsion changes from 44.3 to 22.7° in the (experimental value 41.37°), while the Ph3 torsion changes from 55.1 to 43.7° in the (experimental value 58.28°). As a matter of fact, the Frenkel can be delocalized on several dimers and the crystalline packing will reduce the change in the torsion angles. Consequently, the emission energy is expected to increase, which is in better agreement with the experiment.
4. Conclusions
We have demonstrated that optically biaxial single crystals of 5,6,10b-triazaacephenanthrylene (TAAP) exhibit absorption and fluorescence anisotropy upon JH-aggregation with a face-to-face alignment of the monomers in centrosymmetric dimers. Sole analysis of the optical spectra of TAAP in solution and the solid state does not allow us to define the aggregation type unambiguously. DFT calculations for the TAAP dimer in the gas phase indicate that the lowest singlet excitation is forbidden by symmetry, suggesting H-type aggregation, even though the overall absorpton spectrum is bathochromically shifted, as for the J-type. The calculated value of θ was found to be 54.22°, which is very close to the critical angle of 54.7°, showing an unusual example of the JH-aggregation type with nearly the same absorption bands for both monomer and dimer. The experimental determination of the permament of the TAAP molecule in 1,4-dioxane solution indicates unambiguously that the monomer form is predominantly present in solution.
The π–π interaction between monomer units in the dimer, with an interplanar distance of 3.413 Å between the chromophores and an interaction energy of −11.41 kcal mol−1, are responsible for both the crystal packing arrangement and relative orientations of the absorption and emission transition dipole moments. The absorption and emission spectra calculated for a crystal of TAAP in the Clausius–Mossotti approximation sustain the experimentally determined orientation of the absorption and emission transition dipole moments in the TAAP single crystal.
The π–π interactions are usually one of the major reasons for reduced or even absent fluorescence of materials in aggregates or the solid state. Our findings will aid the understanding of the nature of absorption and fluorescence emission anisotropy, observed for the crystalline JH-aggregates with potential applications as ambipolar transporting organic materials (Park et al., 2013).
Supporting information
https://doi.org/10.1107/S2052252518001987/yc5013sup1.cif
contains datablocks 3358_2a_RT, 3157_2a_LT. DOI:Structure factors: contains datablock shelx. DOI: https://doi.org/10.1107/S2052252518001987/yc50133358_2a_RTsup2.hkl
Structure factors: contains datablock shelx. DOI: https://doi.org/10.1107/S2052252518001987/yc50133157_2a_LTsup3.hkl
Supporting information. DOI: https://doi.org/10.1107/S2052252518001987/yc5013sup4.pdf
For both structures, data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); cell
CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); program(s) used to solve structure: SIR92 (A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori, M. Camalli, J. Appl. Cryst., 27 (1994) 435); program(s) used to refine structure: SHELXL97 (M. Sheldrick, Acta Cryst. A64 (2008) 112); molecular graphics: ORTEP-3 for Windows (L. Farrugia, J. Appl. Cryst., 32 (1999) 837) and Mercury 2.3 (C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M. Towler, J. van de Streek, J. Appl. Cryst., 39 (2006) 453); software used to prepare material for publication: SHELXL97 (M. Sheldrick, Acta Cryst. A64 (2008) 112).C26H15N5O | F(000) = 428 |
Mr = 413.43 | Dx = 1.418 Mg m−3 |
Triclinic, P1 | Melting point: 556 K |
a = 9.3241 (8) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 9.5329 (8) Å | Cell parameters from 2505 reflections |
c = 12.0593 (14) Å | θ = 4.0–76.2° |
α = 83.218 (8)° | µ = 0.73 mm−1 |
β = 66.653 (7)° | T = 293 K |
γ = 80.098 (7)° | Plate, orange |
V = 967.99 (16) Å3 | 0.30 × 0.18 × 0.03 mm |
Z = 2 |
SuperNova, Dual, Cu at zero, Atlas diffractometer | 3681 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 1933 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.126 |
Detector resolution: 10.3756 pixels mm-1 | θmax = 70.0°, θmin = 4.0° |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −11→11 |
Tmin = 0.812, Tmax = 0.979 | k = −11→11 |
14555 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.196 | w = 1/[σ2(Fo2) + (0.0624P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3681 reflections | Δρmax = 0.22 e Å−3 |
293 parameters | Δρmin = −0.24 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0016 (6) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0130 (4) | 0.2795 (4) | 0.4428 (3) | 0.0467 (8) | |
C2 | 0.8709 (4) | 0.3691 (4) | 0.5195 (3) | 0.0448 (8) | |
C3 | 0.7868 (4) | 0.3420 (4) | 0.6411 (3) | 0.0443 (8) | |
C3A | 0.8459 (3) | 0.2170 (4) | 0.6935 (3) | 0.0448 (8) | |
C4 | 0.7891 (4) | 0.1412 (4) | 0.8126 (3) | 0.0491 (9) | |
O4 | 0.6717 (3) | 0.1699 (3) | 0.90211 (19) | 0.0603 (7) | |
N5 | 0.9021 (3) | 0.0175 (3) | 0.8070 (2) | 0.0485 (7) | |
C5A | 1.0257 (3) | 0.0180 (4) | 0.6941 (3) | 0.0455 (8) | |
N6 | 1.1527 (3) | −0.0731 (3) | 0.6552 (2) | 0.0477 (7) | |
C6A | 1.2514 (3) | −0.0425 (4) | 0.5351 (3) | 0.0450 (8) | |
C7 | 1.3944 (4) | −0.1355 (4) | 0.4898 (3) | 0.0519 (9) | |
H7 | 1.4163 | −0.2118 | 0.5390 | 0.062* | |
C8 | 1.5017 (4) | −0.1149 (4) | 0.3739 (3) | 0.0581 (10) | |
H8 | 1.5953 | −0.1771 | 0.3451 | 0.070* | |
C9 | 1.4709 (4) | −0.0026 (4) | 0.3005 (3) | 0.0590 (10) | |
H9 | 1.5442 | 0.0105 | 0.2222 | 0.071* | |
C10 | 1.3315 (4) | 0.0917 (4) | 0.3414 (3) | 0.0573 (10) | |
H10 | 1.3127 | 0.1682 | 0.2911 | 0.069* | |
C10A | 1.2201 (4) | 0.0710 (4) | 0.4583 (3) | 0.0455 (8) | |
N10B | 1.0745 (3) | 0.1651 (3) | 0.5074 (2) | 0.0436 (7) | |
C3A' | 0.9851 (3) | 0.1384 (4) | 0.6249 (3) | 0.0403 (7) | |
N11 | 1.0833 (4) | 0.2935 (4) | 0.3288 (3) | 0.0645 (9) | |
H11 | 1.027 (4) | 0.361 (3) | 0.299 (3) | 0.077* | |
C21 | 0.8262 (4) | 0.4951 (4) | 0.4570 (3) | 0.0516 (9) | |
N22 | 0.7975 (4) | 0.5941 (4) | 0.4013 (3) | 0.0714 (10) | |
C31 | 0.6486 (4) | 0.4427 (4) | 0.7126 (3) | 0.0462 (8) | |
C32 | 0.6516 (4) | 0.4988 (4) | 0.8125 (3) | 0.0568 (10) | |
H32 | 0.7340 | 0.4660 | 0.8380 | 0.068* | |
C33 | 0.5329 (5) | 0.6035 (4) | 0.8748 (3) | 0.0655 (11) | |
H33 | 0.5379 | 0.6439 | 0.9395 | 0.079* | |
C34 | 0.4093 (5) | 0.6465 (5) | 0.8403 (4) | 0.0721 (13) | |
H34 | 0.3290 | 0.7159 | 0.8826 | 0.087* | |
C35 | 0.4010 (4) | 0.5891 (5) | 0.7437 (4) | 0.0677 (12) | |
H35 | 0.3149 | 0.6187 | 0.7220 | 0.081* | |
C36 | 0.5218 (4) | 0.4866 (4) | 0.6788 (3) | 0.0584 (10) | |
H36 | 0.5171 | 0.4480 | 0.6131 | 0.070* | |
C51 | 0.8854 (4) | −0.0909 (4) | 0.9024 (3) | 0.0490 (9) | |
C52 | 1.0124 (4) | −0.1476 (5) | 0.9325 (3) | 0.0668 (12) | |
H52 | 1.1099 | −0.1159 | 0.8911 | 0.080* | |
C53 | 0.9931 (5) | −0.2517 (5) | 1.0248 (4) | 0.0790 (14) | |
H53 | 1.0782 | −0.2900 | 1.0458 | 0.095* | |
C54 | 0.8490 (5) | −0.3002 (5) | 1.0868 (3) | 0.0742 (13) | |
H54 | 0.8373 | −0.3714 | 1.1482 | 0.089* | |
C55 | 0.7234 (4) | −0.2418 (4) | 1.0562 (3) | 0.0648 (11) | |
H55 | 0.6257 | −0.2726 | 1.0983 | 0.078* | |
C56 | 0.7407 (4) | −0.1376 (4) | 0.9635 (3) | 0.0551 (10) | |
H56 | 0.6555 | −0.0994 | 0.9425 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0431 (16) | 0.045 (2) | 0.0458 (17) | −0.0027 (15) | −0.0136 (13) | 0.0033 (15) |
C2 | 0.0441 (16) | 0.039 (2) | 0.0472 (17) | 0.0007 (14) | −0.0181 (14) | 0.0062 (15) |
C3 | 0.0409 (15) | 0.041 (2) | 0.0459 (17) | −0.0015 (14) | −0.0151 (13) | 0.0034 (14) |
C3A | 0.0395 (15) | 0.042 (2) | 0.0427 (16) | 0.0023 (14) | −0.0103 (13) | 0.0067 (14) |
C4 | 0.0414 (16) | 0.048 (2) | 0.0495 (18) | 0.0005 (15) | −0.0129 (14) | 0.0049 (16) |
O4 | 0.0473 (12) | 0.0630 (19) | 0.0481 (13) | 0.0070 (12) | −0.0023 (10) | 0.0037 (12) |
N5 | 0.0387 (13) | 0.048 (2) | 0.0444 (14) | 0.0017 (12) | −0.0073 (11) | 0.0110 (13) |
C5A | 0.0381 (15) | 0.045 (2) | 0.0435 (16) | −0.0014 (14) | −0.0088 (13) | 0.0040 (15) |
N6 | 0.0388 (13) | 0.0433 (19) | 0.0488 (15) | 0.0003 (12) | −0.0089 (11) | 0.0073 (13) |
C6A | 0.0379 (15) | 0.041 (2) | 0.0441 (16) | −0.0015 (14) | −0.0064 (13) | 0.0024 (14) |
C7 | 0.0428 (16) | 0.045 (2) | 0.0571 (19) | 0.0008 (15) | −0.0107 (14) | −0.0017 (17) |
C8 | 0.0456 (17) | 0.054 (3) | 0.058 (2) | −0.0049 (17) | −0.0039 (15) | −0.0017 (18) |
C9 | 0.0497 (18) | 0.055 (3) | 0.054 (2) | −0.0028 (17) | −0.0021 (15) | −0.0018 (18) |
C10 | 0.0505 (18) | 0.055 (3) | 0.0496 (19) | −0.0051 (17) | −0.0047 (15) | 0.0042 (17) |
C10A | 0.0374 (15) | 0.042 (2) | 0.0471 (17) | −0.0034 (14) | −0.0068 (13) | 0.0002 (15) |
N10B | 0.0391 (12) | 0.0394 (18) | 0.0423 (14) | −0.0018 (11) | −0.0090 (10) | 0.0069 (12) |
C3A' | 0.0383 (14) | 0.036 (2) | 0.0398 (15) | −0.0012 (13) | −0.0115 (12) | 0.0056 (14) |
N11 | 0.0569 (18) | 0.075 (3) | 0.0454 (16) | 0.0016 (16) | −0.0106 (13) | 0.0099 (16) |
C21 | 0.0496 (18) | 0.052 (3) | 0.0504 (18) | −0.0035 (16) | −0.0205 (15) | 0.0067 (17) |
N22 | 0.080 (2) | 0.063 (3) | 0.066 (2) | −0.0008 (19) | −0.0327 (18) | 0.0173 (18) |
C31 | 0.0416 (16) | 0.038 (2) | 0.0457 (17) | 0.0020 (14) | −0.0087 (13) | 0.0063 (15) |
C32 | 0.0518 (19) | 0.051 (3) | 0.054 (2) | 0.0002 (17) | −0.0122 (15) | 0.0074 (17) |
C33 | 0.065 (2) | 0.055 (3) | 0.055 (2) | −0.0007 (19) | −0.0039 (17) | 0.0015 (18) |
C34 | 0.061 (2) | 0.058 (3) | 0.062 (2) | 0.004 (2) | 0.0065 (18) | 0.004 (2) |
C35 | 0.0430 (17) | 0.062 (3) | 0.076 (3) | 0.0050 (17) | −0.0117 (17) | 0.023 (2) |
C36 | 0.0496 (18) | 0.058 (3) | 0.059 (2) | 0.0020 (17) | −0.0188 (16) | 0.0093 (18) |
C51 | 0.0434 (16) | 0.053 (3) | 0.0401 (16) | 0.0000 (15) | −0.0104 (13) | 0.0078 (15) |
C52 | 0.0449 (17) | 0.077 (3) | 0.061 (2) | 0.0009 (19) | −0.0132 (16) | 0.020 (2) |
C53 | 0.055 (2) | 0.094 (4) | 0.077 (3) | −0.002 (2) | −0.028 (2) | 0.032 (3) |
C54 | 0.068 (2) | 0.077 (3) | 0.061 (2) | −0.006 (2) | −0.0179 (19) | 0.030 (2) |
C55 | 0.0527 (19) | 0.073 (3) | 0.055 (2) | −0.0111 (19) | −0.0120 (16) | 0.020 (2) |
C56 | 0.0471 (17) | 0.059 (3) | 0.0522 (19) | −0.0028 (16) | −0.0175 (15) | 0.0116 (17) |
C1—N11 | 1.269 (4) | C10A—N10B | 1.438 (4) |
C1—N10B | 1.437 (4) | N10B—C3A' | 1.349 (4) |
C1—C2 | 1.472 (4) | N11—H11 | 0.892 (10) |
C2—C3 | 1.379 (4) | C21—N22 | 1.149 (4) |
C2—C21 | 1.431 (5) | C31—C36 | 1.383 (4) |
C3—C3A | 1.412 (4) | C31—C32 | 1.387 (5) |
C3—C31 | 1.488 (4) | C32—C33 | 1.386 (5) |
C3A—C3A' | 1.375 (4) | C32—H32 | 0.9300 |
C3A—C4 | 1.467 (4) | C33—C34 | 1.359 (5) |
C4—O4 | 1.212 (3) | C33—H33 | 0.9300 |
C4—N5 | 1.428 (4) | C34—C35 | 1.378 (6) |
N5—C5A | 1.392 (3) | C34—H34 | 0.9300 |
N5—C51 | 1.431 (4) | C35—C36 | 1.392 (5) |
C5A—N6 | 1.295 (4) | C35—H35 | 0.9300 |
C5A—C3A' | 1.425 (4) | C36—H36 | 0.9300 |
N6—C6A | 1.402 (4) | C51—C56 | 1.379 (4) |
C6A—C10A | 1.408 (5) | C51—C52 | 1.379 (5) |
C6A—C7 | 1.412 (4) | C52—C53 | 1.378 (5) |
C7—C8 | 1.374 (4) | C52—H52 | 0.9300 |
C7—H7 | 0.9300 | C53—C54 | 1.383 (5) |
C8—C9 | 1.372 (5) | C53—H53 | 0.9300 |
C8—H8 | 0.9300 | C54—C55 | 1.374 (5) |
C9—C10 | 1.391 (5) | C54—H54 | 0.9300 |
C9—H9 | 0.9300 | C55—C56 | 1.383 (5) |
C10—C10A | 1.397 (4) | C55—H55 | 0.9300 |
C10—H10 | 0.9300 | C56—H56 | 0.9300 |
N11—C1—N10B | 118.6 (3) | C1—N10B—C10A | 126.6 (3) |
N11—C1—C2 | 126.9 (3) | N10B—C3A'—C3A | 126.8 (3) |
N10B—C1—C2 | 114.5 (3) | N10B—C3A'—C5A | 122.2 (3) |
C3—C2—C21 | 120.8 (3) | C3A—C3A'—C5A | 110.9 (3) |
C3—C2—C1 | 125.6 (3) | C1—N11—H11 | 110 (3) |
C21—C2—C1 | 113.6 (3) | N22—C21—C2 | 176.3 (4) |
C2—C3—C3A | 115.4 (3) | C36—C31—C32 | 119.4 (3) |
C2—C3—C31 | 121.7 (3) | C36—C31—C3 | 121.9 (3) |
C3A—C3—C31 | 122.8 (3) | C32—C31—C3 | 118.6 (3) |
C3A'—C3A—C3 | 119.4 (3) | C33—C32—C31 | 120.7 (4) |
C3A'—C3A—C4 | 106.4 (3) | C33—C32—H32 | 119.7 |
C3—C3A—C4 | 134.1 (3) | C31—C32—H32 | 119.7 |
O4—C4—N5 | 123.3 (3) | C34—C33—C32 | 119.3 (4) |
O4—C4—C3A | 130.2 (3) | C34—C33—H33 | 120.3 |
N5—C4—C3A | 106.4 (3) | C32—C33—H33 | 120.3 |
C5A—N5—C4 | 109.4 (3) | C33—C34—C35 | 121.1 (4) |
C5A—N5—C51 | 126.3 (3) | C33—C34—H34 | 119.4 |
C4—N5—C51 | 124.3 (3) | C35—C34—H34 | 119.4 |
N6—C5A—N5 | 128.1 (3) | C34—C35—C36 | 119.9 (4) |
N6—C5A—C3A' | 125.2 (3) | C34—C35—H35 | 120.0 |
N5—C5A—C3A' | 106.7 (3) | C36—C35—H35 | 120.0 |
C5A—N6—C6A | 113.3 (3) | C31—C36—C35 | 119.5 (4) |
N6—C6A—C10A | 125.9 (3) | C31—C36—H36 | 120.3 |
N6—C6A—C7 | 115.6 (3) | C35—C36—H36 | 120.3 |
C10A—C6A—C7 | 118.5 (3) | C56—C51—C52 | 120.7 (3) |
C8—C7—C6A | 120.8 (4) | C56—C51—N5 | 119.1 (3) |
C8—C7—H7 | 119.6 | C52—C51—N5 | 120.3 (3) |
C6A—C7—H7 | 119.6 | C53—C52—C51 | 119.1 (4) |
C9—C8—C7 | 120.1 (3) | C53—C52—H52 | 120.4 |
C9—C8—H8 | 119.9 | C51—C52—H52 | 120.4 |
C7—C8—H8 | 119.9 | C52—C53—C54 | 121.0 (4) |
C8—C9—C10 | 121.0 (3) | C52—C53—H53 | 119.5 |
C8—C9—H9 | 119.5 | C54—C53—H53 | 119.5 |
C10—C9—H9 | 119.5 | C55—C54—C53 | 119.1 (4) |
C9—C10—C10A | 119.6 (4) | C55—C54—H54 | 120.5 |
C9—C10—H10 | 120.2 | C53—C54—H54 | 120.5 |
C10A—C10—H10 | 120.2 | C54—C55—C56 | 120.7 (4) |
C10—C10A—C6A | 119.9 (3) | C54—C55—H55 | 119.6 |
C10—C10A—N10B | 122.8 (3) | C56—C55—H55 | 119.6 |
C6A—C10A—N10B | 117.3 (3) | C51—C56—C55 | 119.4 (3) |
C3A'—N10B—C1 | 117.5 (3) | C51—C56—H56 | 120.3 |
C3A'—N10B—C10A | 115.9 (3) | C55—C56—H56 | 120.3 |
N11—C1—C2—C3 | 172.2 (4) | C10—C10A—N10B—C3A' | −174.4 (3) |
N10B—C1—C2—C3 | −7.5 (5) | C6A—C10A—N10B—C3A' | 2.8 (5) |
N11—C1—C2—C21 | −9.7 (5) | C10—C10A—N10B—C1 | 8.3 (5) |
N10B—C1—C2—C21 | 170.6 (3) | C6A—C10A—N10B—C1 | −174.5 (3) |
C21—C2—C3—C3A | −177.7 (3) | C1—N10B—C3A'—C3A | −5.9 (5) |
C1—C2—C3—C3A | 0.2 (5) | C10A—N10B—C3A'—C3A | 176.5 (3) |
C21—C2—C3—C31 | −0.9 (5) | C1—N10B—C3A'—C5A | 172.8 (3) |
C1—C2—C3—C31 | 177.0 (3) | C10A—N10B—C3A'—C5A | −4.8 (5) |
C2—C3—C3A—C3A' | 4.7 (5) | C3—C3A—C3A'—N10B | −1.9 (6) |
C31—C3—C3A—C3A' | −172.1 (3) | C4—C3A—C3A'—N10B | 176.6 (3) |
C2—C3—C3A—C4 | −173.4 (4) | C3—C3A—C3A'—C5A | 179.3 (3) |
C31—C3—C3A—C4 | 9.9 (6) | C4—C3A—C3A'—C5A | −2.2 (4) |
C3A'—C3A—C4—O4 | −180.0 (4) | N6—C5A—C3A'—N10B | 3.4 (6) |
C3—C3A—C4—O4 | −1.8 (7) | N5—C5A—C3A'—N10B | −175.1 (3) |
C3A'—C3A—C4—N5 | −0.1 (4) | N6—C5A—C3A'—C3A | −177.7 (3) |
C3—C3A—C4—N5 | 178.1 (4) | N5—C5A—C3A'—C3A | 3.8 (4) |
O4—C4—N5—C5A | −177.7 (3) | C3—C2—C21—N22 | 176 (6) |
C3A—C4—N5—C5A | 2.5 (4) | C1—C2—C21—N22 | −2 (7) |
O4—C4—N5—C51 | 4.3 (6) | C2—C3—C31—C36 | 55.1 (5) |
C3A—C4—N5—C51 | −175.5 (3) | C3A—C3—C31—C36 | −128.3 (4) |
C4—N5—C5A—N6 | 177.7 (4) | C2—C3—C31—C32 | −121.7 (4) |
C51—N5—C5A—N6 | −4.3 (6) | C3A—C3—C31—C32 | 54.9 (5) |
C4—N5—C5A—C3A' | −3.8 (4) | C36—C31—C32—C33 | −3.3 (5) |
C51—N5—C5A—C3A' | 174.2 (3) | C3—C31—C32—C33 | 173.6 (3) |
N5—C5A—N6—C6A | 178.5 (3) | C31—C32—C33—C34 | 2.9 (6) |
C3A'—C5A—N6—C6A | 0.2 (5) | C32—C33—C34—C35 | −0.8 (6) |
C5A—N6—C6A—C10A | −2.2 (5) | C33—C34—C35—C36 | −0.9 (6) |
C5A—N6—C6A—C7 | 177.7 (3) | C32—C31—C36—C35 | 1.6 (5) |
N6—C6A—C7—C8 | −179.0 (3) | C3—C31—C36—C35 | −175.2 (3) |
C10A—C6A—C7—C8 | 0.9 (5) | C34—C35—C36—C31 | 0.5 (6) |
C6A—C7—C8—C9 | 0.1 (6) | C5A—N5—C51—C56 | −135.2 (4) |
C7—C8—C9—C10 | −0.1 (6) | C4—N5—C51—C56 | 42.5 (5) |
C8—C9—C10—C10A | −1.0 (6) | C5A—N5—C51—C52 | 44.8 (5) |
C9—C10—C10A—C6A | 1.9 (6) | C4—N5—C51—C52 | −137.5 (4) |
C9—C10—C10A—N10B | 179.1 (3) | C56—C51—C52—C53 | −0.1 (6) |
N6—C6A—C10A—C10 | 178.0 (3) | N5—C51—C52—C53 | 179.9 (4) |
C7—C6A—C10A—C10 | −1.9 (5) | C51—C52—C53—C54 | 0.3 (7) |
N6—C6A—C10A—N10B | 0.7 (5) | C52—C53—C54—C55 | −0.8 (7) |
C7—C6A—C10A—N10B | −179.2 (3) | C53—C54—C55—C56 | 1.1 (7) |
N11—C1—N10B—C3A' | −169.9 (3) | C52—C51—C56—C55 | 0.3 (6) |
C2—C1—N10B—C3A' | 9.8 (4) | N5—C51—C56—C55 | −179.6 (3) |
N11—C1—N10B—C10A | 7.4 (5) | C54—C55—C56—C51 | −0.9 (6) |
C2—C1—N10B—C10A | −172.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···N11 | 0.93 | 2.17 | 2.785 (5) | 123 |
C56—H56···O4 | 0.93 | 2.57 | 2.962 (5) | 106 |
C52—H52···N6 | 0.93 | 2.70 | 3.113 (4) | 108 |
C26H15N5O | F(000) = 428 |
Mr = 413.43 | Dx = 1.454 Mg m−3 |
Triclinic, P1 | Melting point: 556 K |
a = 9.2504 (5) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 9.4009 (8) Å | Cell parameters from 5007 reflections |
c = 11.9245 (6) Å | θ = 4.0–78.0° |
α = 84.147 (6)° | µ = 0.75 mm−1 |
β = 67.347 (5)° | T = 120 K |
γ = 81.113 (6)° | Plate, orange |
V = 944.47 (11) Å3 | 0.35 × 0.20 × 0.03 mm |
Z = 2 |
SuperNova, Dual, Cu at zero, Atlas diffractometer | 3772 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 2778 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.109 |
Detector resolution: 10.3756 pixels mm-1 | θmax = 73.0°, θmin = 4.0° |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −11→11 |
Tmin = 0.781, Tmax = 0.978 | k = −10→11 |
19315 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.068 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.217 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1488P)2] where P = (Fo2 + 2Fc2)/3 |
3772 reflections | (Δ/σ)max < 0.001 |
292 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0127 (2) | 0.2815 (3) | 0.4410 (2) | 0.0242 (5) | |
C2 | 0.8696 (2) | 0.3719 (3) | 0.5188 (2) | 0.0227 (5) | |
C3 | 0.7846 (3) | 0.3443 (3) | 0.6409 (2) | 0.0234 (5) | |
C3A | 0.8451 (2) | 0.2187 (3) | 0.6933 (2) | 0.0235 (5) | |
C4 | 0.7883 (2) | 0.1414 (3) | 0.8126 (2) | 0.0242 (5) | |
O4 | 0.67046 (18) | 0.1705 (2) | 0.90269 (14) | 0.0290 (4) | |
N5 | 0.9015 (2) | 0.0185 (2) | 0.80669 (17) | 0.0247 (5) | |
C5A | 1.0253 (2) | 0.0184 (3) | 0.6937 (2) | 0.0229 (5) | |
N6 | 1.1518 (2) | −0.0719 (2) | 0.65480 (17) | 0.0264 (5) | |
C6A | 1.2517 (3) | −0.0418 (3) | 0.5341 (2) | 0.0233 (5) | |
C7 | 1.3942 (3) | −0.1342 (3) | 0.4891 (2) | 0.0270 (5) | |
H7 | 1.4169 | −0.2115 | 0.5400 | 0.032* | |
C8 | 1.5016 (3) | −0.1144 (3) | 0.3722 (2) | 0.0287 (6) | |
H8 | 1.5966 | −0.1786 | 0.3424 | 0.034* | |
C9 | 1.4697 (3) | 0.0001 (3) | 0.2983 (2) | 0.0304 (6) | |
H9 | 1.5443 | 0.0140 | 0.2181 | 0.037* | |
C10 | 1.3308 (3) | 0.0947 (3) | 0.3394 (2) | 0.0283 (6) | |
H10 | 1.3116 | 0.1731 | 0.2880 | 0.034* | |
C10A | 1.2193 (2) | 0.0736 (3) | 0.4571 (2) | 0.0233 (5) | |
N10B | 1.0736 (2) | 0.1659 (2) | 0.50614 (16) | 0.0230 (5) | |
C3A' | 0.9839 (3) | 0.1408 (3) | 0.6241 (2) | 0.0226 (5) | |
N11 | 1.0818 (2) | 0.2969 (3) | 0.32659 (18) | 0.0302 (5) | |
H11 | 1.039 (4) | 0.373 (3) | 0.291 (3) | 0.036* | |
C21 | 0.8237 (2) | 0.4981 (3) | 0.4561 (2) | 0.0248 (5) | |
N22 | 0.7950 (2) | 0.5980 (3) | 0.40017 (19) | 0.0327 (5) | |
C31 | 0.6473 (3) | 0.4448 (3) | 0.7127 (2) | 0.0249 (5) | |
C32 | 0.6504 (3) | 0.5014 (3) | 0.8150 (2) | 0.0273 (5) | |
H32 | 0.7347 | 0.4687 | 0.8418 | 0.033* | |
C33 | 0.5305 (3) | 0.6054 (3) | 0.8778 (2) | 0.0314 (6) | |
H33 | 0.5344 | 0.6461 | 0.9462 | 0.038* | |
C34 | 0.4055 (3) | 0.6499 (3) | 0.8413 (2) | 0.0336 (6) | |
H34 | 0.3239 | 0.7216 | 0.8843 | 0.040* | |
C35 | 0.3984 (3) | 0.5905 (3) | 0.7422 (2) | 0.0336 (6) | |
H35 | 0.3104 | 0.6196 | 0.7191 | 0.040* | |
C36 | 0.5190 (3) | 0.4889 (3) | 0.6765 (2) | 0.0283 (6) | |
H36 | 0.5149 | 0.4494 | 0.6077 | 0.034* | |
C51 | 0.8844 (3) | −0.0908 (3) | 0.90228 (19) | 0.0249 (5) | |
C52 | 1.0130 (3) | −0.1478 (3) | 0.9323 (2) | 0.0324 (6) | |
H52 | 1.1130 | −0.1151 | 0.8895 | 0.039* | |
C53 | 0.9942 (3) | −0.2531 (3) | 1.0254 (2) | 0.0378 (7) | |
H53 | 1.0822 | −0.2929 | 1.0460 | 0.045* | |
C54 | 0.8478 (3) | −0.3011 (3) | 1.0892 (2) | 0.0341 (6) | |
H54 | 0.8358 | −0.3735 | 1.1527 | 0.041* | |
C55 | 0.7200 (3) | −0.2422 (3) | 1.0590 (2) | 0.0298 (6) | |
H55 | 0.6196 | −0.2737 | 1.1027 | 0.036* | |
C56 | 0.7374 (3) | −0.1377 (3) | 0.9658 (2) | 0.0265 (5) | |
H56 | 0.6494 | −0.0981 | 0.9452 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0163 (10) | 0.0287 (13) | 0.0235 (10) | 0.0001 (9) | −0.0052 (8) | 0.0036 (9) |
C2 | 0.0149 (10) | 0.0259 (13) | 0.0238 (11) | 0.0021 (9) | −0.0060 (8) | 0.0020 (9) |
C3 | 0.0167 (10) | 0.0273 (13) | 0.0237 (11) | 0.0000 (9) | −0.0069 (8) | 0.0027 (9) |
C3A | 0.0156 (10) | 0.0262 (13) | 0.0235 (10) | −0.0001 (9) | −0.0039 (8) | 0.0039 (9) |
C4 | 0.0151 (10) | 0.0280 (13) | 0.0253 (11) | 0.0006 (9) | −0.0053 (8) | 0.0023 (9) |
O4 | 0.0187 (8) | 0.0351 (11) | 0.0229 (8) | 0.0045 (7) | −0.0004 (6) | 0.0020 (7) |
N5 | 0.0155 (9) | 0.0289 (12) | 0.0221 (9) | 0.0015 (8) | −0.0018 (7) | 0.0044 (8) |
C5A | 0.0150 (10) | 0.0254 (13) | 0.0227 (11) | −0.0008 (9) | −0.0030 (8) | 0.0046 (9) |
N6 | 0.0166 (9) | 0.0316 (12) | 0.0245 (10) | 0.0007 (8) | −0.0033 (8) | 0.0033 (8) |
C6A | 0.0150 (10) | 0.0255 (13) | 0.0240 (11) | −0.0011 (9) | −0.0026 (8) | 0.0008 (9) |
C7 | 0.0175 (10) | 0.0277 (13) | 0.0307 (12) | 0.0015 (9) | −0.0057 (9) | 0.0014 (10) |
C8 | 0.0174 (10) | 0.0284 (14) | 0.0314 (12) | 0.0010 (9) | −0.0008 (9) | −0.0020 (10) |
C9 | 0.0194 (11) | 0.0361 (15) | 0.0264 (11) | −0.0017 (10) | 0.0007 (9) | −0.0005 (10) |
C10 | 0.0199 (11) | 0.0317 (15) | 0.0256 (11) | 0.0002 (10) | −0.0022 (9) | 0.0024 (10) |
C10A | 0.0149 (10) | 0.0254 (13) | 0.0247 (11) | −0.0003 (9) | −0.0037 (9) | 0.0021 (9) |
N10B | 0.0153 (8) | 0.0271 (11) | 0.0206 (9) | 0.0014 (8) | −0.0026 (7) | 0.0028 (8) |
C3A' | 0.0161 (10) | 0.0273 (13) | 0.0212 (10) | −0.0028 (9) | −0.0044 (8) | 0.0033 (9) |
N11 | 0.0241 (10) | 0.0362 (13) | 0.0233 (10) | 0.0031 (9) | −0.0056 (8) | 0.0056 (9) |
C21 | 0.0169 (10) | 0.0301 (14) | 0.0231 (10) | −0.0014 (9) | −0.0042 (8) | 0.0024 (9) |
N22 | 0.0291 (11) | 0.0349 (13) | 0.0302 (10) | 0.0023 (9) | −0.0106 (8) | 0.0041 (9) |
C31 | 0.0171 (10) | 0.0261 (13) | 0.0244 (10) | 0.0020 (9) | −0.0034 (8) | 0.0053 (9) |
C32 | 0.0196 (10) | 0.0300 (14) | 0.0259 (11) | 0.0013 (10) | −0.0047 (8) | 0.0041 (9) |
C33 | 0.0283 (12) | 0.0288 (14) | 0.0253 (11) | 0.0009 (10) | 0.0003 (9) | 0.0018 (10) |
C34 | 0.0216 (11) | 0.0300 (14) | 0.0309 (12) | 0.0071 (10) | 0.0047 (9) | 0.0056 (10) |
C35 | 0.0183 (11) | 0.0367 (16) | 0.0354 (13) | 0.0031 (10) | −0.0042 (9) | 0.0102 (11) |
C36 | 0.0187 (11) | 0.0316 (14) | 0.0290 (11) | 0.0012 (10) | −0.0067 (9) | 0.0076 (10) |
C51 | 0.0185 (10) | 0.0284 (14) | 0.0207 (10) | 0.0015 (9) | −0.0024 (8) | 0.0034 (9) |
C52 | 0.0162 (10) | 0.0406 (16) | 0.0329 (12) | −0.0017 (10) | −0.0042 (9) | 0.0082 (11) |
C53 | 0.0216 (11) | 0.0490 (18) | 0.0367 (14) | 0.0016 (11) | −0.0100 (10) | 0.0116 (12) |
C54 | 0.0271 (12) | 0.0397 (16) | 0.0272 (11) | −0.0020 (11) | −0.0056 (10) | 0.0134 (10) |
C55 | 0.0241 (11) | 0.0326 (15) | 0.0266 (11) | −0.0040 (10) | −0.0043 (9) | 0.0057 (10) |
C56 | 0.0174 (10) | 0.0310 (14) | 0.0261 (11) | 0.0020 (9) | −0.0058 (8) | 0.0035 (9) |
C1—N11 | 1.268 (3) | C10A—N10B | 1.431 (3) |
C1—N10B | 1.441 (3) | N10B—C3A' | 1.348 (3) |
C1—C2 | 1.483 (3) | N11—H11 | 0.90 (3) |
C2—C3 | 1.382 (3) | C21—N22 | 1.153 (3) |
C2—C21 | 1.434 (3) | C31—C32 | 1.391 (3) |
C3—C3A | 1.419 (3) | C31—C36 | 1.404 (3) |
C3—C31 | 1.481 (3) | C32—C33 | 1.387 (3) |
C3A—C3A' | 1.372 (3) | C32—H32 | 0.9500 |
C3A—C4 | 1.470 (3) | C33—C34 | 1.379 (4) |
C4—O4 | 1.218 (3) | C33—H33 | 0.9500 |
C4—N5 | 1.423 (3) | C34—C35 | 1.386 (4) |
N5—C5A | 1.392 (3) | C34—H34 | 0.9500 |
N5—C51 | 1.432 (3) | C35—C36 | 1.386 (3) |
C5A—N6 | 1.289 (3) | C35—H35 | 0.9500 |
C5A—C3A' | 1.440 (3) | C36—H36 | 0.9500 |
N6—C6A | 1.406 (3) | C51—C52 | 1.387 (3) |
C6A—C7 | 1.406 (3) | C51—C56 | 1.393 (3) |
C6A—C10A | 1.421 (3) | C52—C53 | 1.387 (4) |
C7—C8 | 1.379 (3) | C52—H52 | 0.9500 |
C7—H7 | 0.9500 | C53—C54 | 1.393 (4) |
C8—C9 | 1.390 (4) | C53—H53 | 0.9500 |
C8—H8 | 0.9500 | C54—C55 | 1.385 (3) |
C9—C10 | 1.389 (3) | C54—H54 | 0.9500 |
C9—H9 | 0.9500 | C55—C56 | 1.383 (3) |
C10—C10A | 1.401 (3) | C55—H55 | 0.9500 |
C10—H10 | 0.9500 | C56—H56 | 0.9500 |
N11—C1—N10B | 119.3 (2) | C10A—N10B—C1 | 126.22 (18) |
N11—C1—C2 | 126.3 (2) | N10B—C3A'—C3A | 127.7 (2) |
N10B—C1—C2 | 114.40 (18) | N10B—C3A'—C5A | 121.4 (2) |
C3—C2—C21 | 120.5 (2) | C3A—C3A'—C5A | 110.8 (2) |
C3—C2—C1 | 125.8 (2) | C1—N11—H11 | 115.0 (19) |
C21—C2—C1 | 113.73 (19) | N22—C21—C2 | 176.1 (2) |
C2—C3—C3A | 115.0 (2) | C32—C31—C36 | 119.7 (2) |
C2—C3—C31 | 121.9 (2) | C32—C31—C3 | 118.6 (2) |
C3A—C3—C31 | 122.9 (2) | C36—C31—C3 | 121.6 (2) |
C3A'—C3A—C3 | 119.4 (2) | C33—C32—C31 | 120.1 (2) |
C3A'—C3A—C4 | 106.6 (2) | C33—C32—H32 | 120.0 |
C3—C3A—C4 | 134.0 (2) | C31—C32—H32 | 120.0 |
O4—C4—N5 | 123.7 (2) | C34—C33—C32 | 120.1 (2) |
O4—C4—C3A | 129.9 (2) | C34—C33—H33 | 120.0 |
N5—C4—C3A | 106.42 (18) | C32—C33—H33 | 120.0 |
C5A—N5—C4 | 109.92 (19) | C33—C34—C35 | 120.3 (2) |
C5A—N5—C51 | 126.00 (19) | C33—C34—H34 | 119.8 |
C4—N5—C51 | 124.03 (18) | C35—C34—H34 | 119.8 |
N6—C5A—N5 | 128.6 (2) | C34—C35—C36 | 120.4 (2) |
N6—C5A—C3A' | 125.2 (2) | C34—C35—H35 | 119.8 |
N5—C5A—C3A' | 106.13 (19) | C36—C35—H35 | 119.8 |
C5A—N6—C6A | 114.0 (2) | C35—C36—C31 | 119.4 (2) |
C7—C6A—N6 | 116.1 (2) | C35—C36—H36 | 120.3 |
C7—C6A—C10A | 118.9 (2) | C31—C36—H36 | 120.3 |
N6—C6A—C10A | 125.1 (2) | C52—C51—C56 | 120.4 (2) |
C8—C7—C6A | 121.1 (2) | C52—C51—N5 | 120.1 (2) |
C8—C7—H7 | 119.5 | C56—C51—N5 | 119.6 (2) |
C6A—C7—H7 | 119.5 | C53—C52—C51 | 119.3 (2) |
C7—C8—C9 | 119.5 (2) | C53—C52—H52 | 120.3 |
C7—C8—H8 | 120.2 | C51—C52—H52 | 120.3 |
C9—C8—H8 | 120.2 | C52—C53—C54 | 120.7 (2) |
C10—C9—C8 | 121.3 (2) | C52—C53—H53 | 119.6 |
C10—C9—H9 | 119.3 | C54—C53—H53 | 119.6 |
C8—C9—H9 | 119.3 | C55—C54—C53 | 119.3 (2) |
C9—C10—C10A | 119.6 (2) | C55—C54—H54 | 120.3 |
C9—C10—H10 | 120.2 | C53—C54—H54 | 120.3 |
C10A—C10—H10 | 120.2 | C56—C55—C54 | 120.5 (2) |
C10—C10A—C6A | 119.6 (2) | C56—C55—H55 | 119.7 |
C10—C10A—N10B | 123.1 (2) | C54—C55—H55 | 119.7 |
C6A—C10A—N10B | 117.3 (2) | C55—C56—C51 | 119.7 (2) |
C3A'—N10B—C10A | 116.75 (19) | C55—C56—H56 | 120.1 |
C3A'—N10B—C1 | 117.02 (18) | C51—C56—H56 | 120.1 |
N11—C1—C2—C3 | 171.9 (3) | N11—C1—N10B—C3A' | −170.6 (2) |
N10B—C1—C2—C3 | −7.5 (4) | C2—C1—N10B—C3A' | 8.9 (3) |
N11—C1—C2—C21 | −9.0 (4) | N11—C1—N10B—C10A | 8.5 (4) |
N10B—C1—C2—C21 | 171.5 (2) | C2—C1—N10B—C10A | −172.0 (2) |
C21—C2—C3—C3A | −177.9 (2) | C10A—N10B—C3A'—C3A | 175.9 (2) |
C1—C2—C3—C3A | 1.0 (4) | C1—N10B—C3A'—C3A | −4.9 (4) |
C21—C2—C3—C31 | −2.0 (4) | C10A—N10B—C3A'—C5A | −6.0 (3) |
C1—C2—C3—C31 | 177.0 (2) | C1—N10B—C3A'—C5A | 173.1 (2) |
C2—C3—C3A—C3A' | 3.9 (3) | C3—C3A—C3A'—N10B | −2.0 (4) |
C31—C3—C3A—C3A' | −172.0 (2) | C4—C3A—C3A'—N10B | 175.9 (2) |
C2—C3—C3A—C4 | −173.3 (2) | C3—C3A—C3A'—C5A | 179.7 (2) |
C31—C3—C3A—C4 | 10.8 (4) | C4—C3A—C3A'—C5A | −2.4 (3) |
C3A'—C3A—C4—O4 | 179.8 (3) | N6—C5A—C3A'—N10B | 4.2 (4) |
C3—C3A—C4—O4 | −2.7 (5) | N5—C5A—C3A'—N10B | −174.8 (2) |
C3A'—C3A—C4—N5 | 0.3 (3) | N6—C5A—C3A'—C3A | −177.4 (2) |
C3—C3A—C4—N5 | 177.8 (3) | N5—C5A—C3A'—C3A | 3.6 (3) |
O4—C4—N5—C5A | −177.6 (2) | C3—C2—C21—N22 | 169 (4) |
C3A—C4—N5—C5A | 1.9 (3) | C1—C2—C21—N22 | −10 (4) |
O4—C4—N5—C51 | 4.9 (4) | C2—C3—C31—C32 | −121.9 (3) |
C3A—C4—N5—C51 | −175.6 (2) | C3A—C3—C31—C32 | 53.7 (3) |
C4—N5—C5A—N6 | 177.7 (2) | C2—C3—C31—C36 | 55.0 (4) |
C51—N5—C5A—N6 | −4.8 (4) | C3A—C3—C31—C36 | −129.3 (3) |
C4—N5—C5A—C3A' | −3.3 (3) | C36—C31—C32—C33 | −2.8 (4) |
C51—N5—C5A—C3A' | 174.2 (2) | C3—C31—C32—C33 | 174.2 (2) |
N5—C5A—N6—C6A | 178.7 (2) | C31—C32—C33—C34 | 1.9 (4) |
C3A'—C5A—N6—C6A | −0.1 (4) | C32—C33—C34—C35 | 0.4 (4) |
C5A—N6—C6A—C7 | 177.7 (2) | C33—C34—C35—C36 | −1.9 (4) |
C5A—N6—C6A—C10A | −1.7 (4) | C34—C35—C36—C31 | 1.1 (4) |
N6—C6A—C7—C8 | −179.6 (2) | C32—C31—C36—C35 | 1.2 (4) |
C10A—C6A—C7—C8 | −0.1 (4) | C3—C31—C36—C35 | −175.7 (2) |
C6A—C7—C8—C9 | 1.1 (4) | C5A—N5—C51—C52 | 44.3 (4) |
C7—C8—C9—C10 | −0.6 (4) | C4—N5—C51—C52 | −138.6 (2) |
C8—C9—C10—C10A | −0.8 (4) | C5A—N5—C51—C56 | −136.6 (2) |
C9—C10—C10A—C6A | 1.8 (4) | C4—N5—C51—C56 | 40.5 (3) |
C9—C10—C10A—N10B | −179.9 (2) | C56—C51—C52—C53 | 0.6 (4) |
C7—C6A—C10A—C10 | −1.3 (4) | N5—C51—C52—C53 | 179.7 (2) |
N6—C6A—C10A—C10 | 178.1 (2) | C51—C52—C53—C54 | −0.4 (4) |
C7—C6A—C10A—N10B | −179.7 (2) | C52—C53—C54—C55 | −0.2 (4) |
N6—C6A—C10A—N10B | −0.3 (4) | C53—C54—C55—C56 | 0.6 (4) |
C10—C10A—N10B—C3A' | −174.2 (2) | C54—C55—C56—C51 | −0.4 (4) |
C6A—C10A—N10B—C3A' | 4.1 (3) | C52—C51—C56—C55 | −0.2 (4) |
C10—C10A—N10B—C1 | 6.7 (4) | N5—C51—C56—C55 | −179.4 (2) |
C6A—C10A—N10B—C1 | −174.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···N11 | 0.95 | 2.16 | 2.794 (3) | 123 |
N11—H11···CG7 | 0.90 (3) | 2.59 (3) | 3.128 (3) | 119 (2) |
C56—H56···O4 | 0.95 | 2.55 | 2.950 (3) | 106 |
Acknowledgements
The authors would like to thank Mr Kornel Roztocki for performing the UV–Vis measurements for TAAP in the solid state, Mrs Małgorzata Kuniewicz for the determination of permanent
in 1,4-dioxane, A. Bossi for fruitful discussion, and Dr Mariusz Kępczyński for performing confocal fluorescence three-dimensional imaging of the TAAP single crystal. The research was carried out with equipment purchased with financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program. This research was supported in part by PL-Grid Infrastructure.Funding information
Funding for this research was provided by: European Regional Development Fund (award No. POIG.02.01.00-12-023/08); Polish Innovation Economy Operational Program (contract No. POIG.02.01.00-12-023/08).
References
Allen, F. H. & Bruno, I. J. (2010). Acta Cryst. B66, 380–386. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Avram, C. L. & Frish, L. (2005). Angew. Chem. Int. Ed. 44, 520–554. Google Scholar
Bader, R. F. W. (2003). Atoms in Molecules, A Quantum Theory. NewYork: Oxford University Press. Google Scholar
Basko, B. M., Lobanov, A. N., Pimenov, A. V. & Vitukhnovsky, A. G. (2003). Chem. Phys. Lett. 369, 192–197. CrossRef CAS Google Scholar
Broadbent, D. (2004). Color Res. Appl. 29, 267–272. CrossRef Google Scholar
Brown, P. J., Thomas, S. D., Köhler, A., Wilson, J. S., Kim, J.-S., Ramsdale, C. M., Sirringhaus, H. & Friend, R. (2003). Phys. Rev. B, 67, 064203. CrossRef Google Scholar
Chen, L., Yin, Sh.-Y., Pan, M., Wu, K., Wang, H.-P., Fan, Y. & Su, Ch.-Y. (2016). J. Mater. Chem. C, 4, 6962–6966. CSD CrossRef CAS Google Scholar
Contreras-García, J., Johnson, E. R., Keinan, S., Chaudret, R., Piquemal, J.-P., Beratan, D. N. & Yang, W. (2011). J. Chem. Theory Comput. 7, 625–632. Web of Science PubMed Google Scholar
Davydov, A. S. (1971). In Theory of Molecular Excitons. New York: Plenum Press. Google Scholar
Desiraju, G. R. & Steiner, T. (2001). The Weak Hydrogen Bond in Structural Chemistry and Biology, pp. 198–199. Oxford University Press. Google Scholar
El-Daly, S. A. & Hirayama, S. (1997). J. Photochem. Photobiol. Chem. 110, 59–65. CAS Google Scholar
El Helou, M., Medenbach, O. & Witte, G. (2010). Cryst. Growth Des. 10, 3496–3501. CSD CrossRef CAS Google Scholar
Fabian, J. (2010). Dyes Pigments, 84, 36–53. CrossRef CAS Google Scholar
Fang, H.-H., Yang, J., Feng, J., Yamao, T., Hotta, S. & Sun, H.-B. (2014). Laser Photonic Rev. 8, 687–715. CrossRef Google Scholar
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., et al. (2009). GAUSSIAN09. Revision A.1. Gaussian. Inc., Wallingford, Connecticut, USA. Google Scholar
Ghosh, M., Nath, S., Hajra, A. & Sinha, S. (2013). J. Lumin. 141, 87–92. CrossRef CAS Google Scholar
Gierschner, J. & Park, S. Y. (2013). J. Mater. Chem. C, 1, 5818–5832. CrossRef CAS Google Scholar
Hara, S., Houjou, H., Yoshikawa, I. & Araki, K. (2011). Cryst. Growth Des. 11, 5113–5121. Web of Science CSD CrossRef CAS Google Scholar
Huang, Y.-S., Gierschner, J., Schmidtke, J. P., Friend, R. H. & Beljonne, D. (2011). Phys. Rev. B, 84, 205311. CrossRef Google Scholar
Hunter, Ch. A., Lawson, K. R., Perkins, J. & Urch, Ch. J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 651–669. CrossRef Google Scholar
Inoué, S., Shimomura, O., Goda, M., Shribak, M. & Tran, P. T. (2002). Proc. Natl Acad. Sci. USA, 99, 4272–4277. Google Scholar
Janiak, Ch. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Jezierska-Mazzarello, A., Panek, J. J., Szatyłowicz, H. & Krygowski, T. M. (2012). J. Phys. Chem. A, 116, 460–475. CAS Google Scholar
Kasha, M., Rawls, R. & Ashraf El-Bayoumi, M. (1965). Pure Appl. Chem. 11, 371–392. CrossRef CAS Google Scholar
Keith, T. A. (2010). AIMAII program (Version 10.11.24), https://aim.tkgristmill.com. Google Scholar
Krygowski, T. M., Szatyłowicz, H., Stasyuk, O. A., Dominikowska, J. & Palusiak, M. (2014). Chem. Rev. 114, 6383–6422. CrossRef CAS Google Scholar
Kumar, V., Poonam, Prasad, A. K. & Parmar, V. S. (2003). Nat. Prod. Rep. 20, 565–583. CrossRef CAS Google Scholar
Kumar, S., Subramanian, K., Srinivasan, R., Rajagopalan, K. & Steiner, T. (1998). J. Mol. Struct. 471, 251–255. Web of Science CSD CrossRef CAS Google Scholar
Loots, L. & Barbour, L. J. (2012). The Importance of Pi-Interactions in Crystal Engineering, edited by E. R. T., Tiekink & J. Zukerman-Schpector, pp. 109–124. Chichester: John Wiley. Google Scholar
Lu, X., Fan, S., Wu, J., Jia, X., Wang, Z. S. & Zhou, G. (2014). J. Org. Chem. 79, 6480–6489. CSD CrossRef CAS Google Scholar
Ma, L., Zhang, K., Kloc, Ch., Sun, H., Soci, C., Michel-Beyerle, M. E. & Gurzadyan, G. G. (2013). Phys. Rev. B, 87, 201–203. Google Scholar
McRae, E. G. & Kasha, M. (1958). J. Chem. Phys. 28, 721–722. CrossRef CAS Google Scholar
Michl, J., Ingrouille, J. M., Simmonds, S. J. & Heinrich, M. (2014). Nat. Prod. Rep. 31, 676–693. CrossRef CAS Google Scholar
Nüesch, F. & Grätzel, M. (1995). Chem. Phys. 193, 1–17. Google Scholar
Ostrowska, K., Dudek, K. & Musielak, B. (2016). Heterocycles, 92, 1307–1312. CrossRef CAS Google Scholar
Pan, M., Zhu, Y.-X., Wu, K., Chen, L., Hou, Y.-J., Yin, Sh.-Y., Wang, H.-P., Fan, Y.-N. & Su, Ch.-Y. (2017). Angew. Chem. Int. Ed. 56, 14582–14586. CrossRef CAS Google Scholar
Park, S. K., Varghese, Sh., Kim, J. H., Yoon, S.-J., Kwon, O. K., An, B.-K., Gierschner, J. & Park, S. Y. (2013). J. Am. Chem. Soc. 135, 4757–4764. CSD CrossRef CAS Google Scholar
Rosell, F. I. & Boxer, S. G. (2003). Biochemistry, 42, 177–183. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spano, F. C. (2000). Chem. Phys. Lett. 331, 7–13. CrossRef CAS Google Scholar
Spano, F. C. (2010). Acc. Chem. Res. 43, 429–439. CrossRef CAS Google Scholar
Spano, F. C. & Silva, C. (2014). Annu. Rev. Phys. Chem. 65, 477–500. CrossRef CAS Google Scholar
Varghese, Sh. & Das, S. (2011). J. Phys. Chem. Lett. 2, 863–873. CrossRef CAS Google Scholar
Varughese, S. (2014). J. Mater. Chem. C, 2, 3499–3516. CrossRef CAS Google Scholar
Würthner, F., Kaiser, Th. E. & Saha-Möller, Ch. R. (2011). Angew. Chem. Int. Ed. 50, 3376–3410. Google Scholar
Xu, Zh., Liao, Q., Shi, Q., Zhang, H., Yao, J. & Fu, H. (2012). Adv. Mater. 24, 216–220. Google Scholar
Yamagata, H., Maxwell, D. S., Fan, J., Kittilstved, K. R., Briseno, A. L., Barnes, M. D. & Spano, F. C. (2014). J. Phys. Chem. C, 118, 28842–28854. CrossRef CAS Google Scholar
Zhao, Y. & Truhlar, D. G. (2007). J. Chem. Theory Comput. 3, 569–582. CrossRef Google Scholar
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