Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitro­syl complexes

The complex trans-[RuNO(NH₃)₄F]SiF₆ was synthesized in quantitative yield and the structure was characterized by X-ray diffraction and spectroscopic methods. The complex crystallizes in the non-centrosymmetric space group Pn. Hirshfeld surface analysis revealed that the dominant intermolecular inter­actions are of types H...F and F...O, which are likely to be responsible for the packing of the molecules in a non-centrosymmetric structure. Irradiation with blue light leads to the formation of Ru–ON (metastable state MS1) and Ru–η²-(NO) (metastable state MS2) bond isomers, as shown by IR and UV–Vis spectroscopy. The structural features of the MS1 isomer were elucidated by photocrystallography. The complex exhibits exceptionally good thermal stability of the metastable state MS1, such that it can be populated by light at 290–300 K, which is important for potential applications. The second harmonic (SH) emission can be generated by femtosecond-pulsed irradiation of the complex. The generated SH is rather efficient and stable under long-term exposure. Finally, since both metastable states and harmonic generation can be generated at room temperature, an attempt to drive the SH response by photoisomerization of the nitro­syl ligand was made and is discussed.

Computing details

Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); cell refinement: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

F6Si·FH12N5ORu	F(000) = 349.9500
Mr = 360.27	Dx = 2.487 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
a = 6.7036 (4) Å	Cell parameters from 4735 reflections
b = 7.4260 (4) Å	θ = 2.7–32.8°
c = 10.1296 (7) Å	µ = 1.85 mm^−1
β = 107.469 (6)°	T = 100 K
V = 481.01 (5) Å^3	Block, yellow
Z = 2	0.16 × 0.10 × 0.09 mm

Data collection

SuperNova, Dual, Cu at home/near, Atlas diffractometer	3165 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	3066 reflections with I ≥ 2u(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 10.4508 pixels mm^-1	θmax = 32.9°, θmin = 2.7°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −11→11
Tmin = 0.624, Tmax = 1.000	l = −13→14
8064 measured reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0166P)^2 + 0.2679P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.049	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.64 e Å^−3
3165 reflections	Δρmin = −0.64 e Å^−3
141 parameters	Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876-881.
2 restraints	Absolute structure parameter: −0.02 (2)
16 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Si1	−0.85252 (13)	−0.16577 (9)	−0.50274 (11)	0.00629 (19)
Ru1	−0.366141 (14)	−0.67200 (2)	−0.491860 (12)	0.00485 (5)
N1	−0.3164 (3)	−0.9338 (3)	−0.4128 (2)	0.0085 (4)
H1a	−0.231 (3)	−0.9918 (9)	−0.4510 (16)	0.0102 (5)*
H1b	−0.258 (3)	−0.9293 (3)	−0.3215 (3)	0.0102 (5)*
H1c	−0.4381 (5)	−0.9916 (9)	−0.4323 (18)	0.0102 (5)*
F1	−0.1250 (2)	−0.6094 (2)	−0.33755 (14)	0.0097 (3)
N4	−0.1534 (3)	−0.7105 (4)	−0.6028 (2)	0.0090 (4)
H4a	−0.2225 (3)	−0.730 (3)	−0.6914 (5)	0.0108 (5)*
H4b	−0.074 (2)	−0.6127 (11)	−0.5957 (18)	0.0108 (5)*
H4c	−0.073 (2)	−0.8050 (18)	−0.5687 (14)	0.0108 (5)*
N5	−0.5865 (3)	−0.7186 (3)	−0.6266 (2)	0.0072 (4)
N2	−0.5482 (3)	−0.6287 (4)	−0.3587 (2)	0.0091 (4)
H2a	−0.625 (2)	−0.5298 (16)	−0.3846 (13)	0.0110 (5)*
H2b	−0.632 (2)	−0.7227 (13)	−0.3625 (17)	0.0110 (5)*
H2c	−0.4649 (3)	−0.615 (3)	−0.2725 (4)	0.0110 (5)*
F6	−0.6219 (2)	−0.2236 (2)	−0.38840 (15)	0.0089 (3)
F4	−0.9695 (2)	−0.2098 (3)	−0.38167 (16)	0.0128 (3)
F5	−0.8149 (2)	0.0500 (2)	−0.45111 (15)	0.0121 (3)
F2	−0.7277 (2)	−0.1265 (3)	−0.62083 (16)	0.0132 (3)
F7	−1.0819 (2)	−0.1142 (2)	−0.61521 (16)	0.0136 (3)
N3	−0.3747 (3)	−0.3995 (3)	−0.5456 (2)	0.0092 (4)
H3a	−0.424 (3)	−0.3884 (3)	−0.6372 (2)	0.0110 (5)*
H3b	−0.458 (2)	−0.3404 (6)	−0.5067 (17)	0.0110 (5)*
H3c	−0.2463 (6)	−0.3537 (7)	−0.5159 (18)	0.0110 (5)*
F3	−0.8835 (2)	−0.3861 (2)	−0.55483 (15)	0.0120 (3)
O1	−0.7392 (2)	−0.7420 (3)	−0.71316 (18)	0.0132 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0057 (3)	0.0054 (2)	0.0071 (4)	−0.0003 (3)	0.0010 (3)	0.0000 (3)
Ru1	0.00486 (7)	0.00460 (7)	0.00479 (8)	0.00002 (8)	0.00102 (5)	−0.00048 (9)
N1	0.0095 (9)	0.0067 (9)	0.0099 (10)	−0.0001 (7)	0.0038 (8)	−0.0004 (8)
F1	0.0122 (7)	0.0089 (8)	0.0059 (7)	−0.0015 (6)	−0.0004 (6)	−0.0010 (6)
N4	0.0092 (10)	0.0095 (10)	0.0090 (11)	0.0019 (9)	0.0041 (8)	−0.0006 (9)
N5	0.0057 (9)	0.0080 (10)	0.0080 (10)	0.0008 (8)	0.0022 (7)	−0.0005 (8)
N2	0.0098 (10)	0.0103 (10)	0.0075 (11)	−0.0002 (9)	0.0029 (8)	0.0012 (9)
F6	0.0067 (6)	0.0113 (8)	0.0078 (7)	0.0010 (6)	0.0007 (5)	0.0010 (6)
F4	0.0106 (7)	0.0165 (8)	0.0140 (9)	0.0011 (7)	0.0076 (6)	0.0028 (7)
F5	0.0138 (7)	0.0062 (7)	0.0147 (8)	−0.0006 (5)	0.0018 (5)	−0.0020 (6)
F2	0.0172 (8)	0.0145 (8)	0.0100 (8)	0.0019 (7)	0.0070 (6)	0.0031 (7)
F7	0.0099 (7)	0.0125 (8)	0.0136 (8)	0.0017 (6)	−0.0037 (6)	0.0029 (7)
N3	0.0081 (9)	0.0103 (10)	0.0093 (10)	−0.0010 (8)	0.0029 (8)	−0.0014 (8)
F3	0.0153 (7)	0.0061 (7)	0.0123 (8)	0.0001 (6)	0.0003 (6)	−0.0014 (6)
O1	0.0099 (8)	0.0156 (10)	0.0121 (9)	−0.0017 (7)	0.0002 (7)	−0.0017 (8)

Geometric parameters (Å, º)

Si1—F6	1.6854 (17)	N1—H1b	0.8900
Si1—F4	1.6745 (19)	N1—H1c	0.8900
Si1—F5	1.6808 (17)	N4—H4a	0.8900
Si1—F2	1.678 (2)	N4—H4b	0.8900
Si1—F7	1.6603 (16)	N4—H4c	0.8900
Si1—F3	1.7123 (17)	N5—O1	1.143 (2)
Ru1—N1	2.091 (2)	N2—H2a	0.8900
Ru1—F1	1.9378 (13)	N2—H2b	0.8900
Ru1—N4	2.083 (2)	N2—H2c	0.8900
Ru1—N5	1.7191 (19)	N3—H3a	0.8900
Ru1—N2	2.098 (2)	N3—H3b	0.8900
Ru1—N3	2.092 (2)	N3—H3c	0.8900
N1—H1a	0.8900
F4—Si1—F6	88.95 (9)	N3—Ru1—N5	92.18 (10)
F5—Si1—F6	90.46 (9)	N3—Ru1—N2	92.48 (9)
F5—Si1—F4	91.02 (10)	H1a—N1—Ru1	109.5
F2—Si1—F6	89.05 (8)	H1b—N1—Ru1	109.5
F2—Si1—F4	177.85 (10)	H1b—N1—H1a	109.5
F2—Si1—F5	89.78 (9)	H1c—N1—Ru1	109.5
F7—Si1—F6	178.52 (10)	H1c—N1—H1a	109.5
F7—Si1—F4	90.39 (9)	H1c—N1—H1b	109.5
F7—Si1—F5	90.87 (8)	H4a—N4—Ru1	109.5
F7—Si1—F2	91.60 (9)	H4b—N4—Ru1	109.5
F3—Si1—F6	88.27 (8)	H4b—N4—H4a	109.5
F3—Si1—F4	89.94 (9)	H4c—N4—Ru1	109.5
F3—Si1—F5	178.39 (9)	H4c—N4—H4a	109.5
F3—Si1—F2	89.22 (10)	H4c—N4—H4b	109.5
F3—Si1—F7	90.42 (9)	O1—N5—Ru1	175.9 (2)
F1—Ru1—N1	85.14 (7)	H2a—N2—Ru1	109.5
N4—Ru1—N1	91.30 (9)	H2b—N2—Ru1	109.5
N4—Ru1—F1	85.85 (7)	H2b—N2—H2a	109.5
N5—Ru1—N1	96.74 (10)	H2c—N2—Ru1	109.5
N5—Ru1—F1	177.16 (10)	H2c—N2—H2a	109.5
N5—Ru1—N4	96.21 (9)	H2c—N2—H2b	109.5
N2—Ru1—N1	87.30 (9)	H3a—N3—Ru1	109.5
N2—Ru1—F1	87.14 (7)	H3b—N3—Ru1	109.5
N2—Ru1—N4	172.94 (8)	H3b—N3—H3a	109.5
N2—Ru1—N5	90.82 (9)	H3c—N3—Ru1	109.5
N3—Ru1—N1	171.08 (7)	H3c—N3—H3a	109.5
N3—Ru1—F1	85.94 (7)	H3c—N3—H3b	109.5
N3—Ru1—N4	87.83 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1b···F2^i	0.89	2.02 (1)	2.872 (3)	159 (2)

Symmetry code: (i) x+1/2, −y−1, z+1/2.