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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 FO, 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.
F and FO, 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.Keywords: ruthenium nitrosyl; excited states; linkage isomers; nonlinear optical properties; photocrystallography.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S205252061901357X/dk5089sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S205252061901357X/dk5089Isup2.hkl |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S205252061901357X/dk5089sup3.pdf |
CCDC reference: 1910521
Computing details top
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) top
Crystal data top
| 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) Å3 | Block, yellow |
| Z = 2 | 0.16 × 0.10 × 0.09 mm |
Data collection top
| 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 top
| Refinement on F2 | Primary atom site location: iterative |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.022 | w = 1/[σ2(Fo2) + (0.0166P)2 + 0.2679P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 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 (Å2) top
| 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 (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| 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) top
| 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) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1b···F2i | 0.89 | 2.02 (1) | 2.872 (3) | 159 (2) |
| Symmetry code: (i) x+1/2, −y−1, z+1/2. |
