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Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes
Author(s) -
Mikhailov Artem,
Vuković Vedran,
Kijatkin Christian,
Wenger Emmanuel,
Imlau Mirco,
Woike Theo,
Kostin Gennadiy,
Schaniel Dominik
Publication year - 2019
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s205252061901357x
Subject(s) - photoisomerization , metastability , ruthenium , chemistry , intermolecular force , crystallography , linkage isomerism , photochemistry , molecule , irradiation , femtosecond , ligand (biochemistry) , spectroscopy , isomerization , laser , metal , optics , organic chemistry , biochemistry , physics , receptor , nuclear physics , catalysis , quantum mechanics
The complex trans ‐[RuNO(NH 3 ) 4 F]SiF 6 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–η 2 ‐(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.