TY - JOUR

T1 - Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitro­syl complexes

AU - Mikhailov, Artem

AU - Vuković, Vedran

AU - Kijatkin, Christian

AU - Wenger, Emmanuel

AU - Imlau, Mirco

AU - Woike, Theo

AU - Kostin, Gennadiy

AU - Schaniel, Dominik

PY - 2019/12

Y1 - 2019/12

N2 - 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-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.

AB - 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-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.

KW - excited states

KW - linkage isomers

KW - nonlinear optical properties

KW - photocrystallography

KW - ruthenium nitrosyl

KW - HARMONIC-GENERATION

KW - INDUCED METASTABLE STATES

KW - TRANSITION

KW - NANOPARTICLES

KW - 2ND-HARMONIC GENERATION

KW - METAL

KW - ZNO

KW - SCATTERING

UR - http://www.scopus.com/inward/record.url?scp=85076545116&partnerID=8YFLogxK

U2 - 10.1107/S205252061901357X

DO - 10.1107/S205252061901357X

M3 - Article

C2 - 32830695

AN - SCOPUS:85076545116

VL - 75

SP - 1152

EP - 1163

JO - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

SN - 2052-5192

ER -