Research output: Contribution to journal › Article › peer-review
Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes. / Mikhailov, Artem; Vuković, Vedran; Kijatkin, Christian et al.
In: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, Vol. 75, 12.2019, p. 1152-1163.Research output: Contribution to journal › Article › peer-review
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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 -
ID: 22995190