Ru(py).sub.4./sub.Cl(NO)](PF.sub.6./sub.).sub.2./sub..0.5H.sub.2./sub.O: a model system for structural determination and ab initio calculations of photo-induced linkage NO isomers

0337246 - FZÚ 2012 RIV DK eng J - Journal Article
Cormary, B. - Malfant, I. - Valade, L. - Cointe, M.B.L. - Toupet, L. - Todorova, T. - Delley, B. - Schaniel, D. - Mockus, N. - Woike, T. - Fejfarová, Karla - Petříček, Václav - Dušek, Michal
Ru(py)₄Cl(NO)](PF₆)₂.0.5H₂O: a model system for structural determination and ab initio calculations of photo-induced linkage NO isomers.
Acta Crystallographica Section B-Structural Science. Roč. 65, - (2009), s. 612-623. ISSN 0108-7681
R&D Projects: GA ČR(CZ) GC202/07/J007
Institutional research plan: CEZ:AV0Z10100521
Keywords : metastable phases * photocrystallography * density functional calculations * x-ray diffraction * Jana2006
Subject RIV: BM - Solid Matter Physics ; Magnetism
Impact factor: 1.801, year: 2009

Structure analysis of ground state (GS) and two light-induced (SI and SII) metastable linkage NO isomers of Ru(py)4Cl(NO)](PF6)2.0.5H2O is presented. Illumination of the crystal by a laser with [lambda] = 473 nm at T = 80 K transfers around 92% of the NO ligands from Ru-N-O into the isomeric configuration Ru-O-N (SI). A subsequent irradiation with [lambda] = 980 nm generates about 48% of the side-on configuration Ru< N_O (SII). Heating to temperatures above 200 K or irradiation with light in the red spectral range transfers both metastable isomers reversibly back to the GS. The experimental results are compared with solid-state calculations based on density functional theory (DFT), which reproduce the observed structures with high accuracy concerning bond lengths and angles.
Permanent Link: http://hdl.handle.net/11104/0181292