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Photocrystallography and IR spectroscopy of light‐induced linkage NO isomers in [RuBr(NO) 2 (PCyp 3 ) 2 ]BF 4
Author(s) -
Casaretto Nicolas,
Pillet Sébastien,
Bendeif ElEulmi,
Schaniel Dominik,
Gallien Anna K. E.,
Klüfers Peter,
Woike Theo
Publication year - 2015
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/s2052520615018132
Subject(s) - spectroscopy , materials science , infrared spectroscopy , linkage (software) , chemistry , analytical chemistry (journal) , physics , environmental chemistry , biochemistry , organic chemistry , quantum mechanics , gene
One single photo‐induced linkage NO isomer (PLI) is detected and characterized in the dinitrosyl pentacoordinated compound [RuBr(NO) 2 (PCyp 3 ) 2 ]BF 4 by a combination of photocrystallographic and IR analysis. In the ground state, the molecule adopts a trigonal–bipyramidal structure with the two NO ligands almost linear with angles Ru—N1—O1 = 168.92 (16), Ru—N2—O2 = 166.64 (16)°, and exactly equal distances of Ru—N = 1.7838 (17) and O—N = 1.158 (2) Å. After light irradiation of 405 nm at T = 10 K, the angle of Ru—N2—O2 changes to 114.2 (6)° by rotation of the O atom towards the Br ligand with increased distances of Ru—N2 = 1.992 (6) and N2—O2 = 1.184 (8) Å, forming a bent κ N bonded configuration. Using IR spectroscopy, the optimal wavelength and maximum population of 39 (1)% of the PLI is determined. In the ground state (GS), the two symmetric ν s (NO) and asymmetric ν as (NO) vibrations are measured at 1820 and 1778 cm −1 , respectively. Upon photo‐irradiation, the detection of only one new vibrational ν(NO) stretching band at 1655 cm −1 , assigned to the antisymmetric coupled vibration mode and shifted to lower wavenumbers by −123 cm −1 , supports the photocrystallographic result. These experimental results are supported by additional DFT calculations, which reproduce the structural parameters and vibrational properties of both the ground state and the photo‐induced linkage isomer well. Especially the experimentally characterized molecular structure of the PLI state corresponds to an energy minimum in the calculations; the stabilization of the bent κ N bonded configuration of the PLI state originates from specific intramolecular orbital overlap.