Wavelength-selective photoisomerisation of nitric oxide and nitrite in a rhodium complex

Abstract

Photoinduced linkage isomers (PLIs) of NO and NO₂⁻ are selectively generated by an appropriate choice of irradiation wavelength at low temperature within the same molecular complex [Rh(NO)(NO₂)₂(Bu^t₂PH)₂]. The structures of the PLIs are characterised by photocrystallography and the corresponding vibrational changes by infrared spectroscopy. Using red light about 37% of the κON isonitrosyl PLI can be produced while irradiation with blue light produces about 80% of the (O,O′) chelating NO₂⁻ isomer. Upon heating the NO₂⁻ PLI undergoes several structural transformations, which are characterised by infrared spectroscopy.