Local Force Constants and Charges of the Nitrosyl Ligand in Photoinduced NO Linkage Isomers in a Prototypical Ruthenium Nitrosyl Complex

Photoinduced linkage isomers (PLI) of the NO ligand in transition-metal nitrosyl compounds can be identified by vibrational spectroscopy due to the large shifts of the 001100100 010011000 000000000 000000000 011000100 001100110 000100010 000100100 000101100 000101000 000110000 (NO) stretching vibration. We present a detailed experimental and theoretical study of the prototypical compound K2[RuCl5NO], where (NO) shifts by approximate to 150 cm-1 when going from the N-bound (kappa N) ground state (GS) to the oxygen-bound (kappa O) metastable linkage isomer MS1, and by approximate to 360 cm-1 when going to the side-on (kappa 2N,O) metastable linkage isomer MS2. We show that the experimentally observed N-O stretching modes of the GS, MS1, and MS2 exhibit strong coupling with the Ru-N and Ru-O stretching modes, which can be decoupled using the local mode vibrational theory formalism. From the resulting decoupled pure two-atomic harmonic oscillators the local force constants are determined, which all follow the same quadratic behavior on the wavenumber. A Bader charge analysis shows that the total charge on the NO ligand is not correlated to the observed frequency shift of (NO). Photoinduced NO linkage isomers: total charges on NO are not correlated to the frequency of the NO stretching vibration. Local force constants reveal a significant change in coupling of Ru-N/O and N-O stretching vibrations.