Choi, Jong-Ha;Oh, In-Gyung;Subodh Kumar;Ryoo, Keon-Sang
19
The sharp-line absorption spectrum of microcrystalline samples of cis-[Cr(cycb)$Cl_2$]Cl (cycb=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been measured between 13000 and $16000 cm^{-1}$ at temperatures down to 5K. The 77K emission and excitation spectra, and 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex. The zero-phonon line in the sharp-line absorption spectrum splits into two components by $240 cm^{-1}$ , and the $large ^2$$_E{g}$ splitting can be reproduced by the modem ligand field theory. It is confirmed that nitrogen atoms of the macrocyclic cycb ligand have a strong $\sigma$-donor character, but chloride ligand has weak $\sigma$- nd $\pi$-donor properties toward chromium(III) ion.n.