Inorganic Chemistry, Vol.56, No.19, 11640-11653, 2017
Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines
2,3,9,10,16,17,23.24-Octakis-(9H-carbazol-9-y1) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23.24-octakis-(3,6di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV vis and MCD data are indicative of the interligand charge transfer nature of the broad band observed in 450-500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.