TY - JOUR
T1 - Structures and spectroscopic properties of bis(phthalocyaninato) yttrium and lanthanum complexes
T2 - Theoretical study based on density functional theory calculations
AU - Zhang, Yuexing
AU - Cai, Xue
AU - Zhou, Yang
AU - Zhang, Xianxi
AU - Xu, Hui
AU - Liu, Zhongqiang
AU - Li, Xiyou
AU - Jiang, Jianzhuang
PY - 2007/1/18
Y1 - 2007/1/18
N2 - Density functional theory (DFT) calculations were carried out to describe the molecular structures, molecular orbitals, atomic charges, UV-vis absorption spectra, IR, and Raman spectra of bis(phthalocyaninato) rare earth(III) complexes M(Pc)2 (M = Y, La) as well as their reduced products [M(Pc)2]- (M = Y, La). Good consistency was found between the calculated results and experimental data. Reduction of the neutral M(Pc)2 to [M(Pc)2]- induces the reorganization of their orbitals and charge distribution and decreases the inter-ring interaction. With the increase of ionic size from Y to La, the inter-ring distance of both the neutral and reduced double-decker complexes M(Pc) 2 and [M(Pc)2]- (M = Y, La) increases, the inter-ring interaction and splitting of the Q bands decrease, and corresponding bands in the IR and Raman spectra show a red shift. The orbital energy level and orbital nature of the frontier orbitals are also described and explained in terms of atomic character. The present work, representing the first systemic DFT study on the bis(phthalocyaninato) yttrium and lanthanum complexes sheds further light on clearly understanding structure and spectroscopic properties of bis(phthalocyaninato) rare earth complexes.
AB - Density functional theory (DFT) calculations were carried out to describe the molecular structures, molecular orbitals, atomic charges, UV-vis absorption spectra, IR, and Raman spectra of bis(phthalocyaninato) rare earth(III) complexes M(Pc)2 (M = Y, La) as well as their reduced products [M(Pc)2]- (M = Y, La). Good consistency was found between the calculated results and experimental data. Reduction of the neutral M(Pc)2 to [M(Pc)2]- induces the reorganization of their orbitals and charge distribution and decreases the inter-ring interaction. With the increase of ionic size from Y to La, the inter-ring distance of both the neutral and reduced double-decker complexes M(Pc) 2 and [M(Pc)2]- (M = Y, La) increases, the inter-ring interaction and splitting of the Q bands decrease, and corresponding bands in the IR and Raman spectra show a red shift. The orbital energy level and orbital nature of the frontier orbitals are also described and explained in terms of atomic character. The present work, representing the first systemic DFT study on the bis(phthalocyaninato) yttrium and lanthanum complexes sheds further light on clearly understanding structure and spectroscopic properties of bis(phthalocyaninato) rare earth complexes.
UR - http://www.scopus.com/inward/record.url?scp=33847120916&partnerID=8YFLogxK
U2 - 10.1021/jp066157g
DO - 10.1021/jp066157g
M3 - Article
C2 - 17214477
AN - SCOPUS:33847120916
SN - 1089-5639
VL - 111
SP - 392
EP - 400
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 2
ER -