Premium
A Quantum Chemical Study of the Structure, Bonding Characteristics and Nonlinear Optical Properties of Aryloxido and Salicylaldehydo Derivatives of [XW 5 O 18 ] 3– (X = Zr or Ti)
Author(s) -
Zhuang Jia,
Yan Likai,
Liu Chunguang,
Su Zhongmin
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900011
Subject(s) - chemistry , natural bond orbital , atomic orbital , atom (system on chip) , density functional theory , crystallography , electronic structure , chemical bond , cluster (spacecraft) , charge (physics) , computational chemistry , ligand (biochemistry) , nonlinear optical , molecular orbital , molecule , electron , nonlinear system , organic chemistry , biochemistry , physics , receptor , computer science , programming language , embedded system , quantum mechanics
Abstract The bonding characteristics, first hyperpolarizabilities, and origin of the nonlinear optical (NLO) properties of aryloxido and salicylaldehydo derivatives of [XW 5 O 18 ] 3– (X = Zr or Ti) have been investigated using density functional theory (DFT). The flexible bonding behavior of the linkage oxygen (O L ) atom attracted our attention initially, and NBO analysis revealed that there aret two different kinds of π‐interactions involving the O L atom in these systems. In two aryloxido derivatives (systems 1 and 2 ), O L –metal π‐interactions are largely O L –M p‐d in character, whereas in the salicylaldehydo derivatives (system 3 ) we observed another kind of π‐interaction, namely O L –C p‐p π‐bonding. The differences in molecular composition in our studied systems are very slight. However, the β 0 values differ significantly. Thus, system 3 has the largest β 0 value(559.27 × 10 –30 esu), which is 170 times larger than that of system 1 . This variation can be traced to the different electronic transitions and charge‐transfer characteristics. The heteropolyanion cluster and organic ligand are both electron‐rich groups. A small change in molecular composition or architecture can therefore significantly modify the configuration and overlapping of molecular orbitals, thus causing a “butterfly effect” upon the electronic transitions and charge‐transfer characteristics.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)