Premium
Computational design of organometallic oligomers featuring 1,3‐metal‐carbon bonding and planar tetracoordinate carbon atoms
Author(s) -
Zhao XueFeng,
Yuan CaiXia,
Wang Xiang,
Li JiaJia,
Wu YanBo,
Wang Xiaotai
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24185
Subject(s) - tetracoordinate , carbon fibers , planar , metal , organometallic chemistry , materials science , chemistry , computational chemistry , nanotechnology , organic chemistry , computer science , catalysis , composite material , computer graphics (images) , composite number
Density functional theory computations (B3LYP) have been used to explore the chemistry of titanium–aromatic carbon “edge complexes” with 1,3‐metal‐carbon (1,3‐MC) bonding between Ti and planar tetracoordinate C β . The titanium‐coordinated, end‐capping chlorides are replaced with OH or SH groups to afford two series of difunctional monomers that can undergo condensation to form oxide‐ and sulfide‐bridged oligomers. The sulfide‐linked oligomers have less molecular strain and are more exergonic than the corresponding oxide‐linked oligomers. The HOMO–LUMO gap of the oligomers varies with their composition and decreases with growing oligomer chain. This theoretical study is intended to enrich 1,3‐MC bonding and planar tetracoordinate carbon chemistry and provide interesting ideas to experimentalists. Organometallic complexes with the TiE 2 (E = OH and SH) decoration on the edge of aromatic hydrocarbons have been computationally designed, which feature 1,3‐metal‐carbon (1,3‐MC) bonding between titanium and planar tetracoordinate β‐carbon. Condensation of these difunctional monomers by eliminating small molecules (H 2 O and H 2 S) produce chain‐like oligomers. The HOMO–LUMO gaps of the oligomers decreases with growing oligomer chain, a trend that suggests possible semiconductor properties for oligomers with longer chains. © 2015 Wiley Periodicals, Inc.