Title

Syntheses and characterization of diruthenium metallaynes and charge mobility therein

Date of Award

2004

Availability

Article

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemistry

First Committee Member

Tong Ren, Committee Chair

Abstract

Metallaynes have been exploited for a number of material applications, such as molecular electronic devices, nonlinear optics, liquid crystals and molecular emitters. An area of particular interest to us is the generation of "molecular wires" using linear conjugated metallyne molecules.This dissertation focuses on the studies of the linear conjugated metallaynes based on diruthenium motifs. Two series of Ru2-based metallaynes of general formula Ru2(ap)4(C 2nY) (n = 2--5, Y = Tips, Ph) were synthesized under Hay conditions and a linear relationship between the HOMO-LUMO gaps of Ru2( ap)4(C2nY) versus n was obtained through the electrochemical and optical measurements. The studies of mu-polyyndiyl compounds, [Ru2(ap)4(mu-C2n) (n = 1--4, 6), clearly demonstrated that the polyyndiyl bridge (-C2n -) mediates strong electron delocalization between two Ru2( ap)4-termini. Upon the addition of tetracyanoethylene (TCNE) onto the polyyndiyl bridge in [Ru2(ap) 4]2(mu-C6), the electronic coupling between two Ru2(ap)4 termini was disrupted. In addition, a number of bis(alkynyl) adducts based on the Ru2(DMBA) 4 core were prepared and characterized. Electrochemical and spectroelectrochemical studies of the Fc-capped Ru2(DMBA)4-based compounds revealed the strong electron delocalization through the diruthenium unit.

Keywords

Chemistry, Inorganic

Link to Full Text

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