Issue 40, 2018

Diruthenium(ii)-capped oligothienylethynyl bridged highly soluble organometallic wires exhibiting long-range electronic coupling

Abstract

Organometallic molecular wires with π-conjugation along their molecular backbones are of considerable interest for application in molecular-scale electronics. In this regard, thienylethynyl-based π-conjugated oligomers of three, five and seven thienylethynyl units with –C[triple bond, length as m-dash]C–H termini have been successfully synthesized through stepwise Pd(0)/Cu(I)-catalyzed Sonogashira coupling. The corresponding highly soluble diruthenium(II) diacetylide complexes (O1-Ru2, O3-Ru2, O5-Ru2 and O7-Ru2, respectively) have been prepared by the reaction of cis-Ru(dppe)2Cl2 and NaPF6 in DCM with the corresponding rigid rod-like thienylethynyl oligomers with one, three, five and seven thienylethynyl π-conjugated segments containing alkynyl termini (O1, O3, O5 and O7). These Ru(II)–Cl capped diacetylide complexes have been further functionalized by incorporating a phenylacetynyl moiety to afford [Ru(II)–C[triple bond, length as m-dash]C–Ph]-capped diacetylide organometallic wires (O1-Ru2-Ph, O3-Ru2-Ph, O5-Ru2-Ph and O7-Ru2-Ph). The photophysical properties of the highly soluble thienylethynyl-based oligomers and Ru(II)-organometallic wires have been explored to understand their electronic properties. Electrochemical studies of the binuclear ruthenium(II)-alkynyl complexes showed highly interesting results, revealing long-range electrochemical communication between the two remote Ru(II) termini connected even with five and seven thienylethynyl units. DFT computational studies further support the long range electrochemical communication between the redox active metal termini through heavy participation of the thienylethynyl bridge in the corresponding mono-oxidized mixed valence species of the organometallic wire-like complexes.

Graphical abstract: Diruthenium(ii)-capped oligothienylethynyl bridged highly soluble organometallic wires exhibiting long-range electronic coupling

Supplementary files

Article information

Article type
Paper
Submitted
06 ሜይ 2018
Accepted
11 ጁን 2018
First published
12 ጁን 2018

Dalton Trans., 2018,47, 14304-14317

Diruthenium(II)-capped oligothienylethynyl bridged highly soluble organometallic wires exhibiting long-range electronic coupling

S. Saha Roy, A. Sil, D. Giri, S. Roy Chowdhury, S. Mishra and S. K. Patra, Dalton Trans., 2018, 47, 14304 DOI: 10.1039/C8DT01818A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements