Synlett 2018; 29(08): 999-1007
DOI: 10.1055/s-0036-1591939
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© Georg Thieme Verlag Stuttgart · New York

Unconventional Conjugated Polymers Derived from a Common Set of trans-Enediyne Monomers

Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM 87131, USA   Email: yangqin@unm.edu
› Author Affiliations
The author would like to acknowledge NSF (DMR-1453083) for financial support for this research, and NM EPSCoR (NSF Grant No. IIA-1301346) and USDA (NIFA 2015-38422-24059) for partially supporting the research.
Further Information

Publication History

Received: 26 December 2017

Accepted after revision: 25 January 2018

Publication Date:
15 February 2018 (online)

Abstract

This account describes our recent efforts in the design and synthesis of several series of unconventional conjugated polymers derived from a common set of trans-enediyne (tEDY) monomers. The journey started with a failed attempt, through acyclic diene metathesis of triene monomers, to prepare soluble polyacetylenes (PAs) having cross-conjugated side-groups on alternate double bonds along the main chain. At this seemingly dead end of the project, we found that the tEDY intermediates leading to triene monomers could undergo alkyne metathesis to generate soluble polydiacetylenes (PDAs). Such acyclic enediyne metathesis represents the first example of a solution synthesis of PDAs, in contrast to the conventional topochemical methods. By applying Glaser–Hay-type reaction conditions with selected tEDY monomers, polytriacetylenes were smoothly obtained; these possessed aromatic units directly attached to the polymer main chains, which significantly affected the electronic properties of the polymers. Furthermore, through hydroboration of the tEDY monomers, ‘boron-doped’ polyacetylenes (BDPAs) were prepared that can be considered as PAs with every fourth double bond replaced with a boron atom. These BDPAs represent the first boron main-chain conjugated polymers lacking aromatic units along the backbone, potentially enhancing electronic delocalization along the main chain.

 
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