PubMed Health⌕ Search

PubMed · 16171317

Functional polyacetylenes.

Abstract

Polyacetylene (PA) is a Nobel Prize-winning macromolecule. In this work, PA is molecularly functionalized, which endows it with an array of new functional properties. The molecular functionalization is realized by attachment of functional pendants to the polyene backbone. Our efforts in the catalyst exploration and reaction optimization have led to the syntheses of a large number of PA derivatives carrying functional groups. Polymer reactions are exploited as an alternative route to the functional PAs that are difficult or impossible to access by direct polymerizations of their monomers. The new PAs with appropriate backbone-pendant combinations show various functional properties such as liquid crystallinity, photoconductivity, light emission, ionic susceptibility, photoresistance, chromism, helical chirality, optical nonlinearity, self-assembly, cytocompatibility, and bioactivity. The properties of the PAs are tuned internally and manipulated externally: the former is achieved by changing their molecular structures, especially their functional pendants, while the latter is accomplished by applying thermal, mechanical, electrical, photonic, and chemical stimuli.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Jacky W Y Lam, Ben Zhong Tang. 2005. Functional polyacetylenes.. https://doi.org/10.1021/ar040012f

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

Enantioselective phenylacetylene addition to aldehydes and ketones catalyzed by recyclable polymeric Zn(salen) complex.

New polymeric Zn(salen) complex was employed in the enantioselective phenylacetylene addition to aldehydes and ketones to produce corresponding chiral secondary propargylic alcohols with yields (up to 96%) and enantioselectivity (up to 72%) and tertiary propargylic alcohols with yields (up to 79%) and enantioselectivity (up to 68%) at room temperature, with added advantage of four times reuse with retention of enantioselectivity.

Acetylene↗

Theoretical investigations on the geometric and electronic structures of phenylene-acetylene macrocycles.

The geometric and electronic structures of a series of conjugated macrocycles (phenylene-acetylene macrocycles, PAMs) have been studied theoretically with ab initio and semiempirical molecular orbital methods. The ab initio calculations at the HF/6-31G* level demonstrate that the model molecules may have a planar conformation. Bigger macrocycles, for example, 7PAM, 8PAM, and 9PAM, result in several energy minima. The boatlike conformation is the most energetically favored form. Based on the conformational analysis, a novel method for analyzing the ring-strain energy was proposed and used. In view of their potential applications as electronic materials, the electronic structures of a series of PAMs are also investigated. The LUMO-HOMO gaps of the planar PAMs show an odd-even difference behavior. In addition, the HOMOs of the planar species 3PAM, 5PAM, 7PAM, and 9PAM are doubly degenerated.

Acetylene↗

Carbolithiation of diphenylacetylene as a stereoselective route to (Z)-tamoxifen and related tetrasubstituted olefins.

Carbolithiation of diphenylacetylene can be exploited to generate (E)-1-lithio-1,2-diphenylalkyl-1-enes which can be reacted in situ with triisopropylborate to stereoselectively provide (E)-1,2-diphenyl-1-alkylene boronic acids. These tetrasubstituted vinylboronic acids served as versatile intermediates for the generation of tetrasubstituted olefins with retention of stereochemistry. The application of this method for the stereoselective synthesis of (Z)-tamoxifen and related analogues is described.

Acetylene↗