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The Art of Acetylenic Scaffolding: Rings, Rods, and Switches
Author(s) -
Brøndsted Nielsen Mogens,
Diederich François
Publication year - 2002
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.10022
Subject(s) - isomerization , acetylene , conjugated system , molecular switch , dispersity , homo/lumo , chemistry , scaffold , materials science , carbon fibers , photochemistry , crystallography , polymer chemistry , catalysis , organic chemistry , polymer , molecule , composite material , medicine , biomedical engineering , composite number
Acetylenic scaffolding with derivatives of tetraethynylethene (TEE, 3,4‐diethynylhex‐3‐ene‐1,5‐diyne) and ( E )‐1,2‐diethynylethene (DEE, ( E )‐hex‐3‐ene‐1,5‐diyne) provides carbon‐rich compounds with interesting physicochemical properties. Thus, these modules are building blocks for monodisperse, linearly π‐conjugated oligomers [polytri(acetylene)s, PTAs] extending in length beyond 10nm, and for large, macrocyclic, all‐carbon cores (dehydroannulenes and expanded radialenes) exhibiting strong chromophoric properties. The advanced materials' properties were strongly influenced by the presence of electron‐donating substituents at the lateral positions, decreasing the decreasing the (HOMO–LUMO) gap in both PTAs and expanded radialenes. Arylated TEEs were found to undergo photochemically induced cis – trans isomerization, paving the way for applications as light‐driven molecular switches in optoelectronic devices. Derivatives of 1,3‐diethynylallene are new modules that offer the prospect of scaffolding in an orthogonal manner; that is, they represent precursors for helical oligomers. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 189–198,2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10022