title: Polytwistane.
abstract: Twistane, C10H16, is a classic D2-symmetric chiral hydrocarbon that has been studied for decades due to its fascinating stereochemical and thermodynamic properties. Here we propose and analyze in detail the contiguous linear extension of twistane with ethano (ethane-1,2-diyl) bridges to create a new chiral, C2-symmetric hydrocarbon nanotube called polytwistane. Polytwistane, (CH)n, has the same molecular formula as polyacetylene but is composed purely of C(sp(3))-H units, all of which are chemically equivalent. The polytwistane nanotube has the smallest inner diameter (2.6 Å) of hydrocarbons considered to date. A rigorous topological analysis of idealized polytwistane and a C236H242 prototype optimized by B3LYP density functional theory reveals that the polymer has a nonrepeating, alternating σ-helix, with an irrational periodicity parameter and an instantaneous rise (or lead) angle near 15 °. A theoretical analysis utilizing homodesmotic equations and explicit computations as high as CCSD(T)/cc-pVQZ yields the enthalpies of formation Delta(f)H(0)°(twistane) = -1.7 kcal mol(-1) and Delta(f)H(0)°(polytwistane) = +1.28 kcal (mol CH)(-1), demonstrating that the hypothetical formation of polytwistane from acetylene is highly exothermic. Hence, polytwistane is synthetically viable both on thermodynamic grounds and also because no obvious pathways exist for its rearrangement to lower-lying isomers. The present analysis should facilitate the preparation and characterization of this new chiral hydrocarbon nanotube.
authors.affiliation: Center for Computational Chemistry and Department of Chemistry, University of Georgia, Athens, GA 30602 (USA).
authors.forename: Shiblee R
authors.initials: SR
authors.lastname: Barua
authors.forename: Henrik
authors.initials: H
authors.lastname: Quanz
authors.forename: Martin
authors.initials: M
authors.lastname: Olbrich
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner
authors.forename: Dirk
authors.initials: D
authors.lastname: Trauner
authors.forename: Wesley D
authors.initials: WD
authors.lastname: Allen
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D008958:Models, Molecular; D043942:Nanotubes / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000473:Alkanes
keywords: alkanes; chirality; density functional calculations; nanotubes; stereochemistry; thermodynamics