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Molecules 2017, 22(11), 1900; doi:10.3390/molecules22111900

9,10-Dihydrophenanthrene with Two Spiro(dibenzocycloheptatriene) Units: A Highly Strained Caged Hydrocarbon Exhibiting Reversible Electrochromic Behavior

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
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Received: 19 October 2017 / Revised: 3 November 2017 / Accepted: 3 November 2017 / Published: 4 November 2017
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Abstract

The title dispiro hydrocarbon 1 was designed as a new electrochromic material. This multiply clamped hexaphenylethane-type electron donor was prepared from 2,2’-diiodobiphenyl via biphenyl-2,2’-diylbis(dibenzotropylium) 22+ salt. X-ray analysis of 1 revealed a highly strained structure as reflected by an elongated “ethane” bond [bond length: 1.6665(17) Å] and nearly eclipsed conformation. The weakened bond was cleaved upon two-electron oxidation to regenerate the deeply colored dication 22+. The reversible interconversion between 1 and 22+ is accompanied not only by a drastic color change but also by C–C bond formation/cleavage. Thus, the voltammogram showed a pair of well-separated redox waves, which is characteristic of “dynamic redox (dyrex)” behavior. The tetrahydro derivative of 1 with two units of spiro(dibenzocycloheptadiene), which suffers from more severe steric congestion, was also prepared. The crystallographically determined bond length for the central C–C bond [1.705(4) Å] is greatest among the values reported for 9,9,10,10-tetraaryl-9,10-dihydrophenanthrene derivatives. View Full-Text
Keywords: polycyclic aromatic hydrocarbons; long bond; dynamic redox system; dication; dibenzotropylium; electrochromism; through-bond interaction polycyclic aromatic hydrocarbons; long bond; dynamic redox system; dication; dibenzotropylium; electrochromism; through-bond interaction
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Ishigaki, Y.; Hayashi, Y.; Sugawara, K.; Shimajiri, T.; Nojo, W.; Katoono, R.; Suzuki, T. 9,10-Dihydrophenanthrene with Two Spiro(dibenzocycloheptatriene) Units: A Highly Strained Caged Hydrocarbon Exhibiting Reversible Electrochromic Behavior. Molecules 2017, 22, 1900.

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