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Article

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)
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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MDPI and ACS Style

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. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules22111900

AMA Style

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(11):1900. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules22111900

Chicago/Turabian Style

Ishigaki, Yusuke, Yuki Hayashi, Kazuma Sugawara, Takuya Shimajiri, Wataru Nojo, Ryo Katoono, and Takanori Suzuki. 2017. "9,10-Dihydrophenanthrene with Two Spiro(dibenzocycloheptatriene) Units: A Highly Strained Caged Hydrocarbon Exhibiting Reversible Electrochromic Behavior" Molecules 22, no. 11: 1900. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules22111900

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