A Merry Dance Across the π-Cloud: Tracking the Transformation of a 2,7-Substituted Dihydropyrene Through a Thermally Stimulated Single-Crystal-to-Single-Crystal Reaction

被引：2
|
作者：
Roemer, Max [1 ,5 ]
Gillespie, Angus A. [1 ]
Turner, Gemma F. [1 ]
Flematti, Gavin R. [1 ]
Hobday, Claire L. [2 ,3 ]
Sobolev, Alexandre N. [4 ]
Wild, Duncan A. [1 ]
Nealon, Gareth L. [1 ,4 ]
Piggott, Matthew J. [1 ]
Moggach, Stephen A. [1 ]
Koutsantonis, George A. [1 ]
机构：
[1] Univ Western Australia, Sch Mol Sci, Chem, Crawley, WA 6009, Australia
[2] Univ Edinburgh, Ctr Sci Extreme Condit, Edinburgh EH9 3FJ, Midlothian, Scotland
[3] Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3FJ, Midlothian, Scotland
[4] Univ Western Australia, Ctr Microscopy Characterisat & Anal, Crawley, WA 6009, Australia
[5] Univ Sydney, Sch Chem, Sydney, NSW 2109, Australia
来源：
CRYSTAL GROWTH & DESIGN | 2021年 / 21卷 / 11期
基金：
澳大利亚研究理事会;
关键词：
MOLECULES BEARING SUBSTITUENTS; ORGANIC FRAMEWORK; PHASE-TRANSITION; SOLID-STATE; ELECTRON CLOUD; DIMETHYLDIHYDROPYRENE; METACYCLOPHANEDIENE; REARRANGEMENT; COMPLEXES; RELEASE;
D O I：
10.1021/acs.cgd.1c01013
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The novel 2,7-bis((TIPS)ethynyl)-10b,10c-diethyl-dihydropyrene photochrome (TIPS = triisopropylsilyl) was observed to undergo thermal rearrangement to 2,7-bis(TIPS-ethynyl)-pyrene in the solid state. The transformation proceeds stepwise with ethyl groups "dancing" out of the dihydropyrene core toward the periphery of the polycyclic framework. The formation of two regioisomers occurs initially and is followed by two progressive de-ethylations to give a pyrene. This transformation occurs in the solid crystalline state and represents a unique example of a single-crystal-to-single-crystal (SC-SC) transformation involving C-C bond cleavages with hydrocarbon fragments escaping the ordered crystalline structure. Detailed characterizations of the transformation by in situ temperature-dependent X-ray single-crystal diffraction supported by thermal analysis, HPLC-mass spectrometry experiments, NMR spectroscopy, and theoretical calculations, are reported.
引用
收藏
页码：6558 / 6566
页数：9
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