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Crystal and solution structures of photochromic spirobenzothiopyran. First full characterization of the meta-stable colored species.
MedLine Citation:
PMID:  11798328     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Full elucidation for stable, colorless, and meta-stable colored structures of a new spirobenzothiopyran has been achieved both in the solid state and in a solution. 1',3',3'-Trimethyl-6-nitrospiro[(2H)-1-benzothiopyran-2,2'-indoline] with an ester group as a substituent at the 8-position of 1-sp shows photochromism. The blue-green colored species resulted from UV irradiation (365 nm) in one minute and spontaneously bleaches within one minute in acetone and methanol at 27 degrees C. UV exposure (365 nm) of 1-sp in methanol for 3 h at room temperature results in the growth of deep blue needlelike single crystals of the open form of spirobenzothiopyran, photomerocyanine 1-pmc, whose structures in the solid state and in solution were obtained unambiguously. The X-ray structural analysis of 1-pmc revealed the molecular structure of the zwitterionic photomerocyanine with s-trans,s-trans conformation. 1-pmc is soluble to polar solvents and thermally returns to 1-sp. In the DMSO solution, 1-pmc is found to return slowly to 1-sp (1-pmc gave only 18% of 1-sp for 30 min at 22 degrees C). The detailed NMR studies in DMSO-d(6) including COSY and NOE techniques as well as isotope labeling of the compound showed the structure with s-trans,s-cis conformation in a solution.
Authors:
Masafumi Hirano; Kohtaro Osakada; Hiroyuki Nohira; Akira Miyashita
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  67     ISSN:  0022-3263     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2002 Jan 
Date Detail:
Created Date:  2002-01-18     Completed Date:  2002-04-02     Revised Date:  2003-10-31    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  533-40     Citation Subset:  -    
Affiliation:
Department of Applied Chemistry, Faculty of Engineering, Saitama University, 255 Shimo-ohkubo, Saitama, Saitama 338-8570, Japan. hrc@cc.tuat.ac.jp
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