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Dithiazolo[5,4‐ b :4′,5′‐ d ]phosphole: A Highly Luminescent Electron‐Accepting Building Block
Author(s) -
He Xiaoming,
Woo Alva Y. Y.,
BorauGarcia Javier,
Baumgartner Thomas
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204375
Subject(s) - phosphole , moiety , luminescence , chemistry , fluorene , quantum yield , conjugated system , crystallography , fluorescence , photochemistry , materials science , stereochemistry , organic chemistry , physics , polymer , optoelectronics , quantum mechanics
A family of highly emissive dithiazolo[5,4‐ b :4′,5′‐ d ]phospholes has been designed and synthesized. The structures of two trivalent P species, as well as their corresponding P oxides, have been confirmed by X‐ray crystallography. The parent dithiazolo[5,4‐ b :4′,5′‐ d ]phosphole oxide exhibits strong blue photoluminescence at λ em =442 nm, with an excellent quantum yield efficiency of ϕ PL =0.81. The photophysical properties of these compounds can be easily tuned by extension of the conjugation and modification of the phosphorus center. Compared with the established dithieno[3,2‐ b :2′,3′‐ d ]phosphole system, the incorporation of electronegative nitrogen atoms leads to significantly lowered frontier orbital energy levels, as validated by both electrochemistry and theoretical calculations, thus suggesting that the dithiazolo[5,4‐ b :4′,5′‐ d ]phospholes are valuable, air‐stable, n‐type conjugated materials. These new building blocks have been further applied to the construction of an extended oligomer with fluorene. Extension of the dithiazolophosphole core with triazole units through click reactions also provides a suitable N,N‐chelating moiety for metal binding and a representative molecular species was successfully used as a selective colorimetric and fluorescent sensor for Cu II ions.