Luminescent, Redox-Active Diphenothiazine Dumbbells Expanded by Conjugated Arenes and Heteroarenes

Autor:	Jan Schönhaber, Martina Hauck, Thomas Müller, Raluca Turdean, Karin Memminger, Frank Rominger
Rok vydání:	2010
Předmět:	Photoexcitation Suzuki reaction Chemistry Excited state Organic Chemistry Coplanarity Electronic structure Conjugated system Photochemistry Luminescence Conformational isomerism
Zdroj:	The Journal of Organic Chemistry. 75:8591-8603
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo101997t
Popis:	Dumbbell-shaped diphenothiazines bridged by conjugatively linked (hetero)aromatic moieties were synthesized in a modular fashion by Suzuki-Miyaura coupling in good yields. The electronic structure was studied by DFT computations, determining the geometry optimized lowest energy conformers and scrutinizing the Kohn-Sham FMOs. The torsional deviation from coplanarity is predominantly influencing the electronic structure, i.e., by deviation from ideal overlap and maximal electron transmission. The reversible oxidation potentials assigned to the phenothiazinyl electrophores in most cases can thereby be qualitatively rationalized. All dumbbell-shaped diphenothiazines are strongly luminescent, which can be attributed to extended π-electron conjugation with considerable excited state electronic coupling as a consequence of large structural and electronic distributional changes upon photoexcitation.
Databáze:	OpenAIRE
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