Studies on unimolecular and bimolecular photoprocesses of a newly synthesized selenium compound, 7-chloro-2-phenyl-9H-[1]-benzopyrano[3,2-b]-selenophene-9-one (SeP).
Using steady state/time resolved spectroscopic and electrochemical techniques the spectroscopic and photophysical studies were made on a novel synthesized selenophene compound SeP in nonpolar methylcyclohexane (MCH), polar aprotic acetonitrile (ACN) and polar protic ethanol (EtOH) solvents at the ambient temperature as well as at 77 K. Both from the studies on unimolecular and bimolecular photoprocesses this selenophene compound was found to possess several electronic levels, 1Bb, 1La, 1Lb (all are of pi pi* nature and 1Lb is hidden within 1La band envelop like the characteristics of most of the acenes) and 1(nO pi*) state arising due to carbonyl oxygen atom. In polar ACN environment this nO pi* state disappears because it moves within the envelop of intense 1La band due to large destabilization. Large overlapping of different band systems within the 1La band of SeP was confirmed from the observed depolarization effect. The lack of phosphorescence of SeP both in MCH and EtOH rigid glassy matrix at 77 K has been inferred due to large vibronic interactions between closely lying triplets of the corresponding 1nO pi* and 1Lb states. From the bimolecular investigations, it reveals that SeP acts as a good electron donor in presence of the well known electron acceptor 9 cyanoanthracene (9CNA). Transient absorption spectra measured by laser flash photolysis technique demonstrate the formation of ion-pair when the acceptor is excited. From the analysis of the fluorescence quenching data it seemingly indicates that the major contribution in the diminution of the fluorescence intensity of the acceptor 9CNA in presence of SeP is not only due to the photoinduced electron transfer (ET) but also originates from static type (instantaneous) quenching processes along with external heavy atom effect. The possibility of occurrence of photoinduced ET reaction in Marcus inverted region is hinted.
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A K
AK
Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Calcutta.
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S K
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Mallik
A K
AK
Ganguly
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D000097:Acetonitriles / Q000737:chemistry; D001578:Benzopyrans / Q000737:chemistry*; D004563:Electrochemistry; D000431:Ethanol / Q000737:chemistry; D049449:Luminescence; D016566:Organoselenium Compounds / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013696:Temperature
C442851:7-chloro-2-phenyl-9H-(1)-benzopyrano(3,2-b)-selenophene-9-one; D000097:Acetonitriles; D001578:Benzopyrans; D016566:Organoselenium Compounds; D012997:Solvents; D000431:Ethanol; C032159:acetonitrile