PHOTOINDUCED ELECTRON-TRANSFER AND ENERGY-TRANSFER PROCESSES OF BIACETYL IMPRISONED IN A HEMICARCERAND

Citation
Aj. Parola et al., PHOTOINDUCED ELECTRON-TRANSFER AND ENERGY-TRANSFER PROCESSES OF BIACETYL IMPRISONED IN A HEMICARCERAND, Journal of the American Chemical Society, 118(46), 1996, pp. 11610-11616
Citations number
61
Categorie Soggetti
Chemistry
ISSN journal
00027863
Volume
118
Issue
46
Year of publication
1996
Pages
11610 - 11616
Database
ISI
SICI code
0002-7863(1996)118:46<11610:PEAEPO>2.0.ZU;2-A
Abstract
The energy- and electron-transfer quenching processes of the lowest tr iplet excited state of biacetyl (2,3-butanedione) imprisoned in a hemi carcerand have been systematically investigated in CH2Cl2 solution at room temperature. Twenty potential quenchers have been used, including ten triplet energy accepters (mostly, aromatic hydrocarbons) and nine electron donors (mostly, aromatic amines). Bimolecular rate constants for the quenching processes were obtained by Stern-Volmer analysis an d compared with those found for the quenching of free biacetyl. In the electron-transfer processes, aromatic amines with oxidation potential from +0.015 V (N,N,N',N'-tetramethyl-p-phenylenediamine) to +0.83 V ( diphenylamine) quench free biacetyl at the diffusion-controlled limit, whereas for imprisoned biacetyl the rate constant decreases (roughly in a linear manner) from 4.0 x 10(8) to 1.2 x 10(5) M(-1) s(-1) As far as energy-transfer is concerned, the rate constant for the quenching of free biacetyl increases with decreasing Delta G degrees and reaches the diffusion-controlled plateau value (k(q) similar to 10(10) M(-1) s(-1)) for Delta G degrees similar to 0.1 eV, whereas for imprisoned b iacetyl a scattered, bell-shaped log k(q) vs Delta G degrees plot is o btained, with a maximum value (similar to 10(6) M(-1) s(-1)) much belo w the diffusion-controlled limit. The results obtained show that the w alls of the hemicarcerand allow only very weak electronic interaction between incarcerated triplet biacetyl and external quenchers. A brief discussion of the results obtained in the light of current energy- and electron-transfer theories is presented.