STRUCTURE OF THE TWISTED-INTRAMOLECULAR-CHARGE-TRANSFER EXCITED SINGLET AND TRIPLET-STATES OF 4-(DIMETHYLAMINO)BENZONITRILE AS STUDIED BY NANOSECOND TIME-RESOLVED INFRARED-SPECTROSCOPY

被引：97

作者：

HASHIMOTO, M ^{[1
]}

HAMAGUCHI, H ^{[1
]}

机构：

[1] KANAGAWA ACAD SCI & TECHNOL,KAWASAKI,KANAGAWA 213,JAPAN

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 20期

关键词：

D O I：

10.1021/j100020a008

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Nanosecond time-resolved infrared spectroscopy has been used to study the structure and dynamics of the excited electronic states of 4-(dimethylamino)benzonitrile (DMABN) in polar and nonpolar solvents. In a polar solvent butanol, two distinct transient species were observed. The first species with a few nanosecond lifetime has been identified as the twisted-intramolecular-charge-transfer (TICT) singlet excited state and the second species having an oxygen-sensitive lifetime as the TICT triplet state of DMABN. Both the singlet and triplet TICT states show large downshifts (> 120 cm(-1)) of the C=N stretch frequency, indicating that the charge transfer has a significant effect on the structure of the cyano group. In a nonpolar solvent hexane, only one transient species was detected. This species has been assigned to the non-CT triplet excited state of DMABN from the observed oxygen quenching effect.

引用

页码：7875 / 7877

页数：3

共 16 条

[1] CONSIDERATIONS ON THE DIPOLE-MOMENT OF MOLECULES FORMING THE TWISTED INTRAMOLECULAR CHARGE-TRANSFER STATE
BAUMANN, W
BISCHOF, H
FROHLING, JC
BRITTINGER, C
RETTIG, W
ROTKIEWICZ, K
[J]. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1992, 64 (01) : 49 - 72
[2] ELECTRON-TRANSFER IN FLEXIBLE MOLECULES AND MOLECULAR-IONS
GRABOWSKI, ZR
[J]. PURE AND APPLIED CHEMISTRY, 1993, 65 (08) : 1751 - 1756
[3] GRABOWSKI ZR, 1979, NOUV J CHIM, V3, P443
[4] Hamaguchi H., 1987, Vibrational spectra and structure. A series of Advances. Vol.16, P227
[5] CONSTRUCTION OF A VERSATILE MICROSECOND TIME-RESOLVED INFRARED SPECTROMETER
IWATA, K
HAMAGUCHI, H
[J]. APPLIED SPECTROSCOPY, 1990, 44 (09) : 1431 - 1437
[6] JONKER SA, 1991, CHEM PHYS LETT, V195, P36
[7] IR SPECTRA OF ANION-RADICALS OF AROMATIC MONO-NITRILES, AND ELECTRON TRANSITIONS BETWEEN ANION RADICALS AND NEUTRAL MOLECULES
JUCHNOVS.I
TSVETANO.C
PANAYOTO.I
[J]. MONATSHEFTE FUR CHEMIE, 1969, 100 (06): : 1980 - +
[8] NONRADIATIVE DEACTIVATION AND TRIPLET-STATES IN DONOR ARYL ACCEPTOR COMPOUNDS (DIALKYLAMINOBENZONITRILES)
KOHLER, G
GRABNER, G
ROTKIEWICZ, K
[J]. CHEMICAL PHYSICS, 1993, 173 (02) : 275 - 290
[9] LAU A, 1993, TIME RESOLVED VIBRAT, V6
[10] Lippert E., 1962, ADV MOL SPECTROSC, P443, DOI DOI 10.1016/B978-1-4832-1332-3.50070-6

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