Excited-State Dynamics of Bis(9-fluorenyl)methane and its Derivative 9-(9-Ethylfluorenyl)-9′-fluorenylmethane: Steric Effect on Energetics and Dynamics of Ground- and Excited-State Conformations

被引：2

作者：

Boo, Bong Hyun ^{[1
]}

Lee, Minyung ^{[2
]}

Jeon, Ki-Seok ^{[1
]}

Kim, Seung-Joon ^{[3
]}

机构：

[1] Chungnam Natl Univ, Dept Chem, Taejon 305764, South Korea

[2] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea

[3] HanNam Univ, Dept Chem, Taejon 300791, South Korea

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2014年 / 118卷 / 12期

基金：

新加坡国家研究基金会;

关键词：

INTRAMOLECULAR EXCIMER FORMATION; CORRELATED MOLECULAR CALCULATIONS; DENSITY-FUNCTIONAL THEORY; CONSISTENT BASIS-SETS; GAUSSIAN-BASIS SETS; CONFIGURATION-INTERACTION; EXCITATION-ENERGIES; FLUORESCENCE; APPROXIMATION; DI-9H-FLUOREN-9-YLDIMETHYLSILANE;

D O I：

10.1021/jp411878r

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：

Intramolecular excimer formation of bis(9-fluorenyl)methane (BFM) and 9-(9'-ethylfluorenyl)-9-fluorenylmethane (EFFM), in which an ethyl group is substituted to a 9-H atom in BFM, was studied by means of steady-state and time-resolved fluorescence. Ab initio and DFT calculations enabled the prediction of three conformers as stable species of orthogonal, trans-gauche, and gauche-gauche. The theoretical and experimental results reveal that the substitution effect is also found to appreciably influence the energies, spectroscopy, and kinetics associated with the interconversion of various conformers of the diaryl compounds. We have not observed the rising components in the excimer fluorescence decay of BFM and EFFM in PMMA as observed in the liquid solutions probably because of the existence of the sandwich conformer responsible for the excimer fluorescence prior to the laser irradiation.

引用

页码：2269 / 2278

页数：10

共 34 条

[1] Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory
Bauernschmitt, R
Ahlrichs, R
[J]. CHEMICAL PHYSICS LETTERS, 1996, 256 (4-5) : 454 - 464
[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
[3] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR
BECKE, AD
[J]. PHYSICAL REVIEW A, 1988, 38 (06): : 3098 - 3100
[4] Boo BH, 2005, J PHYS CHEM A, V109, P4280, DOI [10.1021/jp0406621, 10.1021/jp040662l]
[5] Infrared and Raman spectroscopy of bis(4,4-dimethyl-2,5-cyclohexadien-1-ylidene). Vibrational assignment by Hartree-Fock and density functional theory calculations and depolarization method
Boo, BH
Lee, SY
Na, HK
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (16) : 2679 - 2684
[6] Transient Absorption Spectroscopy of Bis(9-fluorenyl)methane: Elucidation of Triplet-Triplet Absorption
Boo, Bong Hyun
[J]. JOURNAL OF THE KOREAN PHYSICAL SOCIETY, 2011, 59 (05) : 3201 - 3204
[7] Fluorescence Spectroscopic and Time-Dependent DFT Studies for Intramolecular Excimer Formation of Di-9H-fluoren-9-yldimethylsilane: Dynamics and Energetics for Conformational Change
Boo, Bong Hyun
Ryu, Su Young
Yoon, Minjoong
Koh, Sang Gon
Park, Kyung Lae
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (34) : 8969 - 8974
[8] Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold
Casida, ME
Jamorski, C
Casida, KC
Salahub, DR
[J]. JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (11) : 4439 - 4449
[9] CONFORMATION-DEPENDENT INTRAMOLECULAR EXCIMER FORMATION IN JET-COOLED 1,3-DIPHENYLPROPANE
CHAKRABORTY, T
LIM, EC
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (49) : 17505 - 17508
[10] CHUNG YB, 1991, CHEM PHYS LETT, V176, P453, DOI 10.1016/0009-2614(91)90236-3

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