Meta-conjugation and excited-state coupling in phenylacetylene dendrimers

被引:99
作者
Gaab, KM [1 ]
Thompson, AL [1 ]
Xu, JJ [1 ]
Martínez, TJ [1 ]
Bardeen, CJ [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
关键词
D O I
10.1021/ja029489h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Traditional pictures of optical properties in phenylacetylene dendrimers view the molecule as a collection of independent chromophores, linked by meta-substitution at the central phenyl ring. While this picture is reasonable for explaining the observed absorption trends, it breaks down in describing the emission behavior. We utilize a combination of ab initio theory and experiment to demonstrate that differences in the absorbing and emitting states can be described using an exciton model with very weak chromophore coupling for the absorption geometry and strong coupling for the emission geometry. This result may have significant implications for the design of energy-funneling dendrimeric molecules. Copyright © 2003 American Chemical Society.
引用
收藏
页码:9288 / 9289
页数:2
相关论文
共 22 条
  • [1] Light-harvesting dendrimers
    Adronov, A
    Fréchet, JMJ
    [J]. CHEMICAL COMMUNICATIONS, 2000, (18) : 1701 - 1710
  • [2] Light harvesting and energy transfer in laser-dye-labeled poly(aryl ether) dendrimers
    Adronov, A
    Gilat, SL
    Fréchet, JMJ
    Ohta, K
    Neuwahl, FVR
    Fleming, GR
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (06) : 1175 - 1185
  • [3] 2ND-ORDER PERTURBATION-THEORY WITH A CASSCF REFERENCE FUNCTION
    ANDERSSON, K
    MALMQVIST, PA
    ROOS, BO
    SADLEJ, AJ
    WOLINSKI, K
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (14) : 5483 - 5488
  • [4] Identification of the light-absorbing states in tolane with potential relevance to self-similar phenylacetylene dendrimers
    Borst, DR
    Chou, SG
    Pratt, DW
    [J]. CHEMICAL PHYSICS LETTERS, 2001, 343 (3-4) : 289 - 295
  • [5] Multireference perturbation theory for large restricted and selected active space reference wave functions
    Celani, P
    Werner, HJ
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (13) : 5546 - 5557
  • [6] Energy transfer in dendritic macromolecules: Molecular size effects and the role of an energy gradient
    Devadoss, C
    Bharathi, P
    Moore, JS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (40) : 9635 - 9644
  • [7] RATE EXPRESSIONS FOR EXCITATION TRANSFER .2. ELECTRONIC CONSIDERATIONS OF DIRECT AND THROUGH-CONFIGURATION EXCITON RESONANCE INTERACTIONS
    HARCOURT, RD
    SCHOLES, GD
    GHIGGINO, KP
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1994, 101 (12) : 10521 - 10525
  • [8] Kasha M., 1965, PURE APPL CHEM, V11, P371, DOI [10.1351/pac196511030371, DOI 10.1351/PAC196511030371]
  • [9] Ultrafast dynamics of electronic excitations in a light-harvesting phenylacetylene dendrimer
    Kleiman, VD
    Melinger, JS
    McMorrow, D
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (24): : 5595 - 5598
  • [10] AN EFFICIENT 2ND-ORDER MC SCF METHOD FOR LONG CONFIGURATION EXPANSIONS
    KNOWLES, PJ
    WERNER, HJ
    [J]. CHEMICAL PHYSICS LETTERS, 1985, 115 (03) : 259 - 267