Evolution of Nonmirror Image Fluorescence Spectra in Conjugated Polymers and Oligomers

被引:21
作者
Gallaher, Joseph K. [1 ,2 ]
Chen, Kai [1 ,2 ]
Huff, Gregory S. [2 ,3 ]
Prasad, Shyamal K. K. [1 ,2 ]
Gordon, Keith C. [2 ,3 ]
Hodgkiss, Justin M. [1 ,2 ]
机构
[1] Victoria Univ Wellington, Sch Chem & Phys Sci, Wellington 6140, New Zealand
[2] MacDiarmid Inst Adv Mat & Nanotechnol, Wellington, New Zealand
[3] Univ Otago, Dept Chem, Dunedin 9016, New Zealand
来源
JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2016年 / 7卷 / 17期
关键词
ABSORPTION-SPECTRA; ENERGY-TRANSFER; PHOTOLUMINESCENCE SPECTROSCOPY; EXCITON RELAXATION; CHARGE SEPARATION; LOWEST SINGLET; TRIPLET-STATES; CHAIN-LENGTH; HEXAMETHYLSEXITHIOPHENE; OLIGOTHIOPHENES;
D O I
10.1021/acs.jpclett.6b01185
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
The nonmirror image relationship between absorption and fluorescence spectra of conjugated polymers contrasts with most organic chromophores and is widely considered a signature of interchromopohore energy funneling. We apply broad-band ultrafast fluorescence spectroscopy to resolve the evolution of fluorescence spectra for dilute solutions of conjugated oligothiophenes, where no energy transfer is possible. Fluorescence spectra evolve from a mirror image of absorption, which lacks vibronic structure, toward a spectrally narrower and vibronically structured species on the hundreds of femtosecond to early picosecond time scale. Our analysis of this fluorescence spectral evolution shows that a broad distribution of torsional conformers is driven to rapidly planarize in the excited state, including in solid films, which is supported by Raman spectroscopy and quantum chemical modeling. Our data have important implications for understanding different energy-transfer regimes that are delineated by structural relaxation.
引用
收藏
页码:3307 / 3312
页数:6
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[1]   The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors [J].
Bakulin, Artem A. ;
Rao, Akshay ;
Pavelyev, Vlad G. ;
van Loosdrecht, Paul H. M. ;
Pshenichnikov, Maxim S. ;
Niedzialek, Dorota ;
Cornil, Jerome ;
Beljonne, David ;
Friend, Richard H. .
SCIENCE, 2012, 335 (6074) :1340-1344
[2]   Ultrafast Relaxation of the Poly(3-hexylthiophene) Emission Spectrum [J].
Banerji, Natalie ;
Cowan, Sarah ;
Vauthey, Eric ;
Heeger, Alan J. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2011, 115 (19) :9726-9739
[3]   Spectral broadening and diffusion by torsional motion in biphenyl [J].
Beenken, WJD ;
Lischka, H .
JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (14)
[4]   THEORETICAL INVESTIGATION OF THE LOWEST SINGLET AND TRIPLET-STATES IN POLY(PARA-PHENYLENE VINYLENE)OLIGOMERS [J].
BELJONNE, D ;
SHUAI, Z ;
FRIEND, RH ;
BREDAS, JL .
JOURNAL OF CHEMICAL PHYSICS, 1995, 102 (05) :2042-2049
[5]   Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers [J].
Beljonne, D ;
Pourtois, G ;
Silva, C ;
Hennebicq, E ;
Herz, LM ;
Friend, RH ;
Scholes, GD ;
Setayesh, S ;
Müllen, K ;
Brédas, JL .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2002, 99 (17) :10982-10987
[6]   Influence of chain length and derivatization on the lowest singlet and triplet states and intersystem crossing in oligothiophenes [J].
Beljonne, D ;
Cornil, J ;
Friend, RH ;
Janssen, RAJ ;
Bredas, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (27) :6453-6461
[7]   Theoretical Study of Torsional Disorder in Poly(3-alkylthiophene) Single Chains: Intramolecular Charge-Transfer Character and Implications for Photovoltaic Properties [J].
Bjorgaard, Josiah A. ;
Kose, Muhammet E. .
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[8]   OPTICAL-EXCITATIONS OF POLY-3-ALKYLTHIOPHENE FILMS AND SOLUTIONS [J].
BOTTA, C ;
LUZZATI, S ;
TUBINO, R ;
BORGHESI, A .
PHYSICAL REVIEW B, 1992, 46 (20) :13008-13016
[9]   A femtosecond fluorescence study of vibrational relaxation and cooling dynamics of UV dyes [J].
Braem, Olivier ;
Penfold, Thomas J. ;
Cannizzo, Andrea ;
Chergui, Majed .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2012, 14 (10) :3513-3519
[10]   Regio-Regular Oligo and Poly(3-hexyl thiophene): Precise Structural Markers from the Vibrational Spectra of Oligomer Single Crystals. [J].
Brambilla, Luigi ;
Tommasini, Matteo ;
Botiz, Ioan ;
Rahimi, Khosrow ;
Agumba, John O. ;
Stingelin, Natalie ;
Zerbi, Giuseppe .
MACROMOLECULES, 2014, 47 (19) :6730-6739