PMID- 24410238
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20140818
LR  - 20140113
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 140
IP  - 1
DP  - 2014 Jan 7
TI  - Electronic and vibronic properties of a discotic liquid-crystal and its charge 
      transfer complex.
PG  - 014903
LID - 10.1063/1.4856815 [doi]
AB  - Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible 
      light absorption and rapid charge transfer characteristics, being favorable 
      properties for photovoltaic (PV) applications. We present a detailed study of the 
      electronic and vibrational properties of the prototypic 1:1 mixture of discotic 
      2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone 
      (TNF). It is shown that intermolecular charge transfer occurs in the ground state 
      of the complex: a charge delocalization of about 10(-2) electron from the HAT6 
      core to TNF is deduced from both Raman and our previous NMR measurements [L. A. 
      Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. 
      Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 
      13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor 
      interface. A combined analysis of density functional theory calculations, 
      resonant Raman and UV-VIS absorption measurements indicate that fast relaxation 
      occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal 
      modes with lower lying electronic states. Relatively slower relaxation in the 
      visible region the excited CT-band of the complex is also indicated, which likely 
      involves motions of the TNF nitro groups. The fast quinoidal relaxation process 
      in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single 
      benzene unit, suggesting that the underlying vibronic coupling mechanism can be 
      generic for polyaromatic hydrocarbons. Both the presence of ground state CT 
      dipoles and relatively slow relaxation processes in the excited CT band can be 
      relevant concerning the design of DLC based organic PV systems.
FAU - Haverkate, Lucas A
AU  - Haverkate LA
AD  - Reactor Institute Delft, Faculty of Applied Sciences, Delft University of 
      Technology, Mekelweg 15, 2629JB Delft, The Netherlands.
FAU - Zbiri, Mohamed
AU  - Zbiri M
AD  - Institut Laue Langevin, 38042 Grenoble Cedex 9, France.
FAU - Johnson, Mark R
AU  - Johnson MR
AD  - Institut Laue Langevin, 38042 Grenoble Cedex 9, France.
FAU - Carter, Elizabeth
AU  - Carter E
AD  - Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, 
      NSW 2008, Australia.
FAU - Kotlewski, Arek
AU  - Kotlewski A
AD  - ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL∕136 
      Delft, The Netherlands.
FAU - Picken, S
AU  - Picken S
AD  - ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL∕136 
      Delft, The Netherlands.
FAU - Mulder, Fokko M
AU  - Mulder FM
AD  - Reactor Institute Delft, Faculty of Applied Sciences, Delft University of 
      Technology, Mekelweg 15, 2629JB Delft, The Netherlands.
FAU - Kearley, Gordon J
AU  - Kearley GJ
AD  - Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, 
      NSW 2234, Australia.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
EDAT- 2014/01/15 06:00
MHDA- 2014/01/15 06:01
CRDT- 2014/01/14 06:00
PHST- 2014/01/14 06:00 [entrez]
PHST- 2014/01/15 06:00 [pubmed]
PHST- 2014/01/15 06:01 [medline]
AID - 10.1063/1.4856815 [doi]
PST - ppublish
SO  - J Chem Phys. 2014 Jan 7;140(1):014903. doi: 10.1063/1.4856815.