Tuning the Direction of Intramolecular Charge Transfer and the Nature of the Fluorescent State in a T-Shaped Molecular Dyad

被引:27
作者
Felouat, Abdellah [1 ]
D'Aleo, Anthony [1 ]
Charaf-Eddin, Azzam [1 ,2 ]
Jacquemin, Denis [2 ,3 ]
Le Guennic, Boris [4 ]
Kim, Eunsun [5 ]
Lee, Kwang Jin [5 ]
Woo, Jae Heun [5 ]
Ribierre, Jean-Charles [5 ]
Wu, Jeong Weon [5 ]
Fages, Frederic [1 ]
机构
[1] Aix Marseille Univ, CNRS, CINaM UMR 7325, F-13288 Marseille, France
[2] Univ Nantes, Lab CEISAM, UMR CNRS 6230, F-44322 Nantes 3, France
[3] Inst Univ France, F-75005 Paris 05, France
[4] Univ Rennes 1, CNRS, Inst Sci Chim Rennes, UMR 6226, F-35042 Rennes, France
[5] Ewha Womans Univ, Dept Phys, CNRS, Ewha Int Res Ctr, Seoul, South Korea
基金
新加坡国家研究基金会; 欧洲研究理事会;
关键词
DENSITY-FUNCTIONAL THEORY; PHOTOINDUCED ELECTRON-TRANSFER; PI-CONJUGATED MOLECULES; PHOTOPHYSICAL PROPERTIES; EXCITED-STATES; THIOPHENE DENDRIMERS; TRANSFER EMISSION; TWISTED DONOR; CRUCIFORM; OLIGOTHIOPHENE;
D O I
10.1021/acs.jpca.5b03699
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
Controlling photoinduced intramolecular charge transfer at the molecular; scale is key to the development of molecular devices for nanooptoelectronics. Here, we describe the design, synthesis, electronic characterization, and photophysical properties of two electron donor acceptor molecular systems that consist of tolane and BF2-containing curcuminoid chromophoric subunits connected in a T-shaped arrangement. The two pi-conjugated segment intersect at the electron acceptor dioxaborine core. From steady-state electronic absorption and fluorescence emission, we find that the photophysics of the dialkylamino-substituted analogue is governed by the occurrence of two closely lying excited states. From DFT calculations, we show that excitation in either of these two states results in a distinct shift of the electron density, whether it occurs along the eurcuminoid or tolane moiety. Femtosecond transient absorption spectroscopy confirmed these findings. As a consequence, the nature of the emitting state and the photophysical properties are strongly dependent on solvent polarity. Moreover, these characteristics can also be switched by protonation or complexation at the nitrogen atom of the amino group. These features set new approaches toward the construction of a three-terminal molecular system in which the lateral branch would transduce a change of electronic state and ultimately control charge transport in a molecular-scale device.
引用
收藏
页码:6283 / 6295
页数:13
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