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

        Felouat, Abdellah,D’Alé,o, Anthony,Charaf-Eddin, Azzam,Jacquemin, Denis,Le Guennic, Boris,Kim, Eunsun,Lee, Kwang Jin,Woo, Jae Heun,Ribierre, Jean-Charles,Wu, Jeong Weon,Fages, Fré,dé American Chemical Society 2015 The Journal of physical chemistry A Vol.119 No.24

        <P>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 BF<SUB>2</SUB>-containing curcuminoid chromophoric subunits connected in a T-shaped arrangement. The two π-conjugated segments 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 curcuminoid 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.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpcafh/2015/jpcafh.2015.119.issue-24/acs.jpca.5b03699/production/images/medium/jp-2015-03699g_0001.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/jp5b03699'>ACS Electronic Supporting Info</A></P>

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        Ethynylene-analogues of hemicurcuminoids: Synthesis and ground- and excited properties of their boron difluoride complexes

        Š,tefane, Bogdan,Pož,gan, Franc,Kim, Eunsun,Choi, Eunyoung,Ribierre, Jean-Charles,Wu, Jeong Weon,Ponce-Vargas, Miguel,Le Guennic, Boris,Jacquemin, Denis,Canard, Gabriel,Zaborova, Elena,Fages Applied Science Publishers 2017 Dyes and pigments Vol.141 No.-

        <P><B>Abstract</B></P> <P>The synthesis, characterization and (TD)-DFT calculations of the electrochemical and photophysical properties of novel ethynylene-analogues of hemicurcuminoids are described. These dyes are both emissive in solution and in the solid state. While compounds that emit through an efficient charge transfer (CT) state show solvatochromic behaviour associated with low fluorescence quantum yields, those lacking of donor groups show high fluorescence quantum yields of 70–80%, in solution. The latter dyes also present the advantage to emit in the solid state in the visible region with fluorescence quantum yields up to 23%. Their condensed phase spectrum can be bathochromically shifted to the near infrared region (742 nm) by appending a strong donor group.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Synthesis of new fluorophores based on hemicurcuminoid boron difluoride. </LI> <LI> Photophysical study reveals strong emission of the dyes not containing charge transfer states. </LI> <LI> Fluorescence properties of dyes in their condensed phase show aggregation induced emission. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

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