Corrente Giuseppina Anna, Parisi Francesco, Maltese Vito, Cospito Sante, Imbardelli Daniela, La Deda Massimo, Beneduci Amerigo
Laboratory of Physical Chemistry, Materials and Processes for Industry, Environment and Cultural Heritage, Department of Chemistry and Chemical Technologies, University of Calabria, Via P. Bucci, Cubo 15D, 87036 Arcavacata di Rende, Italy.
Laboratory of Inorganic Molecular Materials, Department of Chemistry and Chemical Technologies, Institute of Nanotechnology CNR-Nanotec, University of Calabria, Via P. Bucci, Cubo 14C, 87036 Arcavacata di Rende, Italy.
Molecules. 2021 Nov 11;26(22):6818. doi: 10.3390/molecules26226818.
Electrofluorochromic devices (EFCDs) that allow the modulation of the light emitted by electroactive fluorophores are very attractive in the research field of optoelectronics. Here, the electrofluorochromic behaviour of a series of squaraine dyes was studied for the first time. In solutions, all compounds are photoluminescent with maxima located in the range 665-690 nm, characterized by quantum yields ranging from 30% to 4.1%. Squaraines were incorporated in a polymer gel used as an active layer in all-in-one gel switchable EFCDs. An aggregation induced quenching occurs in the gel phase, causing a significant decrease in the emission quantum yield in the device. However, the squaraines containing the thieno groups (thienosquaraines, TSQs) show a panchromatic emission and their electrofluorochromism allows the tuning of the fluorescence intensity from 500 nm to the near infrared. Indeed, the application of a potential difference to the device induces a reversible quenching of their emission that is significantly higher and occurs at shorter switching times for TSQs-based devices compared to the reference squaraine dye (DIBSQ). Interestingly, the TSQs fluorescence spectral profile becomes more structured under voltage, and this could be explained by the shift of the aggregates/monomer equilibrium toward the monomeric species, due to electrochemical oxidation, which causes the disassembling of aggregates. This effect may be used to modulate the colour of the fluorescence light emitted by a device and paves the way for conceiving new electrofluorochromic materials based on this mechanism.
能够调制电活性荧光团发射光的电致荧光变色器件(EFCDs)在光电子学研究领域极具吸引力。在此,首次研究了一系列方酸菁染料的电致荧光变色行为。在溶液中,所有化合物均具有光致发光特性,其最大发射波长位于665 - 690 nm范围内,量子产率在30%至4.1%之间。方酸菁被掺入一种聚合物凝胶中,用作一体化凝胶可切换EFCDs的活性层。在凝胶相中发生聚集诱导猝灭,导致器件中的发射量子产率显著降低。然而,含噻吩基的方酸菁(噻吩方酸菁,TSQs)呈现全色发射,并且它们的电致荧光变色特性使得荧光强度能够从500 nm调至近红外。实际上,给器件施加电位差会导致其发射发生可逆猝灭,与参考方酸菁染料(DIBSQ)相比,基于TSQs的器件的猝灭程度显著更高且发生的切换时间更短。有趣的是,TSQs的荧光光谱轮廓在电压作用下变得更加规整,这可以通过聚集体/单体平衡向单体物种的移动来解释,这是由于电化学氧化导致聚集体解体。这种效应可用于调制器件发射的荧光颜色,并为基于此机制构思新型电致荧光变色材料铺平了道路。