Segura Camilo, Ormazabal-Toledo Rodrigo, García-Beltrán Olimpo, Squeo Benedetta M, Bachmann Cristian, Flores Catalina, Osorio-Román Igor O
Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Ñuñoa, Región Metropolitana, Chile.
Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmaceúticas, Universidad de Chile, Dr. Carlos Lorca Tobar 964, Independencia, Región Metropolitana, Chile.
Chemistry. 2024 Feb 16;30(10):e202302940. doi: 10.1002/chem.202302940. Epub 2023 Dec 28.
Aggregation-Induced Emission (AIE) luminogens have garnered significant interest due to their distinctive applications in different applications. Among the diverse molecular architectures, those based on triphenylamine and thiophene hold prominence. However, a comprehensive understanding of the deactivation mechanism both in solution and films remains lacking. In this study, we synthesized and characterized spectroscopically two AIE luminogens: 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carbaldehyde (TTY) and 5'-(4-(bis(4-methoxyphenyl)amino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde (TTO). Photophysical and theoretical analyses were conducted in both solution and PMMA films to understand the deactivation mechanism of TTY and TTO. In diluted solutions, the emission behavior of TTY and TTO is influenced by the solvent, and the deactivation of the excited state can occur via locally excited (LE) or twisted intramolecular charge transfer (TICT) state. In PMMA films, rotational and translational movements are constrained, necessitating emission solely from the LE state. Nevertheless, in the PMMA film, excimers-like structures form, resulting in the emergence of a longer wavelength band and a reduction in emission intensity. The zenith of emission intensity occurs when molecules are dispersed at higher concentrations within PMMA, effectively diminishing the likelihood of excimer-like formations. Luminescent Solar Concentrators (LSC) were fabricated to validate these findings, and the optical efficiency was studied at varying concentrations of luminogen and PMMA.
聚集诱导发光(AIE)发光剂因其在不同应用中的独特用途而备受关注。在各种分子结构中,基于三苯胺和噻吩的结构尤为突出。然而,目前仍缺乏对其在溶液和薄膜中的失活机制的全面理解。在本研究中,我们合成了两种AIE发光剂并进行了光谱表征:5-(4-(双(4-甲氧基苯基)氨基)phenyl)噻吩-2-甲醛(TTY)和5'-(4-(双(4-甲氧基苯基)氨基)phenyl)-[2,2'-联噻吩]-5-甲醛(TTO)。在溶液和聚甲基丙烯酸甲酯(PMMA)薄膜中进行了光物理和理论分析,以了解TTY和TTO的失活机制。在稀释溶液中,TTY和TTO的发射行为受溶剂影响,激发态的失活可通过局域激发(LE)或扭曲分子内电荷转移(TICT)状态发生。在PMMA薄膜中,旋转和平移运动受到限制,仅需从LE状态发射。然而,在PMMA薄膜中会形成准分子样结构,导致出现更长波长的波段并降低发射强度。当分子以较高浓度分散在PMMA中时,发射强度达到峰值,有效降低了准分子样形成的可能性。制备了发光太阳能聚光器(LSC)以验证这些发现,并研究了在发光剂和PMMA不同浓度下的光学效率。