Abuhadba Sara, Lin Neo, Maltese Anthony, Ferek Michelle, Chen Angela, Fuqua Charlotte, Martzloff Rilee, Mani Tomoyasu, Esipova Tatiana V
Department of Chemistry and Biochemistry, Loyola University Chicago, Chicago, Illinois 60660, United States.
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, United States.
J Phys Chem B. 2024 Dec 19;128(50):12549-12558. doi: 10.1021/acs.jpcb.4c06886. Epub 2024 Dec 8.
π-Extended BODIPY compounds are a compelling class of fluorophores known for their red or near-infrared (NIR) emission and high quantum yields, which are crucial for applications in materials science, solar cells, and biomedical imaging. Our recent study shows that we can use a dibenzo-fused BODIPY as a singlet-driven red photoredox catalyst by installing a simple electron donor group. Despite their potential in these applications, knowledge of electron transfer reactions involving dibenzo-fused BODIPY is still scarce. This paper presents the synthesis and systematic photophysical investigations of donor-acceptor (D-A) and donor-bridge-acceptor (D-bridge-A) series of dibenzo-fused BODIPY with ,'-diethylaniline fragments serving as an electron donor. We examined the effects of methyl substituents and bridge length on the rates of photoinduced electron transfer (PeT). Through steady-state and time-resolved optical spectroscopy, electrochemistry, and density functional theory calculations, we elucidated how these simple structural modifications controlled the PeT rates and examined their impacts on catalytic activities in atom transfer radical addition (ATRA) reactions. Our results support previous studies on the (D-A) design of red heavy atom-free photocatalysts.
π-扩展的BODIPY化合物是一类引人注目的荧光团，以其红色或近红外（NIR）发射和高量子产率而闻名，这对于材料科学、太阳能电池和生物医学成像中的应用至关重要。我们最近的研究表明，通过安装一个简单的电子供体基团，我们可以将二苯并稠合的BODIPY用作单线态驱动的红色光氧化还原催化剂。尽管它们在这些应用中具有潜力，但涉及二苯并稠合BODIPY的电子转移反应的知识仍然匮乏。本文介绍了以,'-二乙苯胺片段作为电子供体的供体-受体（D-A）和供体-桥-受体（D-bridge-A）系列二苯并稠合BODIPY的合成及系统的光物理研究。我们研究了甲基取代基和桥长度对光诱导电子转移（PeT）速率的影响。通过稳态和时间分辨光谱、电化学以及密度泛函理论计算，我们阐明了这些简单的结构修饰如何控制PeT速率，并研究了它们对原子转移自由基加成（ATRA）反应中催化活性的影响。我们的结果支持了先前关于无重原子红色光催化剂（D-A）设计的研究。
