近日，青岛大学胡继祥团队研究了光活性配合物中电子转移动力学的溶剂配位定向控制。相关论文发表在2025年10月9日出版的《结构化学》杂志上。

光致变色材料在防伪器件、光开关和分子传感器等方面的应用备受关注。然而，溶剂分子，特别是配位溶剂，对电子转移（ET）光致变色系统的影响仍然知之甚少。

研究组合成了一系列同构金属-有机配合物（MOCs）， [Mn(ADC)(L)]_n （ADC = 9,10-蒽二羧酸，L = DMF为1，DMA为2，MEA为3，DMSO为4）来研究其溶剂-变色行为。这些MOCs在室温氙灯照射下均表现出典型的自由基致变色现象。值得注意的是，配位溶剂分子显著调节光致变色反应速率。在所研究的化合物中，化合物1的反应最快，而化合物3的反应最慢。这种速率的变化与它们结构内最佳电子转移路径长度的差异有关。

具体来说，溶剂分子调节CH···π相互作用距离与它们的位阻和电子性质有关。短C-H···π路径在光激发下促进更有效的电子转移，从而导致更快的光致变色响应速率。此外，光照激发了光生成自由基和Mn²⁺中心之间的磁耦合，导致室温磁化强度显著增加，显示出光磁响应。该研究表明，协调溶剂选择有效地控制了光致ET行为，为设计先进的光活性材料提供了新的见解。

附：英文原文

Title: Solvent-coordination directed control of electron transfer dy-namics in photoactive complexes

Author: anonymous

Issue&Volume: 2025-10-09

Abstract: Photochromic materials attract significant attention for their applications in anticounterfeiting devices, optical switches and molecular sensors. However, the influence of solvent molecules, particularly coordinated solvents, on electron transfer (ET) photochromic systems remains poorly understood. In this study, we synthesized a series of isostructural metal-organic complexes (MOCs), [Mn(ADC)(L)]n (ADC = 9,10-anthracenedicarboxylic acid, L = DMF for 1, DMA for 2, MEA for 3, and DMSO for 4) to investigate the solvent-chromic behavior. All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature. It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate. Among the compounds studied, compound 1 exhibits the fastest response, while compound 3 shows the slowest. This variation in rate correlates with differences in the optimal electron transfer (ET) path length within their structures. Specifically, solvent molecules regulate the CH···π interaction distance through their steric hindrance and electronic properties. Shorter CH···π paths facilitate more efficient electron transfer upon photoexcitation, thus leading to faster photochromic response rates. Furthermore, illumination actuates magnetic couplings between photogenerated radicals and Mn2+ centers, resulting in a significant increase in room-temperature magnetization, demonstrating a photomagnetic response. This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior, providing new insights for designing advanced photoactive materials.

DOI: 10.1016/j.cjsc.2025.100753

Source: https://cjsc.ac.cn/cms/issues/899