Sittig Maria, Tom Jessica C, Elter Johanna K, Schacher Felix H, Dietzek Benjamin
Department of Functional Interfaces, Leibniz Institute of Photonic Technology Jena, Albert-Einstein-Strasse 9, 07745, Jena, Germany.
Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743, Jena, Germany.
Chemistry. 2021 Jan 13;27(3):1072-1079. doi: 10.1002/chem.202003815. Epub 2020 Dec 4.
Quinoline photobases exhibit a distinctly higher pK in their electronically excited state than in the ground state, thereby enabling light-controlled proton transfer reactions, for example, in molecular catalysis. The absorption of UV light translates to a pK jump of approximately 10 units, as established for small-molecule photobases. This contribution presents the first synthesis of quinoline-based polymeric photobases prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. The integration of quinolines as photobase chromophores within copolymers offers new possibilities for light-triggered proton transfer in nanostructured materials, that is, in nanoparticles, at surfaces, membranes and interfaces. To exploit the light-triggered reactivity of photobases within such materials, we first investigated how the ground- and excited-state properties of the quinoline unit changes upon polymer integration. To address this matter, we combined absorption and emission spectroscopy with time-resolved transient-absorption studies to reveal photoinduced proton-transfer dynamics in various solvents. The results yield important insights into the thermodynamic and kinetic properties of these polymeric quinoline photobases.
喹啉光碱在其电子激发态下的pK值比基态下明显更高,从而能够实现光控质子转移反应,例如在分子催化中。对于小分子光碱而言,紫外光的吸收会导致pK值跃升约10个单位。本文首次报道了通过可逆加成-断裂链转移(RAFT)聚合制备喹啉基聚合物光碱。将喹啉作为光碱发色团整合到共聚物中,为纳米结构材料(即纳米颗粒、表面、膜和界面)中的光触发质子转移提供了新的可能性。为了利用此类材料中光碱的光触发反应性,我们首先研究了喹啉单元在聚合物整合后其基态和激发态性质如何变化。为了解决这个问题,我们将吸收光谱和发射光谱与时间分辨瞬态吸收研究相结合,以揭示在各种溶剂中的光致质子转移动力学。结果为这些聚合物喹啉光碱的热力学和动力学性质提供了重要见解。