Kleine Alexander, Mankel Charlotte, Hainthaler Andrea, Wächtler Maria, Dietzek-Ivanšić Benjamin, Schubert Ulrich S, Jäger Michael
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany.
Institute for Physical Chemistry (IPC), Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany.
Inorg Chem. 2024 Dec 9;63(49):23233-23247. doi: 10.1021/acs.inorgchem.4c03693. Epub 2024 Nov 24.
In this contribution, the divergent modular synthesis of photoredox-active dyads, triads and a tetrad descending from one ligand precursor is presented by combining "chemistry-on-the-ligand", stepwise complexation and "chemistry-on-the-complex" with minimal synthetic efforts. In the final step, Pd-mediated borylation and subsequent Suzuki-Miyaura cross-coupling was employed to introduce the different (multi)donor moieties at the preassembled P-A dyad subunit. The (spectro-)electrochemical data revealed preserved redox properties of the subunits and minimal driving force for oxidative quenching by the naphthalene diimide-based (NDI) acceptor and, thus, high-energy charge separated (CS) states. Time-resolved transient absorption and emission data revealed the formation of long-lived CS states in the polymer-based triads, i.e., the CS lifetime is extended by 2 orders of magnitude in comparison to the molecular triad. The long-lived CS state (13.2 μs) of the conjugated polycarbazole (Carb) multidonor demonstrates that the rational modular design and efficient synthesis of advanced photoredox-active assemblies can be readily achieved by late-stage diversification utilizing the "chemistry-on-the-complex" approach.
在本论文中，通过结合“配体上的化学”、逐步络合和“络合物上的化学”，以最小的合成工作量，展示了从一种配体前体出发，光氧化还原活性二元体、三元体和四元体的发散式模块化合成。在最后一步中，采用钯介导的硼化反应及随后的铃木-宫浦交叉偶联反应，在预组装的P-A二元体亚基上引入不同的（多）供体部分。（光谱）电化学数据表明，亚基的氧化还原性质得以保留，基于萘二酰亚胺（NDI）受体的氧化猝灭驱动力极小，因此形成了高能电荷分离（CS）态。时间分辨瞬态吸收和发射数据表明，基于聚合物的三元体中形成了长寿命的CS态，即与分子三元体相比，CS寿命延长了2个数量级。共轭聚咔唑（Carb）多供体的长寿命CS态（13.2 μs）表明，利用“络合物上的化学”方法进行后期多样化，可以轻松实现先进光氧化还原活性组装体的合理模块化设计和高效合成。
