Synthesis and photophysics of a novel photocatalyst for hydrogen production based on a tetrapyridoacridine bridging ligand
Synthesis and photophysics of a novel photocatalyst for hydrogen production based on a tetrapyridoacridine bridging ligand
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DOI：
10.1016/j.chemphys.2011.11.027
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发表时间：
2012-01-17
期刊：
影响因子：
2.3
通讯作者：
Dietzek, Benjamin
中科院分区：
文献类型：
--
作者：
Karnahl, Michael;Kuhnt, Christian;Dietzek, Benjamin
分子光催化剂可以根据对其化学和光物理性质的深入了解，在分子水平上选择性地调整其功能。该贡献报告了新型分子光催化剂 [(tbbpy)(2)Ru(tpac)PdCl2](2+) RutpacPd（其中 tpac = 四吡啶并[3,2-a:2',3'-c:3 '',2 ''-h:2''',3'''-j]吖啶）及其单核结构单元的合成和光物理表征。此外，还介绍了 RutpacPd 的详细光催化活性测量结果。与经过充分研究的 RutpphzPd（其中 tpphz = 四吡啶并[3,2-a:2',3'-c:300,2 ''-h: 2''',3'''-j]吩嗪）配合物相比，将 tpac 配体引入分子框架中提供了一条减少水影响的潜在途径。水对 tpphz-配体中电子转移过程的明显影响源于水与吩嗪氮原子形成氢键的可能性，并且当用吖啶单元取代吩嗪时可能会减少。将详细讨论这种结构变化对催化性能和潜在的超快分子内电荷转移行为的影响。 (C) 2011 Elsevier B.V. 保留所有权利。
Molecular photocatalysts allow for selectively tuning their function on a molecular level based on an in-depth understanding of their chemical and photophysical properties. This contribution reports the synthesis and photophysical characterization of the novel molecular photocatalyst [(tbbpy)(2)Ru(tpac)PdCl2](2+) RutpacPd (with tpac = tetrapyrido[3,2-a:2',3'-c:3 '',2 ''-h:2''',3'''-j]acridine) and its mononuclear building block. Furthermore, detailed photocatalytic activity measurements of RutpacPd are presented. The introduction of the tpac-ligand into the molecular framework offers a potential route to reduce the impact of water as compared to the well-studied class of RutpphzPd (with tpphz = tetrapyrido[3,2-a:2',3'-c:300,2 ''-h: 2''',3'''-j] phenazine) complexes. The distinct impact of water on the electron-transfer processes in tpphz-ligands stems from the possibility of water to form hydrogen bonds to the phenazine nitrogen atoms and will potentially reduced when replacing the phenazine by the acridine unit. The effect of this structural variation on the catalytic properties and the underlying ultrafast intramolecular charge transfer behavior will be discussed in detail. (C) 2011 Elsevier B. V. All rights reserved.