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Aromatic β‐Diketone as a Novel Anchoring Ligand in Iridium(III) Complexes for Dye‐Sensitized Solar Cells
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-07-27 , DOI: 10.1002/ejic.202000372 Stanislav I. Bezzubov 1 , Irina S. Zharinova 2 , Alfiya A. Khusyainova 2 , Yuri M. Kiselev 3 , Ilya V. Taydakov 4 , Evgenia A. Varaksina 4 , Mikhail T. Metlin 4 , Aiyyna S. Tobohova 4 , Vladislav M. Korshunov 4 , Sergei A. Kozyukhin 2 , Vladimir D. Dolzhenko 3
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-07-27 , DOI: 10.1002/ejic.202000372 Stanislav I. Bezzubov 1 , Irina S. Zharinova 2 , Alfiya A. Khusyainova 2 , Yuri M. Kiselev 3 , Ilya V. Taydakov 4 , Evgenia A. Varaksina 4 , Mikhail T. Metlin 4 , Aiyyna S. Tobohova 4 , Vladislav M. Korshunov 4 , Sergei A. Kozyukhin 2 , Vladimir D. Dolzhenko 3
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A novel β‐diketone ligand bearing a thiophene moiety and an anchoring Ph‐COOCH3 unit has been designed, prepared and used in synthesis of cyclometalated benzimidazole‐based iridium(III) complexes for application in dye‐sensitized solar cells (DSSC). The replacement of traditional 4,4'‐dicarboxy‐2,2'‐bipyridine by this aromatic β‐diketone results in excellent tuning the redox potentials and excited state properties of these IrIII complexes, one of which exhibits good efficiency when used as a dye in DSSC. All the complexes demonstrate reversible redox behavior, with oxidation potentials (Ir4+/Ir3+) strongly depending on the electron‐donor/withdrawing nature of the substituents in the cyclometalated ligands. Surprisingly, the latter has just a little effect on their luminescence spectra, in which structured emission bands are observed. Time‐resolved spectroscopic studies in combination with DFT calculations show that the complexes emit light by mixed 3MLCT–3LC excited states predominantly composed of the diketone ligand‐centered triplet state.
中文翻译：
芳香族β-二酮作为染料敏化太阳能电池铱（III）配合物中的新型配体
已经设计，制备了一种新型的带有噻吩部分和锚定Ph-COOCH 3单元的β-二酮配体，并用于合成环金属化的苯并咪唑基铱（III）配合物，用于染料敏化太阳能电池（DSSC）。用这种芳香族β-二酮替代传统的4,4'-二羧基-2,2'-联吡啶可很好地调节这些Ir III配合物的氧化还原电势和激发态性质，其中一种用作α-二酮时表现出良好的效率。 DSSC中的染料。所有配合物均表现出可逆的氧化还原行为，具有氧化电位（Ir 4+ / Ir 3+）在很大程度上取决于环金属化配体中取代基的电子给体/吸收性质。令人惊讶的是，后者对其发光光谱几乎没有影响，在该光谱中观察到结构化的发射带。结合DFT计算的时间分辨光谱研究表明，复合物通过3 MLCT- 3 LC混合激发态发光，这些激发态主要由以二酮配体为中心的三重态组成。
更新日期：2020-09-09
中文翻译：
芳香族β-二酮作为染料敏化太阳能电池铱（III）配合物中的新型配体
已经设计，制备了一种新型的带有噻吩部分和锚定Ph-COOCH 3单元的β-二酮配体，并用于合成环金属化的苯并咪唑基铱（III）配合物，用于染料敏化太阳能电池（DSSC）。用这种芳香族β-二酮替代传统的4,4'-二羧基-2,2'-联吡啶可很好地调节这些Ir III配合物的氧化还原电势和激发态性质，其中一种用作α-二酮时表现出良好的效率。 DSSC中的染料。所有配合物均表现出可逆的氧化还原行为，具有氧化电位（Ir 4+ / Ir 3+）在很大程度上取决于环金属化配体中取代基的电子给体/吸收性质。令人惊讶的是，后者对其发光光谱几乎没有影响，在该光谱中观察到结构化的发射带。结合DFT计算的时间分辨光谱研究表明，复合物通过3 MLCT- 3 LC混合激发态发光，这些激发态主要由以二酮配体为中心的三重态组成。
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