Dynamic dimer copper coordination redox shuttles
Dynamic dimer copper coordination redox shuttles
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DOI：
10.1016/j.chempr.2021.10.017
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发表时间：
2022-02-10
期刊：
影响因子：
23.5
通讯作者：
Freitag, Marina
中科院分区：
文献类型：
--
作者：
Benesperi, Iacopo;Michaels, Hannes;Freitag, Marina
基于金属配位络合物的常规氧化还原介体通过金属中心的氧化态的变化进行电子转移。然而，电子转移动力学偏移时，preorganized配体约束的配位球的重组向优选的氧化态。相反，我们在这里报告二聚铜（II/I）氧化还原电对，其中两个金属中心的氧化/还原程度决定了二聚体和单体复合物的动态形成：二聚体（Cu（I））2过渡到单体的Cu（II）。双（噻唑/吡咯）-联吡啶四齿配体稳定独特的氧化还原系统的两种氧化态。动态二聚体氧化还原介体提供了一种可行的双电子氧化还原机制，通过抑制复合和快速电荷传输来开发高效的混合太阳能电池。密度泛函理论计算揭示了内部重组能量低至0.27 eV的单电子转移，标志着二聚络合物上级氧化还原系统的单一复合物作为液体和潜在的固态电解质。
Conventional redox mediators based on metal coordination complexes undergo electron transfer through the change in oxidation state of the metal center. However, electron transfer kinetics are offset toward preferred oxidation states when preorganized ligands constrain the reorganization of the coordination sphere. In contrast, we report here on dimeric copper(II/I) redox couples, wherein the extent of oxidation/reduction of two metal centers dictates the dynamic formation of dimer and monomer complexes: the dimeric (Cu(I))2 transitions to monomers of Cu(II). The bis(thiazole/ pyrrole)-bipyridine tetradentate ligands stabilize both oxidation states of the unique redox systems. The dynamic dimer redox mediators offer a viable two-electron redox mechanism to develop efficient hybrid solar cells through inhibited recombination and rapid charge transport. Density functional theory calculations reveal inner reorganization energies for single-electron transfer as low as 0.27 eV, marking the dimeric complexes superior redox systems over single complexes as liquid and potentially solid-state electrolytes.