Substituent effects on through-space intervalence charge transfer in cofacial metal–organic frameworks,Faraday Discussions

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Substituent effects on through-space intervalence charge transfer in cofacial metal–organic frameworks
Faraday Discussions ( IF 3.3 ) Pub Date : 2021-07-12 , DOI: 10.1039/d1fd00021g
Patrick W Doheny ₁ , Carol Hua _{1,

2} , Bun Chan ₃ , Floriana Tuna ₄ , David Collison ₄ , Cameron J Kepert ₁ , Deanna M D'Alessandro ₁

Affiliation

Electroactive metal–organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure–function relationships that govern the charge transfer mechanisms is required. Chemical or electrochemical reduction of the framework [Zn(BPPFTzTz)(tdc)]·2DMF, hereafter denoted ZnFTzTz (where BPPFTzTz = 2,5-bis(3-fluoro-4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole), generates mixed-valence states with optical signatures indicative of through-space intervalence charge transfer (IVCT) between the cofacially stacked ligands. Fluorination of the TzTz ligands influences the IVCT band parameters relative to the unsubstituted parent system, as revealed through Marcus–Hush theory analysis and single crystal UV-Vis spectroscopy. Using a combined experimental, theoretical and density functional theory (DFT) analysis, important insights into the effects of structural modifications, such as ligand substitution, on the degree of electronic coupling and rate of electron transfer have been obtained.

中文翻译：

取代基对共面金属-有机框架中空间间隔电荷转移的影响

电活性金属有机框架（MOF）是一类有吸引力的材料，因为它们具有多功能的 3 维结构，其性质可以通过改变组件的氧化还原状态来调节。为了实现这些材料的基本和应用目标，需要更深入地了解控制电荷转移机制的结构 - 功能关系。骨架 [Zn(BPPFTzTz)(tdc)]·2DMF 的化学或电化学还原，以下表示为ZnFTzTz（其中 BPPFTzTz = 2,5-双（3-氟-4-（吡啶-4-基）苯基）噻唑并[5 ,4- d]噻唑），产生具有光学特征的混合价态，指示共面堆叠配体之间的空间间隔电荷转移（IVCT）。正如 Marcus-Hush 理论分析和单晶 UV-Vis 光谱所揭示的那样，TzTz 配体的氟化作用会影响相对于未取代母体系统的 IVCT 带参数。使用组合的实验、理论和密度泛函理论 (DFT) 分析，已经获得了对结构修饰（例如配体取代）对电子耦合程度和电子转移速率影响的重要见解。

更新日期：2021-07-12

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