ABSTRACT The straightforward synthesis of redox-active arylazothioformamide (ATF) ligands allows for electronic diversity as to measure the weak-binding interactions of transition metal salts in supramolecular coordination complexes. A small library of para-substituted ATFs was created with varied electronic components to evaluate how electron-donating and electron-withdrawing groups alter binding association constants. Following full characterisation, including single-crystal X-ray diffraction, UV-Vis titration studies were performed using copper(I) salts to assess the Host:Guest binding. Simultaneously, substitutions were evaluated computationally by modelling the Gibbs’ Free Energy change of the rotational barriers from ligand crystal structures to the predicted metal coordinating species and the various complexes. The multi-model association calculations and experimental measurements interplay to help limit error propagations and reliably predict the more accurate binding models. Through a thorough investigation it was found that experimentally, each ligand supports a 2:1 binding model yet may employ unique binding mechanisms to achieve that model. GRAPHICAL ABSTRACT

中文翻译：

---

取代对氧化还原活性芳基偶氮硫甲酰胺配体和铜（I）盐结合相互作用的影响

摘要 氧化还原活性芳基硫代甲酰胺 (ATF) 配体的直接合成允许电子多样性，以测量超分子配位配合物中过渡金属盐的弱结合相互作用。使用各种电子元件创建了一个小型对位取代 ATF 库，以评估给电子和吸电子基团如何改变结合缔合常数。在包括单晶 X 射线衍射在内的完整表征之后，使用铜 (I) 盐进行 UV-Vis 滴定研究以评估 Host:Guest 结合。同时，通过模拟从配体晶体结构到预测的金属配位物质和各种配合物的旋转势垒的吉布斯自由能变化，以计算方式评估取代。多模型关联计算和实验测量相互作用，有助于限制误差传播并可靠地预测更准确的绑定模型。通过彻底调查发现，在实验上，每个配体支持 2:1 结合模型，但可能采用独特的结合机制来实现该模型。图形概要