Metal node engineering in combination with modularity, topological diversity, and porosity of metal–organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal−property trends, i.e., connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectance spectroscopies, and density functional theory calculations. The results of Bader charge analysis and studies employing the Voronoi–Dirichlet partition of crystal structures are also presented. As an example of frameworks with different nodal arrangements, we have chosen MOFs with mononuclear, binuclear, and pentanuclear nodes, primarily consisting of first-row transition metals, that are incorporated in HHTP-, BTC-, and NIP-systems, respectively (HHTP³⁻ = triphenylene-2,3,6,7,10,11-hexaone; BTC³⁻ = 1,3,5-benzenetricarboxylate; and NIP²⁻ = 5-nitroisophthalate). Through probing framework electronic profiles, we demonstrate structure–property relationships, and also highlight the necessity for both comprehensive analysis of trends in metal properties, and novel avenues for preparation of heterometallic multinuclear isoreticular structures, which are critical components for on-demand tailoring of properties in heterometallic systems.

中文翻译：

---

异金属多核节点指导MOF电子行为

金属节点工程与模块化，拓扑多样性和金属有机框架（MOF）的孔隙度相结合，可以推动能源和光电领域的发展。在这项研究中，我们将重点放在具有多核异金属节点的MOF上，以建立金属特性趋势，即，利用感应耦合等离子体质谱，电导率测量，X射线光电子和漫反射光谱学以及密度泛函理论计算，将原子尺度的变化与宏观材料的性能联系起来。还介绍了Bader电荷分析的结果以及采用Voronoi–Dirichlet晶体结构进行研究的结果。作为具有不同节点排列的框架的示例，我们选择了具有单核，双核和五核节点的MOF，这些节点主要由第一行过渡金属组成，分别结合在HHTP，BTC和NIP系统中（HHTP ^3- =三亚苯基-2,3,6,7,10,11-己酮; BTC ^3- = 1,3,5-苯三羧酸酯; NIP ^2-= 5-硝基间苯二甲酸酯）。通过探查框架电子轮廓，我们证明了结构与属性之间的关系，并强调了对金属特性趋势进行综合分析的必要性，以及制备异金属多核等网状结构的新颖途径的必要性，这是按需定制特性的关键组件在异金属系统中。