Heterometallic multinuclear nodes directing MOF electronic behavior

Abstract

<p>Metal node engineering in combination with modularity, topological diversity, and porosity of metal–organic frameworks (MOFs) could advance energy and optoelectronic sectors.</p>

Water-Driven Structural Transformation in Cobalt Trimesate Metal-Organic Frameworks

“…All the patterns reported in Figure 1a,b were equivalent, and they were all different from the patterns reported for other metal trimesates. The structures used for the comparison were obtained by search in articles collection databases [24,[35][36][37][38][39][40][41][42][43][44][45][46]48,[51][52][53][54] and in the Cambridge Structural Database (CCSD, [55]) using as a query in ConQuest one cobalt atom bound to one oxygen atom of a BTC linker and coordinated to two additional oxygen atoms through a single bond. The most intense reflection of the pattern was centered at 10.2 • , corresponding with a d-spacing of 8.7 Å.…”

“…The first material reported as a metal-organic framework by Yaghi et al in 1995 was a cobalt trimesate [36]. Other cobalt trimesates were reported since then for very different applications [37][38][39][40][41][42][43][44][45]. Among them, Co 3 (BTC) [46] is particularly interesting for energy related applications.…”

Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks

“… 78 Thus, these examples demonstrated that integration of actinides or transition metals can significantly affect the electronic profiles of actinide-containing materials. However, to build a correlation between electronic properties and metal node nuclearity, similar to that reported for transition metal-based MOFs, 90 large samples of data and application of a systematic approach is necessary.…”

Heterometallic Actinide‐Containing Photoresponsive Metal‐Organic Frameworks: Dynamic and Static Tuning of Electronic Properties

“…Although there are clear benefits to this approach, the majority of literature reports focus on crystallographic aspects as the first step for understanding the structure of actinide-hybrids,a nd only very recently have studies providing am ore fundamental glimpse into material properties emerged. [27][28][29][30] This aspect highlights that the field of actinide-containing metal-organic materials is ar elatively new direction that will grow substantially during the next decade.T his sector faces challenges such as the development of safety protocols and material instability,b ut foreshadows the possibility of solving challenges related to radioactive waste accumulation through new directions focused on practical applications. [31] Herein, we tailor optoelectronic properties of heterometallic An-MOFs,M IV -MOFs (M = Ua nd Th), through the design of heterometallic nodes,integration of stimuli-responsive organic moieties,a nd inclusion of redox-active guests (Scheme 1).…”

“…Merging the distinct advantages of MOFs (e.g., ultra‐high porosity, crystallinity, robustness, and modularity) with the characteristics of actinides (e.g., large cations and f ‐electrons) could be the key to repurposing radionuclide waste or even extend future applications of actinide‐based hybrids to the practical realm. Although there are clear benefits to this approach, the majority of literature reports focus on crystallographic aspects as the first step for understanding the structure of actinide‐hybrids, and only very recently have studies providing a more fundamental glimpse into material properties emerged [27–30] . This aspect highlights that the field of actinide‐containing metal‐organic materials is a relatively new direction that will grow substantially during the next decade.…”