Conductive Metal‐Organic Frameworks: Electronic Structure and Electrochemical Applications

Abstract

Smarter and minimization of devices are consistently substantial to shape the energy landscape. Significant amounts of endeavours have come forward as promising steps to surmount this formidable challenge. It is undeniable that material scientists were contemplating smarter material beyond purely inorganic or organic materials. To our delight, metal‐organic frameworks (MOFs), an inorganic‐organic hybrid scaffold with unprecedented tunability and smart functionalities, have recently started their journey as an alternative. In this review, we focus on such propitious potential of MOFs that was untapped over a long time. We cover the synthetic strategies and (or) post‐synthetic modifications towards the formation of conductive MOFs and their underlying concepts of charge transfer with structural aspects. We addressed theoretical calculations with the experimental outcomes and spectroelectrochemistry, which will trigger vigorous impetus about intrinsic electronic behaviour of the conductive frameworks. Finally, we discussed electrocatalysts and energy storage devices stemming from conductive MOFs to meet energy demand in the near future.

Morphology induced enhanced photoconductivity of a phthalocyanine-based benzimidazole linked two-dimensional conjugated covalent organic polymer

“…2,[8][9][10][11][12] In this regard, 2D polymers with columnar assemblies, so called 2D covalent organic frameworks (COFs), have emerged as ideal platforms for constructing photoconductive devices since they fulfil both descript criteria, but have the shortcoming of requiring elaborate structural design and considerable synthetic effort to obtain specific alignment. [13][14][15][16][17][18][19] Moreover, studies also report that such design also increases the photo responsive speed of polymers compared to disordered 2D p-conjugated polymers. 8 However, one should note that, while 2D columnar assembly increases the conductivity of the generated electricity due to additional conductive pathways, at the same time it causes a reduction of electric generation due to limited absorption of photons by adsorbents.…”

“…2,8–12 In this regard, 2D polymers with columnar assemblies, so called 2D covalent organic frameworks (COFs), have emerged as ideal platforms for constructing photoconductive devices since they fulfil both descript criteria, but have the shortcoming of requiring elaborate structural design and considerable synthetic effort to obtain specific alignment. 13–19 Moreover, studies also report that such design also increases the photo responsive speed of polymers compared to disordered 2D π-conjugated polymers. 8…”

Ferroelectric coordination metal complexes based on structural and electron dynamics

“…Such materials exhibit a variety of interesting properties that originate from electron dynamics associated with the metal centres (e.g. magnetism, luminescence, and redox-activity), [34][35][36][37][38][39][40][41][42][43] while maintaining the characteristics of organic ferroelectrics, while ferroelectric metal complexes might be expected to exhibit unique synergistic properties/phenomena that are derived from the co-occurrence of structural and electron dynamics. To date, investigations concerned with ferroelectric metal complexes have been mainly conducted on porous metal-organic frameworks (MOFs) and organic-inorganic perovskites also containing porous structures, in which their polarity has been realized by the ordering of solvent molecules within the pores and/or the presence of polar bridging ligands.…”

Crystal Packing-Driven Selective Hg(II) Ion Sensing Using Thiazolothiazole-Based Water-Stable Zinc Metal–Organic Framework

“…Luminescent metal–organic frameworks (MOFs) with high porosity and unparalleled tunability have been used in versatile applications, such as chemical sensing, bioimaging, energy-efficient light-emitting diodes, etc., to surmount the formidable challenges. − The tailor-made luminescent MOFs have been utilized in the selective sensing of various ions, solvent molecules, and in pharmaceuticals. ,,− Particularly, a selective and sensitive mercury­(II) ion sensing in MOFs is attributed to either having a nitrogen probe in the scaffold to coordinate with Hg­(II) or sulfur center to bind strongly due to a soft acid-soft base interaction (Table S1). However, the favorable interaction of soft acid Hg­(II) and hard base oxygen rendering sensitive and selective mercury sensing, albeit having nitrogen and sulfur center in the framework material, is elusive.…”