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.
Due to the atomic precession and exotic photophysical properties, silver cluster assembled materials (CAMs) are explored as functional nanomaterials in recent times. Although a few numbers of thiolate protected silver...
A soft acid-soft base interaction is highly predictable. However, we demonstrate how the crystal packing of the newly synthesized zinc framework [Zn 2 (5-AIA) 2 (DPTTZ)]•DMF (where 5-AIA = 5-aminoisophthalic acid, DPTTZ = N,N′-di(4-pyridyl)thiazolo- [5,4-d]thiazole, DMF = N,N′-dimethylformamide) directs an unexpected interaction between the soft acid Hg(II) and the hard base oxygen instead of having a soft center like nitrogen and sulfur in the system attributed to a strong solvent interaction and a favorable ionic radius of Hg(II) ion for oxygen chelation. This engenders selective Hg(II) ion sensing through a "turn-off" emission quenching in water (limit of detection = (2.174 ± 0.06) × 10 −9 M) along with natural water resources and in a broad pH range. A quantum-chemical calculation elucidates the turn-off quenching mechanism and favorable Hg(II) interaction with encompassed oxygen atoms inside the framework.
We report the reversible polymorphic phase transition of [Ni6(PET)12] (PET = phenylethanethiol) and its effect on the conductivity. This cluster's self-assembly leads to two polymorphic structures with distinct conductivity, caused...
We demonstrate direct evidence of photoinduced through-space intervalence charge transfer (IVCT) between two cofacially arranged redox-active pairs in metal-organic frameworks and their dynamic variation with their molecular separation. Two homologous MOFs [Co 2 (NDC) 2 (DPTTZ) 2 ]. DPTTZ. DMF, 1 and [Co 2 (BDC) 2 (DPTTZ) 2 ]. DMF, 2 (where NDC = naphthalene dicarboxylate, BDC = benzene dicarboxylate, DPTTZ = N, N'-di(4-pyridyl)thiazolo- [5,4d]thiazole, DMF = N, N'-dimethyl formamide) are considered for this, whose intra-dimer distance of redox-active DPTTZ ligands differs ca. 1 Å from one system to another. Spectroelectrochemical study detects the formation of IVCT band at the NIR region between cofacially oriented DPTTZ molecules in both MOFs. Transient spectroscopy shows faster charge separation as well as charge recombination when intra-dimer distance is lesser (in MOF 2) due to stronger electronic coupling. We quantify the extent of IVCT by charge transfer integral calculation; and also by optical pump terahertz probe spectroscopy, where MOF 2 shows three times higher carrier mobility due to lesser inter-DPTTZ distance than MOF 1. These findings reveal a more localized aspect of through-space IVCT between cofacially organized redox-active pair in a three-dimensional framework.
Emissive inorganic-organic hybrid materials open up a new prospect of fast and efficient heavy metal ion sensing in aqueous medium. Here, we demonstrate a highly sensitive Lead (II) ion detection...
Charge‐transfer excited state (CTES) defines the ability to split photon energy into work producing redox equivalents suitable for photocatalysis. Here, we report inter‐net CTES formation within a two‐fold catenated crystalline metal–organic framework (MOF), constructed with two linkers, N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide (DPNDI) and 2,6‐dicarboxynaphthalene (NDC). The structural flexibility puts two complementary linkers from two nets in a proximal position to interact strongly. Supported by the electrochemical and steady‐state electronic spectroscopic data, this ground‐state interaction facilitates forming CTES that can be populated by direct excitation. We map the dynamics of the CTES which persists over a few nanoseconds and highlight the utilities of such relatively long‐lived CTES as enhanced conductivity of the MOF under light over that measured in dark and as a proof‐of‐the‐principle test, photo‐reduction of methyl viologen under white light.
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