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Rina, Yesmin Akter; Schmidt, Joseph A. R.
doi: 10.1039/d4dt00826jpmid: 38757291
This perspective summarizes our group's extensive research in the realm of organometallic lanthanide complexes, while also placing the catalytic reactions supported by these species within the context of known lanthanide catalysis worldwide, with a specific focus on phosphorus-based catalytic reactions such as intermolecular hydrophosphination and hydrophosphinylation. α-Metalated N,N-dimethylbenzylamine ligands have been utilized to generate homoleptic lanthanide complexes, which have subsequently proven to be highly active lanthanum-based catalysts. The main goal of our research program has been to enhance the catalytic efficiency of lanthanum-based complexes, which began with initial successes in the stoichiometric synthesis of organometallic lanthanide complexes and utilization of these species in catalytic hydrophosphination reactions. Not only have these species supported traditional lanthanide catalysis, such as the hydrophosphination of heterocumulenes like carbodiimides, isocyanates, and isothiocyanates, but they have also been effective for a plethora of catalytic reactions tested thus far, including the hydrophosphinylation and hydrophosphorylation of nitriles, hydrophosphination and hydrophosphinylation of alkynes and alkenes, and the heterodehydrocoupling of silanes and amines. Each of these catalytic transformations is meritorious in its own right, offering new synthetic routes to generate organic scaffolds with enhanced functionality while concurrently minimizing both waste generation and energy consumption. Objectives: We aim for the research summary presented herein to inspire and encourage other researchers to investigate f-element based stoichiometric and catalytic reactions. Our efforts in this field began with the recognition that potassium salts of benzyldimethylamine preferred deprotonation at the α-position, rather than the ortho-position, and we wondered if this regiochemistry would be retained in the formation of lanthanide complexes. The pursuit of this simple idea led first to a series of structurally fascinating homoleptic organometallic lanthanide complexes with surprisingly good stability. Fundamental studies of the protonolysis chemistry of these complexes ultimately revealed highly versatile lanthanide-based precatalysts that have propelled a catalytic investigation spanning more than a decade. We anticipate that this summative perspective will animate the synthetic as well as biological communities to consider La(DMBA)3-based catalytic methods in the synthesis of functionalized organic scaffolds as an atom-economic, convenient, and efficient methodology. Ultimately, we envision our work making a positive impact on the advancement of novel chemical transformations and contributing to progress in various fields of science and technology.
Zhu, Shaohua; Pang, Haijun; Sun, Zhe; Ullah Khan, Shifa; Mustafa, Ghulam; Ma, Huiyuan; Wang, Xinming; Yang, Guixin
doi: 10.1039/d4dt01261epmid: 38961702
Platinum-based catalysts exhibit outstanding electrocatalytic performance in the hydrogen evolution reaction (HER). However, platinum-based catalysts face significant challenges due to their rarity and high cost. This paper endeavors to shed light on a promising alternative: polyoxometalate (POM)-based catalysts, which possess significant potential for the synthesis of non-noble metal-based catalysts for the HER. Utilizing POMs as raw materials to assemble POM-derived materials, including POM-derived crystalline materials, metal sulfides, phosphides, carbides, nitrides, and so on, has emerged as an effective approach for the synthesis of hydrogen evolution electrocatalysts. This approach offers advantages in both stability and electrocatalytic performance. This comprehensive review navigates through latest progress in the assembly strategy and HER performance of POM-based crystal materials, alongside discussion on transition metal compounds derived from POMs, such as carbides, phosphides, and sulfides. Besides, future developments in POM-derived electrocatalyst regulation of the electrochemical HER are prospected.
Kimberly, Tanner Q.; Frasch, Michelle H.; Kauzlarich, Susan M.
doi: 10.1039/d4dt01322kpmid: 39046257
The field of 2D nanomaterials is ever-growing with a myriad of synthetic advancements that have been used to obtain such materials. There are top-down, as well as bottom-up, fabrication methods for obtaining 2D nanomaterials; however, synthesis of 2D nanomaterials from solution offers a simple scalable way to control size, shape, and surface. This review outlines the recent advances in colloidal polyol synthesis of 2D nanomaterials and provides perspectives on the similarities and differences in various syntheses. Various materials classes are presented and discussed, including metals, oxides, chalcogenides, and halides, that can be synthesized as 2D nanomaterials via a polyol process. Throughout the literature, polyol media is demonstrated to be versatile not only as a solvent and reducing agent for metal precursors but also as a binding and shape-directing agent for many 2D nanomaterials. Polyols also offer the ability to dissolve various surfactants and additives that can further control the morphology and composition of various nanomaterials. In this review, we outline the various 2D materials that have been realized via the solution polyol route.
Dilinaer, A. Dina; J. Jobin, Gabriel; Drover, Marcus W.
doi: 10.1039/d4dt01550apmid: 38976284
The use of metal catalysts to accelerate an organic transformation has proven indispensable for access to structural motifs having applications across medicinal, polymer, materials chemistry, and more. Most catalytic approaches have cast transition metals in the “leading role”; these players mediate important reactions such as C–C cross coupling and the hydrogenation of unsaturated bonds. These catalysts may require collaboration, featuring Lewis acidic or basic additives to promote a desired reaction outcome. Lewis acids can serve to accelerate reactions by way of substrate stabilization and/or activation, and as such, are valuable in optimizing catalytic transformations. A burgeoning area of chemical research which unifies these concepts has thus sought to develop transition metal complexes having ambiphilic (containing a Lewis basic and acidic unit) ligands. This approach takes advantage of metal–ligand cooperativity to increase the efficiency of a given chemical transformation, leveraging intramolecular interactions between a transition metal and an adjacent secondary ligand site. While this has shown significant potential to facilitate challenging and important transformations, there remains unexplored depth for creativity and future advancement. This Frontier highlights inter- and intramolecular combinations of transition metals and Lewis acids that together, provide a collaborative platform for chemical synthesis.
Tan, Bojun; Dou, Jinkang; Yang, Xiong; Li, Wenjie; Zhang, Jing; Zhang, Pengfeng; Mo, Hongchang; Lu, Xinming; Wang, Bozhou; Liu, Ning
doi: 10.1039/d4dt01537apmid: 38980718
Energetic Metal–Organic Framework (EMOF) compounds have gained significant attention in recent years as a hot research topic in the fields of explosives and propellants. This article provides an overview of the latest research progress of EMOFs in various areas, including heat-resistant explosives, burning rate catalysts and initiating explosives. It discusses the recent development trends of high-energy EMOFs, such as high-dimensional and solvent-free structural design, simplified and scalable synthesis conditions, environmentally friendly manufacturing processes with tunable structures, high-energy, low-sensitivity and multifunctional target products. The challenges and issues faced by EMOFs in heat-resistant explosives, burning rate catalysts and initiating explosives are presented. Furthermore, the key research directions for future applications of EMOFs in the fields of explosives and propellants are discussed, including solvent-free high-dimensional EMOFs design and synthesis, precise modulation of EMOFs molecular composition and pore structure, improvement of accurate prediction methods for physicochemical properties of high-energy EMOFs, low-cost large-scale production and development of multifunctional composite EMOFs as energetic materials, exploration of influencing factors, and comprehensive study on the application of novel and high-performance multifunctional EMOFs.
Ma, Zhen-Sha; Yang, Hui; Xing, Kai; Zhou, Kang; Lu, Gonghao; Liu, Xiao-Yuan
doi: 10.1039/d4dt01729cpmid: 39082122
In the present work, we report a “two-in-one” strategy to construct single-linker-based pillar-layered metal–organic frameworks (PL-MOFs) guided by reticular chemistry via an in situ “one-pot” approach. Two carboxyl groups and one pyridine group are integrated into one molecular skeleton to form bifunctional organic linkers via the reaction of pyridine-containing aldehyde and bicarboxylate-containing o-phenylenediamine. During the synthesis of organic linkers, two zinc-based PL-MOFs, non-interpenetrated HIAM-3016-op and two-fold interpenetrated HIAM-3017-op, can be simultaneously constructed. The different interpenetrations for these two PL-MOFs can be attributed to the increased length of the pyridine-containing moiety. HIAM-3017-op can be utilized for Cr2O72− detection with excellent sensitivity and selectivity. The present work not only provides a novel insight to design and prepare PL-MOFs with specific structures guided by reticular chemistry, but also indicates the universality of the in situ “one-pot” strategy to construct porous materials.
Mohri, Akinori; Oami, Yuki; Sadakiyo, Masaaki
doi: 10.1039/d4dt01424cpmid: 39101225
We report superionic conduction in a Mg2+-containing covalent organic framework (COF) at intermediate temperature in the absence of guest vapors. A COF containing Mg2+ carriers and polyethylene oxide (PEO) chains in its channels (TPB-PEO-9-COF-Mg) was synthesized. TPB-PEO-9-COF-Mg showed superionic conductivity above 10−4 S cm−1 under dry N2 at 160 °C.
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