Molecular Engineering of Metal Complexes for Electrocatalytic Carbon Dioxide Reduction: From Adjustment of Intrinsic Activity to Molecular Immobilization. | LitMetric
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.
Published: November 2022
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Article Abstract
The electrocatalytic CO reduction reaction (ECO RR) is one promising method for storing intermittent clean energy in chemical bonds and producing fuels. Among various kinds of catalysts for ECO RR, molecular metal complexes with well-defined structures are convenient for studies of their rational design, structure-reactivity relationships, and mechanisms. In this Review, we summarize the molecular engineering of several N-based metal complexes including Re/Mn bipyridine compounds and metal macrocycles, concluding with general modification strategies to devise novel molecular catalysts with high intrinsic activity. Through physical adsorption, covalent linking, and formation of a periodic backbone, these active molecules can be heterogenized into immobilized catalysts with more practical prospects. Finally, significant challenges and opportunities based on molecular catalysts are discussed.
Noncovalent interactions (NCI) play a central role in numerous physical, chemical, and biological phenomena. An accurate description of NCI is the key to success for any theoretical study in such areas. Although quantum mechanics (QM) methods such as dispersion-corrected density functional theory are sufficiently accurate, their applications are practical only for <300 atoms and <100 ps of simulation time.
Small cell lung cancer (SCLC) is an aggressive neuroendocrine tumor with the poorest prognosis among all types of lung cancer. Developing an effective comprehensive strategy remains a key focus. We herein present the first documented case of a 68-year-old man with limited-stage SCLC who has maintained a complete response (CR) for over 30 months to date.
Chloride ions play vital roles in a variety of biological and environmental processes, making their accurate and efficient detection critical for both research and practical applications. In this perspective, we explore the recent advancements in the development of metal complex-based probes for chloride ion detection, with a focus on complexes involving transition and lanthanide metals. These probes offer remarkable selectivity and sensitivity, achieved through diverse mechanisms such as metal coordination, hydrogen bonding, electrostatic interactions, and halogen or chalcogen bonding.
Three 1-(anthracene-9-ylmethyl)-3-isopropyl-imidazol-2-thione Zn(II) halide complexes (1-3) and one 1-(anthracene-9-ylmethyl)-3-isopropyl-imidazol-2-selone Zn(II) dichloride complex (4) were synthesized and characterized. Complexes 2, 3, and 4 exhibited distorted tetrahedral geometries, while complex 1 adopted a regular tetrahedral geometry. All these complexes displayed emission in the crystalline state, with complex 3 emitting in the yellow region and complex 1 and 4 in the blue region, while complex 2 gave a bluish-green emission.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Jiangwan Campus, Fudan University, Shanghai 200438, China.
The phosphaguanidinate rare-earth-metal bis(aminobenzyl) complexes [(PhP)C(NCHPr-2,6)]Ln(CHCH NMe-) (Ln = Y(1-Y) and Lu(1-Lu)) were synthesized by the protonolysis of (PhP)[C(NHR)(NR)] (R = 2,6-(Pr)CH) with Ln(CHCHNMe-) (Ln = Y and Lu). Interestingly, the ring-opening rearrangement product [-MeNCHCHC(NCHPr-2,6)]Lu(CHCHNMe-)[O(CH)PPh] (2) was obtained when the acid-base reaction was carried out in THF solution at 60 °C for 36 h. Additionally, the trinuclear homometallic yttrium multimethyl/methylidene complex {[(PhP)C(NCHPr-2,6)]Y(μ-Me)}(μ-Me)(μ-CH) (3) was synthesized by the treatment of 1-Y with AlMe (2 equiv.
