{"title":"Approaching through the chronicles of species with low-valent silicon and their transition metal complexes: Structure, bonding and potential catalytic applications","authors":"Sourav Singha Roy, Herbert W. Roesky","doi":"10.1016/j.ccr.2025.216657","DOIUrl":"10.1016/j.ccr.2025.216657","url":null,"abstract":"<div><div>Compounds with low-valent silicon characterized by an oxidation state lower than +IV (the most stable oxidation state for silicon) represent one of the fascinating and rapidly emerging fields of research in main-group chemistry. The primary challenge associated with the research involving compounds with low-valent silicon is their synthesis and isolation due to their high reactivity and tendency to attain the most stable oxidation state. Despite the challenges associated with compounds of low-valent silicon, their study is crucial as their unique reactivity can be explored for various catalytic transformations. In addition, compounds of low-valent silicon can serve as ligands to transition metals, which can lead to the formation of metal complexes that may have potential for catalytic applications. The review commences with the highlights of the milestone discoveries in the field of compounds with low-valent silicon. The next section of the review discusses the structure and bonding properties of different classes of compounds with low-valent silicon according to their oxidation state [+II (silylene, disilene, disilyne and silyliumylidene ion) and 0 (silylone)]. The subsequent section provides insights into different binding modes of compounds with low-valent silicon to transition metals. A detailed emphasis is given on some notable examples of transition metal complexes supported compounds with low-valent silicon as ligands, focusing on their synthesis, characterization, and potential catalytic applications.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216657"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wail Al Zoubi , Yujun Sheng , Iftikhar Hussain , Heo Seongjun , Nokeun Park
{"title":"Multi-principal element nanoparticles: Synthesis strategies and machine learning prediction","authors":"Wail Al Zoubi , Yujun Sheng , Iftikhar Hussain , Heo Seongjun , Nokeun Park","doi":"10.1016/j.ccr.2025.216656","DOIUrl":"10.1016/j.ccr.2025.216656","url":null,"abstract":"<div><div>Multi-principal element nanoparticles (MPENs) are an emerging class of nano-materials with widespread applications in electrocatalysis owing to their tunable performances and high chemical stability. The extensive chemical compositional space and high surface area become even more significant at the nanoscale level. MPENs exhibit unique properties, including multi-element synergy, high configuration entropy, and long-range atomic ordering with distinct sublattices of semimetallic or metallic components. These characteristics endow MPENs with outstanding catalytic performance and chemical stability, making them promising candidates for high-entropy alloy (HEA). This review details common synthesis approaches for MPENs. The combination of experimental validation with computational preselection provide an efficient method for optimizing MPENs compositions and enhancing their properties for energy-related applications. In addition, we report on the machine-learning (ML) algorithms and review novel ML models related to atomistic simulations and atomic interactions in thermodynamic studies. We also summarize the ML models for macroscale properties, including lattice structures and phase formations. Instances phase formation through ML-derived order parameters and predictive rules is presented to demonstrate the workflow. In addition, we examine research challenges, including ML-guided opposite materials design and uncertainty quantification.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216656"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qian Li , Chenhui Wang , Hongxia Yao , Chunmei He , Changfa Guo , Yong Hu
{"title":"Cocatalysts for photocatalysis: Comprehensive insight into interfacial charge transfer mechanism by energy band theory","authors":"Qian Li , Chenhui Wang , Hongxia Yao , Chunmei He , Changfa Guo , Yong Hu","doi":"10.1016/j.ccr.2025.216652","DOIUrl":"10.1016/j.ccr.2025.216652","url":null,"abstract":"<div><div>Cocatalysts have played an important role to reach high-efficiency photocatalysis with semiconductor photocatalysts. Various compositions and microstructures of inorganic and organic nanomaterials have been proposed as cocatalysts, however, consistent understanding on charge transfer mechanism at heterogenous interfaces has not been achieved yet. In this review, the existing cocatalysts are first re-sorted in terms of composition and band structure into (semi)metals, metal compounds (narrow- and wide-bandgap), nonmetals and hybrids, focusing on the underlying mechanism for charge transfer pathway at various cocatalyst–semiconductor interfaces according to energy band theory. Significantly, the polarity of Schottky contact and Ohmic contact for a semiconductor-(semi)metal heterojunction is highlighted, wherein Schottky junctions for electron transfer can be deemed as Ohmic junctions for hole transfer, and vice versa. The specific charge transfer pathway depends on the type of semiconductors, magnitude of interfacial band bending barrier, as well as that whether the metal has plasmic resonance effect. Furthermore, the function of cocatalysts (reduction- or oxidation-type) is distinguished in terms of charge transfer pathway, and consistent understanding on the roles of narrow-bandgap metal-compound cocatalysts is achieved, no matter they are deemed as semimetals or semiconductors in previous studies. Finally, the comprehensive insight into charge transfer pathways at various semiconductor-cocatalyst interfaces is obtained, which provides universal criteria to investigate carrier kinetics within heterojunction photocatalysts.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216652"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recent updates on cadmium indium sulfide (CdIn2S4 or CIS) photo-catalyst: Synthesis, enhancement strategies and applications","authors":"Shabnam Sambyal , Anita Sudhaik , Sonu Sonu , Pankaj Raizada , Vishal Chaudhary , Van-Huy Nguyen , Aftab Aslam Parwaz Khan , Chaudhery Mustansar Hussain , Pardeep Singh","doi":"10.1016/j.ccr.2025.216653","DOIUrl":"10.1016/j.ccr.2025.216653","url":null,"abstract":"<div><div>Photocatalytic technology harnesses solar energy to address the global energy crisis while offering sustainable solutions for environmental applications. Among emerging photocatalysts, Cadmium indium sulfide (CdIn<sub>2</sub>S<sub>4</sub> or CIS) stands out due to its excellent visible light absorption, optimal bandgap, non-toxicity, durability, notable catalytic efficiency, and tunable morphology, making it an appealing candidate for diverse photocatalytic applications. The intrinsic electronic, chemical, physical, and optical properties of CIS nanomaterials are highly tunable, rendering them promising candidates for diverse photocatalytic applications. However, CIS has undergone extensive modifications and optimization to attain excellent photocatalytic activity. The crystalline properties and basic photocatalytic mechanism were deliberated by density functional theory (DFT) calculations. This review provides a comprehensive insight into numerous modification techniques of CIS, including doping, surface defects, metal deposition, carbon loading and heterojunction formation, with effective activity of CIS-based heterojunction. Subsequently, the CIS-based photocatalysts for photocatalytic degradation, photocatalytic reduction of carbon dioxide, hydrogen evolution and hydrogen peroxide production applications from the previous five years will be examined and concluded with an eye toward the future. This review offers an in-depth and critical analysis of these aspects, demonstrating a perspective not previously presented.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216653"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recent progress and advancement on zinc-based materials for water splitting: Structure-property-performance correlation","authors":"Baghendra Singh, Apparao Draksharapu","doi":"10.1016/j.ccr.2025.216647","DOIUrl":"10.1016/j.ccr.2025.216647","url":null,"abstract":"<div><div>The ongoing energy upheaval and atmospheric pollution are among the most pressing challenges facing society today. To address these issues, the establishment of effective methods for electrochemical energy conversion offers a promising path forward. Recently, Zn-based materials have attracted a lot of interest as possible solutions in this field. Their appeal relies upon their precisely modified structural and electronic features, three-dimensional architectures, extensive surface areas, numerous active sites, robust stability, and enhanced mass transport and diffusion characteristics. They are very well suited for use in energy conversion and storage because of these characteristics. Several papers have been published over the past few years, which are investigating the potential of Zn-based materials in various techniques for energy conversion. However, no comprehensive review is available, that systematically discusses the Zn-based materials for energy conversion. This review offers a thorough examination of the advancements in Zn-derivatives for applications in key energy conversion processes, including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) involving electrochemical, photoelectrochemical, and photocatalytic water splitting. The review delves into the electrical as well as structure-related features, and performance of Zn-based materials, highlighting the role of modulating structural, morphological, and electronic properties in enhancing catalytic activity. Furthermore, the structure-property-performance relationship has been discussed in the context of improving activity, stability, and overall efficiency in water-splitting applications. The review addresses the challenges and possible directions for the industry going ahead while highlighting the potential of zinc-based materials to support the invention of environmentally conscious water-splitting technology.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216647"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shouhao Wei , Mohamed K. Albolkany , Li Zhao , Bo Liu
{"title":"Supramolecular chemistry for carbon dioxide capture","authors":"Shouhao Wei , Mohamed K. Albolkany , Li Zhao , Bo Liu","doi":"10.1016/j.ccr.2025.216655","DOIUrl":"10.1016/j.ccr.2025.216655","url":null,"abstract":"<div><div>The ever-increasing global warming and environmental deterioration call for carbon emission reduction, however current carbon capture technologies are not fairly efficient to come into effect, considering their high energy-consumption and economic-cost. This review renews supramolecular chemistry for carbon dioxide capture, in which specific supramolecular chemical interaction between absorbent host and carbon dioxide guest guarantees the high selectivity and low binding energy of non-chemical bonds. Supramolecular interactions enable easy carbon dioxide release and absorbent regeneration for cycling. This review is outlined starting with introducing the background of carbon capture, utilization and storage (CCUS). In this context, we are discussing the difficulties faced in emission reduction, particularly due to the high energy demands and economic costs of extracting carbon dioxide (CO<sub>2</sub>) from flue gas. Afterwards, the fundamentals and mechanism of supramolecular chemistry are presented followed by discussing the advantages and limitations of CO<sub>2</sub> hydrates as the first generation of supramolecular chemical CO<sub>2</sub> capture materials. The typical supramolecular materials, including calixarenes, pillararenes etc., are demonstrated while discussing the CO<sub>2</sub> diffusion behaviors in the supramolecules lattice for capture. Newly developed the third-generation supramolecular hydrogen-bond ionic framework (HIF) materials are introduced and elaborated. Using HIF materials, the reversible CO<sub>2</sub> capture and release could be achieved at mild conditions, and thus shows great promise for practical CO<sub>2</sub> capture from flue gas in industry. At the end of review, we discuss the potential industrial applications of supramolecular chemistry for carbon capture, proposing HIF materials with their tunable structures as a promising candidate for improving CO<sub>2</sub> capture efficiency aiming to relief both energy consumption and economic cost burdens.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216655"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yu Chen , Zongkang Guo , Jing Li , Kemin Wang , Jin Huang
{"title":"Smart nucleic acid nanodrug delivery system for precision therapeutics","authors":"Yu Chen , Zongkang Guo , Jing Li , Kemin Wang , Jin Huang","doi":"10.1016/j.ccr.2025.216673","DOIUrl":"10.1016/j.ccr.2025.216673","url":null,"abstract":"<div><div>Nucleic acid nano carriers, characterized by programmability, degradability, and high biosafety, have found widespread applications across various fields. With the rapid advancement of nanotechnology, smart nucleic acid nanodrug delivery systems (NDDSs) have demonstrated significant potential for precise and safe therapy. This review summarizes the latest advancements in smart nucleic acid NDDSs, adopting a bottom-up approach. First, we summarize the fundamental functional nucleic acid units essential for realizing smart NDDSs, considering targeting, responsiveness, and therapeutic potential. These units are strategically incorporated into nanocarriers to develop functionally sophisticated smart NDDSs. Accordingly, we outline several construction strategies for self-assembled nanocarriers, such as Y(X)-shaped monomer self-assembly, rolling circle amplification (RCA), hybridization chain reaction (HCR), DNA origami, DNA polyhedron and hybrid assembly. Furthermore, we explore the diverse applications of smart NDDSs in drug delivery, encompassing small molecule drugs, nucleic acid drugs, protein drugs, and co-delivery systems. Finally, we discuss the challenges of clinical translation of smart nucleic acid NDDSs and future research directions. This review aims to deepen researchers' understanding of the design, construction, and potential applications of these systems, thereby advancing their clinical development and enhancing their effectiveness in precision medicine.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216673"},"PeriodicalIF":20.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ishfaq Ahmad Rather , Fei Wang , Rafia Siddiqui , Meiyue Zhang , Wei Zhou , Xiao Cai , Qing He
{"title":"Covalent organic cages in supramolecular separation","authors":"Ishfaq Ahmad Rather , Fei Wang , Rafia Siddiqui , Meiyue Zhang , Wei Zhou , Xiao Cai , Qing He","doi":"10.1016/j.ccr.2025.216648","DOIUrl":"10.1016/j.ccr.2025.216648","url":null,"abstract":"<div><div>Covalent organic cages (COCs), distinguished by their discrete, three-dimensional architectures with customizable cavities, represent a rapidly advancing class of molecular materials with broad applications, including microreactors, heterogeneous catalysis, high-permeability membranes, and porous liquids. Recent advancements in synthetic strategies and supramolecular chemistry have enabled a diverse range of COC structures, which, like metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and porous organic polymers (POPs), provide high surface areas, accessible porosities, and tunable architectures. Unlike these extended porous networks, COCs are composed of discrete, solvent-soluble units, facilitating enhanced dispersion, processability, and recyclability. Their dynamic features, including reversible polymorphism and supramolecular interactions, support dissociation and recombination, further enhancing their adaptability and shape persistence. This review examines recent progress in the use of COCs for supramolecular separations, with a focus on their utility in separating gases, ions, enantiomers, and positional isomers, as well as in the development of pure and hybrid porous membranes. By synthesizing current findings, we aim to assist researchers in designing COCs tailored to specific industrial separation applications, highlighting the increasing relevance of these materials in separation science.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216648"},"PeriodicalIF":20.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Karl Ridier , Ayman Hoblos , Stéphane Calvez , Maciej Lorenc , William Nicolazzi , Saioa Cobo , Lionel Salmon , Lucie Routaboul , Gábor Molnár , Azzedine Bousseksou
{"title":"Optical properties and photonic applications of molecular spin-crossover materials","authors":"Karl Ridier , Ayman Hoblos , Stéphane Calvez , Maciej Lorenc , William Nicolazzi , Saioa Cobo , Lionel Salmon , Lucie Routaboul , Gábor Molnár , Azzedine Bousseksou","doi":"10.1016/j.ccr.2025.216628","DOIUrl":"10.1016/j.ccr.2025.216628","url":null,"abstract":"<div><div>We review the current knowledge on the optical properties of molecular spin-crossover (SCO) materials, which exhibit reversible switching between low-spin and high-spin electronic configurations, as well as their use for practical applications in the fields of optics and photonics. We focus on the physical origins and magnitude of the complex refractive index change (both real and imaginary parts) in SCO materials, including a brief excursion to less-studied lower frequency ranges (THz–Hz). Until now, the optical property changes have primarily been used as a means of detection to characterize the SCO phenomenon itself (particularly at the nanometric scale) or to develop optical sensors for monitoring variations in an external stimulus. However, more recently, optical signal processing and modulation have also been explored using SCO nanomaterials as active elements in tunable photonic devices. Herein, we review the current state of the art of such functional devices, showing that molecular SCO compounds are emerging as a promising class of phase-change materials with high potential for specific active photonic applications, particularly in the visible spectral range. Key results on light-induced spin transitions and the photoswitching dynamics of SCO materials are also briefly reviewed in the context of photonic devices. Finally, the results of recent studies reporting strong light-matter coupling phenomena between SCO molecules and confined electromagnetic fields in resonant optical cavities are also discussed, with, in sight, the fascinating perspectives of manipulating the molecular properties using light.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216628"},"PeriodicalIF":20.3,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724463","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yida Pang , Fang Zhao , Yuting Wang , Qiao Song , Qian Wang , Junrong Li , Ruiping Zhang , Yao Sun
{"title":"Beyond chemotherapy: Spatiotemporal activation of metal complexes for deep-tissues precision medicine","authors":"Yida Pang , Fang Zhao , Yuting Wang , Qiao Song , Qian Wang , Junrong Li , Ruiping Zhang , Yao Sun","doi":"10.1016/j.ccr.2025.216664","DOIUrl":"10.1016/j.ccr.2025.216664","url":null,"abstract":"<div><div>Metal-based complexes have emerged as powerful agents in anticancer therapy, demonstrating exceptional activity and positioning themselves as highly promising candidates in the field. Among these, platinum-based antitumor drugs are extensively employed in current chemotherapy protocols. However, their clinical utility is significantly constrained by challenges such as drug resistance, non-specific biodistribution, and irreversible toxicities. Recent advances underscore that precise spatiotemporal activation of metal-based drugs through external radiation offers a novel mechanism of action distinct from conventional chemotherapy. This approach enhances therapeutic efficacy while simultaneously mitigating side effects and cross-resistance, addressing pivotal limitations inherent to traditional metal-based therapeutics. External stimuli, including near-infrared (NIR) light, ultrasound (US), and X-rays, possess superior tissue penetration compared to ultraviolet-visible light, rendering them particularly advantageous for targeting deep-seated tumors. Within this framework, we comprehensively review recent developments in the activation of metal-based drugs <em>via</em> NIR light, US, and X-rays, with a focus on molecular metal complexes, supramolecular coordination complexes, and metal-organic frameworks. Critical aspects covered include their design principles, photophysical and photochemical properties, and biomedical applications. Finally, we address the difficulties and future directions for the biomedical field and clinical translation of these metal complexes.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"535 ","pages":"Article 216664"},"PeriodicalIF":20.3,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}