Pub Date : 2026-02-09DOI: 10.1021/acs.accounts.5c00851
Xin Zhang, Liu Leo Liu
For many years, carbenes were regarded as fleeting intermediates, elusive to both isolation and direct observation. This perception was overturned when Bertrand isolated the first singlet carbene in 1988, followed by Arduengo’s synthesis of a crystalline N-heterocyclic carbene (NHC) in 1991. This not only demonstrates that carbenes can be tamed under ambient conditions but also ushered in a new era in which such species found widespread and indispensable applications in synthetic chemistry and materials science. Aluminylenes/alanediyls (R–Al), the aluminum analogs of carbenes, feature a monovalent aluminum center in the +I oxidation state bearing a pair of nonbonding electrons and two vacant orbitals. For a long time, however, these species remained largely confined to the realm of theory or could be inferred only under extreme conditions. Although the first Al(I) compound, (Cp*Al)4, was isolated by Schnöckel in 1991 and a monomeric, dicoordinate Al(I) complex [HC(CMeNDipp)2]Al (Dipp = 2,6-diisopropylphenyl) was reported by Roesky in 2000, free monocoordinate aluminylenes eluded isolation until 2020–2021. In this period, Power and Tuononen realized the isolation of AriPr8–Al (AriPr8 = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2), while we and Hinz independently disclosed a stable carbazolyl-aluminylene, [N]–Al ([N] = 3,6-di-tert-butyl-1,8-bis(3,5-di-tert-butylphenyl)carbazolyl). These discoveries collectively establish aluminylenes as an accessible class of low-valent main-group species and open new avenues for their exploration in synthetic chemistry and beyond.
{"title":"Aluminylenes: Synthesis, Reactivity, and Catalysis","authors":"Xin Zhang, Liu Leo Liu","doi":"10.1021/acs.accounts.5c00851","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00851","url":null,"abstract":"For many years, carbenes were regarded as fleeting intermediates, elusive to both isolation and direct observation. This perception was overturned when Bertrand isolated the first singlet carbene in 1988, followed by Arduengo’s synthesis of a crystalline N-heterocyclic carbene (NHC) in 1991. This not only demonstrates that carbenes can be tamed under ambient conditions but also ushered in a new era in which such species found widespread and indispensable applications in synthetic chemistry and materials science. Aluminylenes/alanediyls (R–Al), the aluminum analogs of carbenes, feature a monovalent aluminum center in the +I oxidation state bearing a pair of nonbonding electrons and two vacant orbitals. For a long time, however, these species remained largely confined to the realm of theory or could be inferred only under extreme conditions. Although the first Al(I) compound, (Cp*Al)<sub>4</sub>, was isolated by Schnöckel in 1991 and a monomeric, dicoordinate Al(I) complex [HC(CMeNDipp)<sub>2</sub>]Al (Dipp = 2,6-diisopropylphenyl) was reported by Roesky in 2000, free monocoordinate aluminylenes eluded isolation until 2020–2021. In this period, Power and Tuononen realized the isolation of Ar<sup>iPr8</sup>–Al (Ar<sup>iPr8</sup> = C<sub>6</sub>H-2,6-(C<sub>6</sub>H<sub>2</sub>-2,4,6-<sup><i>i</i></sup>Pr<sub>3</sub>)<sub>2</sub>-3,5-<sup><i>i</i></sup>Pr<sub>2</sub>), while we and Hinz independently disclosed a stable carbazolyl-aluminylene, [N]–Al ([N] = 3,6-di-<i>tert</i>-butyl-1,8-bis(3,5-di-<i>tert</i>-butylphenyl)carbazolyl). These discoveries collectively establish aluminylenes as an accessible class of low-valent main-group species and open new avenues for their exploration in synthetic chemistry and beyond.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"89 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146009","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}
Pub Date : 2026-02-09DOI: 10.1021/acs.accounts.5c00843
Kang Li, Jing Li, Pu Wang, Yong Pei
Ligand-protected gold nanoclusters (Au NCs) occupy a unique region between molecules and bulk metals, garnering significant attention due to their atomically precise structure and size- and structure-dependent optical properties. Notably, their tunable emission characteristics, excellent photostability, and biocompatibility make them promising candidates for bioimaging, sensing, and optoelectronic applications. However, the relatively low photoluminescence quantum yield (PLQY) of most Au NCs hinders their practical application. Furthermore, the low PLQY of Au NCs is closely associated with their complex excited-state dynamics: the interactions between the metal core and ligand shell, coupled with the strong spin–orbit coupling (SOC) effect, collectively induce diverse excited-state relaxation pathways, which render the regulatory mechanism of photoluminescence (PL) difficult to decipher precisely.
{"title":"Theoretical Insights on the Regulatory Mechanisms of Structure and Doping on the Photoluminescence of Ligand Protected Gold Nanoclusters","authors":"Kang Li, Jing Li, Pu Wang, Yong Pei","doi":"10.1021/acs.accounts.5c00843","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00843","url":null,"abstract":"Ligand-protected gold nanoclusters (Au NCs) occupy a unique region between molecules and bulk metals, garnering significant attention due to their atomically precise structure and size- and structure-dependent optical properties. Notably, their tunable emission characteristics, excellent photostability, and biocompatibility make them promising candidates for bioimaging, sensing, and optoelectronic applications. However, the relatively low photoluminescence quantum yield (PLQY) of most Au NCs hinders their practical application. Furthermore, the low PLQY of Au NCs is closely associated with their complex excited-state dynamics: the interactions between the metal core and ligand shell, coupled with the strong spin–orbit coupling (SOC) effect, collectively induce diverse excited-state relaxation pathways, which render the regulatory mechanism of photoluminescence (PL) difficult to decipher precisely.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"31 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146145928","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}
Pub Date : 2026-02-09DOI: 10.1021/acs.accounts.5c00839
Juan Kong, An-An Liu, Hai-Yan Xie, Dai-Wen Pang
Quantum dots (QDs), a remarkable inorganic semiconductor nanocrystal capable of converting light energy into electrical, chemical, thermal, and other forms of energy, can be used to create super living systems through their fusion with cells, which hold tremendous potential for biomedical applications. Although considerable efforts have been devoted to delivering in vitro synthesized QDs into cells via endocytosis or electroporation, these approaches often suffer from poor biocompatibility, uncontrolled uptake pathways, and nonspecific intracellular interactions. Moreover, to satisfy the stringent demands of biological environments, QDs produced through conventional synthetic routes typically require extensive postsynthetic treatments, such as phase transfer into aqueous media and surface functionalization, which can irreversibly disrupt their surface structure and substantially compromise their photoluminescence quantum yield and photostability. Consequently, the exceptional optical properties of QDs are difficult to fully maintain when applied in physiological environments.
{"title":"Biologically Adaptable Quantum Dots: Intracellular in Situ Synthetic Strategy and Mechanism","authors":"Juan Kong, An-An Liu, Hai-Yan Xie, Dai-Wen Pang","doi":"10.1021/acs.accounts.5c00839","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00839","url":null,"abstract":"Quantum dots (QDs), a remarkable inorganic semiconductor nanocrystal capable of converting light energy into electrical, chemical, thermal, and other forms of energy, can be used to create super living systems through their fusion with cells, which hold tremendous potential for biomedical applications. Although considerable efforts have been devoted to delivering in vitro synthesized QDs into cells via endocytosis or electroporation, these approaches often suffer from poor biocompatibility, uncontrolled uptake pathways, and nonspecific intracellular interactions. Moreover, to satisfy the stringent demands of biological environments, QDs produced through conventional synthetic routes typically require extensive postsynthetic treatments, such as phase transfer into aqueous media and surface functionalization, which can irreversibly disrupt their surface structure and substantially compromise their photoluminescence quantum yield and photostability. Consequently, the exceptional optical properties of QDs are difficult to fully maintain when applied in physiological environments.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"161 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146210","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}
Pub Date : 2026-02-06DOI: 10.1021/acs.accounts.5c00724
Jiao Zhou, Ashim Nandi, Yan Xu, Jing An, Arieh Warshel, Ziwei Huang
Viral proteases are essential enzymes required for viral replication and assembly, making them prime antiviral drug targets. However, under the selective pressure of protease inhibitors, viruses can acquire mutations that reduce drug binding efficacy, posing significant challenges in both chronic infections (e.g., HIV, HCV) and acute infections like COVID-19, where mutations in the SARS-CoV-2 main protease (Mpro) have been reported to compromise the efficacy of drugs such as nirmatrelvir. To address these challenges, mainstream strategies in combating viral protease drug resistance mutations include combination therapies and targeting evolutionarily conserved regions of viral proteases. By disrupting multiple stages of the viral lifecycle or focusing on functionally indispensable residues, these strategies aim to develop next-generation antivirals that remain effective against evolving viral mutations.
{"title":"Combating Antiviral Drug Resistance: A Multipronged Strategy","authors":"Jiao Zhou, Ashim Nandi, Yan Xu, Jing An, Arieh Warshel, Ziwei Huang","doi":"10.1021/acs.accounts.5c00724","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00724","url":null,"abstract":"Viral proteases are essential enzymes required for viral replication and assembly, making them prime antiviral drug targets. However, under the selective pressure of protease inhibitors, viruses can acquire mutations that reduce drug binding efficacy, posing significant challenges in both chronic infections (e.g., HIV, HCV) and acute infections like COVID-19, where mutations in the SARS-CoV-2 main protease (M<sup>pro</sup>) have been reported to compromise the efficacy of drugs such as nirmatrelvir. To address these challenges, mainstream strategies in combating viral protease drug resistance mutations include combination therapies and targeting evolutionarily conserved regions of viral proteases. By disrupting multiple stages of the viral lifecycle or focusing on functionally indispensable residues, these strategies aim to develop next-generation antivirals that remain effective against evolving viral mutations.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"39 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129663","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.accounts.5c00837
Huizhen Ma, Di Ma, Pengfei Liu, Hao Wang, Xiao-Dong Zhang
<p><p>ConspectusNear-infrared II (NIR-II, 1000-3000 nm), also defined as shortwave infrared (SWIR) imaging, offers reduced light scattering and low tissue absorption, enabling centimeter-scale penetration and high signal-to-noise ratios. It has become a powerful tool for fundamental biomedical research and clinicopathological diagnosis. Metal clusters, with their discrete, molecule-like electronic structures, exhibit exceptional NIR-II luminescence. Notably, atomically precise clusters with well-defined three-dimensional coordination allow fine-tuning of NIR-II optical properties through atomic engineering, ligand design, and surface modification. Their ultrasmall (∼2 nm) size further supports efficient renal clearance, low toxicity, and excellent biocompatibility, highlighting their promise for clinical translation. Moreover, coupling metal clusters with advanced NIR-II imaging technologies and artificial intelligence enables high-resolution, deep-tissue visualization with enhanced sensitivity and accuracy. Therefore, achieving high-performance biomedical imaging and fulfilling clinical needs require a comprehensive understanding of the luminescence mechanisms of serial atomically precise clusters and their corresponding microscopic imaging methods, together with the parallel development of dedicated artificial-intelligence tools to fully unlock their application potential.In this Account, we summarize the NIR-II luminescence properties, imaging techniques, biomedical applications, and biosafety of atomically precise metal clusters. We begin by presenting their crystal structures, as a clear understanding of atomic arrangements is essential for precise property control. We then outline key photophysical parameters, emission wavelength, and quantum yield (QY), followed by NIR-II luminescence mechanisms and strategies for their rational tailoring, which underpin the design of next-generation imaging probes. We further highlight the synergistic integration of metal clusters with advanced imaging technology, enabling high signal-to-noise imaging of disease progression and spatially resolved phenotyping of pathological tissue. This section includes wide-field imaging, three-dimensional microscopy imaging, and emerging artificial intelligence assisted image processing. We next examine major NIR-II biomedical applications, including tumor progression, neurological imaging, and clinical pathology visualization, and other lesions imaging associated with diverse diseases. Finally, we evaluate the biosafety of metal clusters, focusing on the effects of size, surface chemistry and renal clearance, to inform their safe and effective clinical translation.This Account presents the fundamental physics and NIR-II luminescence of atomically precise metal clusters, detailing their emission wavelengths, QYs, luminescence mechanisms, and tuning strategies. Coupling these clusters with advanced imaging technology and deep learning enables high-resolution imaging with
{"title":"Atomically Precise Metal Clusters for NIR-II Imaging.","authors":"Huizhen Ma, Di Ma, Pengfei Liu, Hao Wang, Xiao-Dong Zhang","doi":"10.1021/acs.accounts.5c00837","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00837","url":null,"abstract":"<p><p>ConspectusNear-infrared II (NIR-II, 1000-3000 nm), also defined as shortwave infrared (SWIR) imaging, offers reduced light scattering and low tissue absorption, enabling centimeter-scale penetration and high signal-to-noise ratios. It has become a powerful tool for fundamental biomedical research and clinicopathological diagnosis. Metal clusters, with their discrete, molecule-like electronic structures, exhibit exceptional NIR-II luminescence. Notably, atomically precise clusters with well-defined three-dimensional coordination allow fine-tuning of NIR-II optical properties through atomic engineering, ligand design, and surface modification. Their ultrasmall (∼2 nm) size further supports efficient renal clearance, low toxicity, and excellent biocompatibility, highlighting their promise for clinical translation. Moreover, coupling metal clusters with advanced NIR-II imaging technologies and artificial intelligence enables high-resolution, deep-tissue visualization with enhanced sensitivity and accuracy. Therefore, achieving high-performance biomedical imaging and fulfilling clinical needs require a comprehensive understanding of the luminescence mechanisms of serial atomically precise clusters and their corresponding microscopic imaging methods, together with the parallel development of dedicated artificial-intelligence tools to fully unlock their application potential.In this Account, we summarize the NIR-II luminescence properties, imaging techniques, biomedical applications, and biosafety of atomically precise metal clusters. We begin by presenting their crystal structures, as a clear understanding of atomic arrangements is essential for precise property control. We then outline key photophysical parameters, emission wavelength, and quantum yield (QY), followed by NIR-II luminescence mechanisms and strategies for their rational tailoring, which underpin the design of next-generation imaging probes. We further highlight the synergistic integration of metal clusters with advanced imaging technology, enabling high signal-to-noise imaging of disease progression and spatially resolved phenotyping of pathological tissue. This section includes wide-field imaging, three-dimensional microscopy imaging, and emerging artificial intelligence assisted image processing. We next examine major NIR-II biomedical applications, including tumor progression, neurological imaging, and clinical pathology visualization, and other lesions imaging associated with diverse diseases. Finally, we evaluate the biosafety of metal clusters, focusing on the effects of size, surface chemistry and renal clearance, to inform their safe and effective clinical translation.This Account presents the fundamental physics and NIR-II luminescence of atomically precise metal clusters, detailing their emission wavelengths, QYs, luminescence mechanisms, and tuning strategies. Coupling these clusters with advanced imaging technology and deep learning enables high-resolution imaging with","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":17.7,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122955","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}
Pub Date : 2026-02-04DOI: 10.1021/acs.accounts.6c00063
Seunghoon Lee, Woojin Park, Cheol Ho Choi
In the originally published article, the affiliation of the corresponding author Cheol Ho Choi was incorrectly listed as “Department of Chemistry, Seoul National University, Seoul 151–747, South Korea.” The correct affiliation is “Department of Chemistry, Kyungpook National University, Daegu 41566, South Korea.” The change is reflected in the authorship of this Correction. This article has not yet been cited by other publications.
在最初发表的文章中，通讯作者Cheol Ho Choi的所属单位被错误地列为“首尔国立大学化学系，首尔151-747，韩国”。正确的隶属关系是“韩国庆北国立大学化学系，大邱41566”。这一变化反映在这一更正的作者。这篇文章尚未被其他出版物引用。
{"title":"Correction to “Expanding Horizons in Quantum Chemical Studies: The Versatile Power of MRSF-TDDFT”","authors":"Seunghoon Lee, Woojin Park, Cheol Ho Choi","doi":"10.1021/acs.accounts.6c00063","DOIUrl":"https://doi.org/10.1021/acs.accounts.6c00063","url":null,"abstract":"In the originally published article, the affiliation of the corresponding author Cheol Ho Choi was incorrectly listed as “Department of Chemistry, Seoul National University, Seoul 151–747, South Korea.” The correct affiliation is “Department of Chemistry, Kyungpook National University, Daegu 41566, South Korea.” The change is reflected in the authorship of this Correction. This article has not yet been cited by other publications.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"294 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110755","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}
Pub Date : 2026-02-04DOI: 10.1021/acs.accounts.5c00694
Xing Huang,Wei Xu
ConspectusCoordination polymers (CPs) and metal–organic frameworks (MOFs) are highly valued for applications in gas storage, separation, and catalysis, but their electronic applications have been limited by low electrical conductivity and charge mobility. The rise of conjugated coordination polymers (c-CPs) has changed this scenario entirely. c-CPs utilize planar, conjugated ligands with ortho-donor coordination groups (−OH, −SH, −NH2, −SeH) to form extended lattices with transition metals, enabling strong d−π conjugation and exceptional charge transport properties.In this Account, we trace our decade-long efforts to develop a distinctive family of c-CPs: those based on the small yet versatile ligand, benzenehexathiol (BHT). We highlight how the small BHT ligand and its soft −SH donors, compared with hexahydroxytriphenylene (HHTP) and hexaaminotriphenylene (HATP) used in conducting CPs and MOFs, promote stronger metal–ligand coupling, enhanced charge delocalization, and richer coordination chemistry, underpinning the high conductivity and structure diversity of BHT-based c-CPs. We detail the innovative synthetic strategies, such as interfacial synthesis and redox modulation, that enable us to obtain a series of high-crystalline, high-conductivity BHT-based c-CPs. This family of materials has consistently broken records, achieving metallic conductivities exceeding 103 S·cm–1 and charge mobilities up to 400 cm2·V–1·s–1. Notably, they provide a versatile platform for discovering exotic quantum phenomena that are rare in framework materials. Our exploration led to the first CP-based superconductor, Cu3BHT, and has revealed candidates for topological phases such as Weyl semimetal in Ag3BHT and Kondo lattice in CuAg4BHT.We conclude by emphasizing how the structure diversity of BHT-based c-CPs dictates their exceptional chemical and physical properties. This Account is more than a summary. It is a blueprint for the design of the next generation of electrically conducting CPs, illustrating how rational ligand design and synthetic control are able to not only advance electronic material exploration but also open new frontiers in quantum materials research.
{"title":"Benzenehexathiol-Based Conjugated Coordination Polymers: A Decade of Breakthroughs in High Conductivity and Quantum Phenomena","authors":"Xing Huang,Wei Xu","doi":"10.1021/acs.accounts.5c00694","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00694","url":null,"abstract":"ConspectusCoordination polymers (CPs) and metal–organic frameworks (MOFs) are highly valued for applications in gas storage, separation, and catalysis, but their electronic applications have been limited by low electrical conductivity and charge mobility. The rise of conjugated coordination polymers (c-CPs) has changed this scenario entirely. c-CPs utilize planar, conjugated ligands with ortho-donor coordination groups (−OH, −SH, −NH2, −SeH) to form extended lattices with transition metals, enabling strong d−π conjugation and exceptional charge transport properties.In this Account, we trace our decade-long efforts to develop a distinctive family of c-CPs: those based on the small yet versatile ligand, benzenehexathiol (BHT). We highlight how the small BHT ligand and its soft −SH donors, compared with hexahydroxytriphenylene (HHTP) and hexaaminotriphenylene (HATP) used in conducting CPs and MOFs, promote stronger metal–ligand coupling, enhanced charge delocalization, and richer coordination chemistry, underpinning the high conductivity and structure diversity of BHT-based c-CPs. We detail the innovative synthetic strategies, such as interfacial synthesis and redox modulation, that enable us to obtain a series of high-crystalline, high-conductivity BHT-based c-CPs. This family of materials has consistently broken records, achieving metallic conductivities exceeding 103 S·cm–1 and charge mobilities up to 400 cm2·V–1·s–1. Notably, they provide a versatile platform for discovering exotic quantum phenomena that are rare in framework materials. Our exploration led to the first CP-based superconductor, Cu3BHT, and has revealed candidates for topological phases such as Weyl semimetal in Ag3BHT and Kondo lattice in CuAg4BHT.We conclude by emphasizing how the structure diversity of BHT-based c-CPs dictates their exceptional chemical and physical properties. This Account is more than a summary. It is a blueprint for the design of the next generation of electrically conducting CPs, illustrating how rational ligand design and synthetic control are able to not only advance electronic material exploration but also open new frontiers in quantum materials research.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"8 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111196","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}
Pub Date : 2026-01-30DOI: 10.1021/acs.accounts.5c00712
Shiqing Huang,Guoqing Xu,Zelong Qiao,Danyang Li,Panpan Sun,Dapeng Cao
ConspectusAtomically dispersed M-N-C catalysts, owing to their high metal utilization and well-defined local structure, have been extensively applied in oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) for clean energy devices, such as fuel cells, metal-air batteries, and water electrolyzers. However, traditional trial-and-error approaches to synthesize M-N-C catalysts are significantly time-consuming and resource/labor-intensive and have a low success rate. With the burgeoning development of artificial intelligence (AI) and related computational techniques (such as density functional theory (DFT) and machine-learning (ML)) in heterogeneous catalysis, theory-driven experimental paradigm exerts a huge potential to guide experimental synthesis of M-N-C catalysts and simultaneously reveal the corresponding catalytic mechanisms, which greatly save research and development costs and would speed up applications of clean energies.In this Account, our emphasis is placed on theory-driven experimental discovery of highly efficient M-N-C catalysts, especially single- and dual-atom catalysts (SACs/DACs) for ORR and OER. Indeed, it is a common goal to quantitatively reveal the structure-property relationship of catalysts. Although energy descriptors depending on the adsorption free energy have been proposed by Nørskov et al., they cannot yet achieve the direct prediction of catalyst performance from the intrinsic structure without DFT calculations. Therefore, structure descriptors have been proposed by our group to achieve the direct prediction of catalyst performance from its intrinsic structure and have been successfully applied to four kinds of M-N-C catalysts, including SACs, axial coordination ligand decorated SACs (ACL-SACs), defect-SACs and DACs, which are summarized here. In addition, the key effects of the axial pre-adsorption microenvironment reconstruction of M-N-C catalysts under working conditions and the O2 adsorption step without proton-electron transfer on catalytic performance are discussed, and a new high-throughput (HTP) screening method was proposed, and a series of highly efficient DACs were screened. To accurately describe the interaction between the catalytic surface and intermediates, the "BASED" theory was proposed, and its origin and importance in surface catalysis are also summarized. Driven by the above structure descriptors, high throughput screening method, and "BASED" theory, a series of M-N-C SACs/DACs (such as Fe-N-C, Co-N-C, Cu-N-C, Fe-Mn-N-C, and Fe-Cu-N-C, Mn-Co-N-C) with outstanding performance in half-cells and related devices were synthesized. In short, the theory-driven experimental synthesis of M-N-C catalysts play a pivotal role in propelling the development of heterogeneous M-N-C electrocatalysts and also provide a new research paradigm to develop high-performance catalysts for other reactions and applications.
{"title":"Theory-Driven Experimental Discovery of M-N-C Electrocatalysts.","authors":"Shiqing Huang,Guoqing Xu,Zelong Qiao,Danyang Li,Panpan Sun,Dapeng Cao","doi":"10.1021/acs.accounts.5c00712","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00712","url":null,"abstract":"ConspectusAtomically dispersed M-N-C catalysts, owing to their high metal utilization and well-defined local structure, have been extensively applied in oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) for clean energy devices, such as fuel cells, metal-air batteries, and water electrolyzers. However, traditional trial-and-error approaches to synthesize M-N-C catalysts are significantly time-consuming and resource/labor-intensive and have a low success rate. With the burgeoning development of artificial intelligence (AI) and related computational techniques (such as density functional theory (DFT) and machine-learning (ML)) in heterogeneous catalysis, theory-driven experimental paradigm exerts a huge potential to guide experimental synthesis of M-N-C catalysts and simultaneously reveal the corresponding catalytic mechanisms, which greatly save research and development costs and would speed up applications of clean energies.In this Account, our emphasis is placed on theory-driven experimental discovery of highly efficient M-N-C catalysts, especially single- and dual-atom catalysts (SACs/DACs) for ORR and OER. Indeed, it is a common goal to quantitatively reveal the structure-property relationship of catalysts. Although energy descriptors depending on the adsorption free energy have been proposed by Nørskov et al., they cannot yet achieve the direct prediction of catalyst performance from the intrinsic structure without DFT calculations. Therefore, structure descriptors have been proposed by our group to achieve the direct prediction of catalyst performance from its intrinsic structure and have been successfully applied to four kinds of M-N-C catalysts, including SACs, axial coordination ligand decorated SACs (ACL-SACs), defect-SACs and DACs, which are summarized here. In addition, the key effects of the axial pre-adsorption microenvironment reconstruction of M-N-C catalysts under working conditions and the O2 adsorption step without proton-electron transfer on catalytic performance are discussed, and a new high-throughput (HTP) screening method was proposed, and a series of highly efficient DACs were screened. To accurately describe the interaction between the catalytic surface and intermediates, the \"BASED\" theory was proposed, and its origin and importance in surface catalysis are also summarized. Driven by the above structure descriptors, high throughput screening method, and \"BASED\" theory, a series of M-N-C SACs/DACs (such as Fe-N-C, Co-N-C, Cu-N-C, Fe-Mn-N-C, and Fe-Cu-N-C, Mn-Co-N-C) with outstanding performance in half-cells and related devices were synthesized. In short, the theory-driven experimental synthesis of M-N-C catalysts play a pivotal role in propelling the development of heterogeneous M-N-C electrocatalysts and also provide a new research paradigm to develop high-performance catalysts for other reactions and applications.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"93 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089056","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}
Pub Date : 2026-01-27DOI: 10.1021/acs.accounts.5c00828
He-Qi Zheng, Qi Zhang, Yuanjing Cui, Guodong Qian
Near-infrared (NIR) light, especially NIR-II light (1000–2000 nm), has shown extensive applications in military and civilian fields such as night vision, biomedicine, optical communication, and noninvasive detection due to its superior penetration capabilities, invisibility to human eyes, less background interference, and low optical loss in optical fibers. The development of photonic materials that can absorb or emit NIR light thus has attracted great interest. Recently, metal–organic frameworks (MOFs), which were assembled by metal nodes and organic ligands, have emerged as particularly exciting crystalline porous materials due to their prospective applications in various fields, such as gas storage and separation, chemical sensing, catalysis, proton conduction, and drug delivery. The abundant and tailorable structures, as well as permanent porosity of MOFs, render them highly promising for NIR photonic applications. MOFs allow the rational and tunable design of NIR photonic materials by the judicious incorporation of NIR-responsive inorganic and organic units with the desired functionalities. In addition, the permanent porosity of MOFs greatly extends their opportunities toward NIR photonic materials. As ordered porous materials, MOFs are able to encapsulate diverse NIR-responsive photonic species, such as lanthanide ions, organic dyes, metal complexes, perovskite quantum dots, lanthanide-doped nanoparticles, etc., into the pores or structural-defect spaces for novel NIR photonic properties. More importantly, the well-organized and tunable pores can provide identical secondary environments around photonic species and control the intermolecular interactions as well as energy/charge transfer process between guests and MOFs, thus bringing much flexibility to pursue excellent or novel NIR photonic properties.
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Pub Date : 2026-01-26DOI: 10.1021/acs.accounts.5c00818
Guo Tian, Zining Wang, Chenxi Zhang, Fei Wei
Modern catalysis has traditionally focused on the optimization of isolated active sites; however, industrial-scale chemical manufacturing relies on the integration of reaction, transfer, separation, and feedback operations. The disconnection between these two disciplines─catalysis and process engineering─creates a fundamental gap between molecular precision and process efficiency. Bridging this gap requires reimagining the catalyst not as a static reactive surface, but as a nano miniaturized chemical process, where sequential unit operations are spatially and kinetically coordinated within a single material framework. Consequently, achieving such process intensification at the catalytic scale represents one of the frontier challenges in sustainable chemistry and materials design.
{"title":"Nano Bifunctional Catalysts as Miniaturized Chemical Processes for COx-to-Aromatics Conversion","authors":"Guo Tian, Zining Wang, Chenxi Zhang, Fei Wei","doi":"10.1021/acs.accounts.5c00818","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00818","url":null,"abstract":"Modern catalysis has traditionally focused on the optimization of isolated active sites; however, industrial-scale chemical manufacturing relies on the integration of reaction, transfer, separation, and feedback operations. The disconnection between these two disciplines─catalysis and process engineering─creates a fundamental gap between molecular precision and process efficiency. Bridging this gap requires reimagining the catalyst not as a static reactive surface, but as a nano miniaturized chemical process, where sequential unit operations are spatially and kinetically coordinated within a single material framework. Consequently, achieving such process intensification at the catalytic scale represents one of the frontier challenges in sustainable chemistry and materials design.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"7 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048350","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}
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