Accounts of Chemical Research最新文献

{"title":"","authors":"Piyush Gupta,  and , Claudia Turro*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00221","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422774","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":"Dirhodium(II,II) Complexes as Panchromatic Single-Molecule Photocatalysts for Hydrogen Evolution.","authors":"Piyush Gupta, Claudia Turro","doi":"10.1021/acs.accounts.5c00221","DOIUrl":"10.1021/acs.accounts.5c00221","url":null,"abstract":"<p><p>ConspectusThe growing global energy demand and climate change have prompted a shift from carbon-based fuels to sustainable energy sources. Hydrogen production by harnessing solar energy and using abundant proton sources represents an attractive approach to addressing this crisis. Single-molecule single-chromophore photocatalysts, capable of both absorbing the incident photon and catalyzing the chemical transformation, are able to circumvent energy losses present in multicomponent systems that require a photosensitizer and a catalyst, often employing additional redox relay molecules. The series of complexes derived from <i>cis</i>-[Rh<sub>2</sub>(μ-DPhF)<sub>2</sub>(μ-bncn)<sub>2</sub>]<sup>2+</sup> (<b>1</b>; DPhF = <i>N</i>,<i>N</i>'-diphenylformamidinate, bncn = benzo[<i>c</i>]cinnoline) discussed in this Account presents robust and air-stable single-molecule photocatalysts with panchromatic absorption from the ultraviolet spectral region to the near-infrared (NIR), with high turnover frequencies of ∼20 to 30 h<sup>-1</sup> under red light irradiation. For comparison, other single-molecule hydrogen-evolving photocatalysts reported to date exhibit low photocatalytic efficiency, are not operable in the visible or NIR regions, and are unstable under an ambient atmosphere.Through ground state photophysical characterization and theoretical calculations, the highest occupied molecular orbital (HOMO) in this class of complexes was assigned to be centered on the Rh<sub>2</sub>(δ*)/Form(π/nb) MO, while the lowest occupied MO (LUMO) is localized on bncn(<i>π*</i>), with the lowest-energy absorption attributed to the HOMO → LUMO singlet metal/ligand-to-ligand charge transfer (<sup>1</sup>ML-LCT) transition. Emission observed at 77 K was assigned to arise from the <sup>3</sup>ML-LCT state with an estimated excited-state reduction potential of ∼+1.0 V vs Ag/AgCl, making these complexes strong oxidizing agents upon illumination. The <sup>3</sup>ML-LCT lifetimes of these complexes at room temperature range from 1 to 33 ns and are influenced by the presence of a low-lying metal-centered (<sup>3</sup>MC) state.Experiments designed to elucidate the mechanism for photocatalytic proton reduction have shown that the parent Rh<sub>2</sub>(II,II) molecule, [<b>Rh</b><sub><b>2</b></sub>], undergoes two sequential photon absorption and reduction events generating [<b>Rh</b><sub><b>2</b></sub>]<sup>2-</sup>, thus storing two redox equivalents. The ability of the singly reduced complex, [<b>Rh</b><sub><b>2</b></sub>]<sup>-</sup>, to absorb a photon and oxidize substrates in solution from its excited state to generate [<b>Rh</b><sub><b>2</b></sub>]<sup>2-</sup> represents a critical step in the catalytic cycle. Both isolated [<b>Rh</b><sub><b>2</b></sub>]<sup>-</sup> and [<b>Rh</b><sub><b>2</b></sub>]<sup>2-</sup> species are able to produce hydrogen in acidic media, making multiple simultaneous pathways possible during photocatalysis; however, the latter was shown ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1913-1923"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197659","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":"","authors":"Brady R. Layman, Daniel M. Carrel and Jeffrey E. Dick*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00135","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422771","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":"","authors":"Ming-Qiang Qi, Ming-Hao Du, Xiang-Jian Kong*, La-Sheng Long* and Lan-Sun Zheng, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00151","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422775","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":"","authors":"Junjuan Shi,  and , Ming Wang*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00209","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422770","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":"","authors":"Paulina Szymczak, Wojciech Zarzecki, Jiejing Wang, Yiqian Duan, Jun Wang, Luis Pedro Coelho, Cesar de la Fuente-Nunez* and Ewa Szczurek*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.0c00594","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144343168","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":"","authors":"Lian-Wei Ye, Han-Shi Hu, W. H. Eugen Schwarz and Jun Li*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00233","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422777","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":"Physical Origin and Periodicity of the Highest Oxidation States in Heavy-Element Chemistry.","authors":"Lian-Wei Ye, Han-Shi Hu, W H Eugen Schwarz, Jun Li","doi":"10.1021/acs.accounts.5c00233","DOIUrl":"10.1021/acs.accounts.5c00233","url":null,"abstract":"<p><p>ConspectusThe exploitation of combustion of materials stands as a cornerstone of early human development. A theoretical framework for this field began to take shape only around 1700 and finally achieved a sound foundation through the electronic quantum-chemical oxidation concepts of the 20th century. Eventually, a decade ago the IUPAC defined the essential rules for a unique definition of atomic oxidation states (OS) or OS numbers in molecules and extended structures. In specific cases, however, these rules need be tailored to specific chemical observations, including amazing experiences with the heaviest elements. We review our findings and updated interpretations, particularly with regard to previously unexpected trends in the highest oxidation states (HOS) of heavy atomic compounds.The HOS is a qualitative integer parameter for characterizing the chemistry of an element. It is determined by three basic factors: (i) by the number <i>g</i> of loosely bound electrons in the atom's valence shell, usually related to its group number <i>G</i> in the periodic table (<i>g = G</i> mod 10, with mod meaning <i>g</i> = 2 to 8 for <i>G</i> = 12-18); (ii) by the fraction of these <i>g</i> electrons that can be chemically activated and may fall below <i>g</i> toward the end of a series; and (iii) by the local and long-range \"environmental\" conditions (mainly the interaction strengths of the ligands), which range from those in normal life, laboratories and industry, to more extreme conditions such as deep inside the Earth, outside in cosmic space, or in special laboratories.In recent years, our group has systematically investigated the regularity of the HOS over the periodic table, in particular the electronic structures of compounds of various d- (transition metals) and f-block elements (lanthanides and actinides), applying both density-functional approximations and more advanced quantum-chemical methods. Details of the HOS values in the border ranges of feasibility, depending on thermodynamic environment and ligand-interaction capabilities, are conceptually analyzed, incorporating also discoveries of other researchers. The patterns of the HOS from the light s- and sp- to the heavy d- and f-block elements are elucidated, showing systematic deviations from simple textbook rules. The particularly large and small Core-Valence (CV) orbital-energy gaps at, respectively, the upper-right and lower-left corners of the periodic table interrupt the regular trends of the HOS of the sp-block elements, causing HOS < <i>g</i> (as for O or Pt) or HOS > <i>g</i> (as for Cs or Ra). On the other hand, the d-transition metals (TM) and also the actinide 5f-series (An) in the middle of the periodic table show a more uniform variation of the HOS with one common maximum at 8(±1), while the lanthanide 4f-series (Ln) shows two lower HOS maxima, due to their peculiarly small 4f-orbital radii and varying energies.Our report is intended both as a summary of knowledge, as a distil","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1903-1912"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126109","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":"Multiphase Electrochemiluminescence of Microdroplets and Radical Salts.","authors":"Brady R Layman, Daniel M Carrel, Jeffrey E Dick","doi":"10.1021/acs.accounts.5c00135","DOIUrl":"10.1021/acs.accounts.5c00135","url":null,"abstract":"<p><p>ConspectusOver the past decade, experiments involving microdroplets have challenged the framework of chemistry. These droplets constitute a multiphase system, where the dynamic interplay between solid, liquid, and gas influences reactions. Multiphase systems are prevalent in nature and possess unique physicochemical properties. However, in chemistry, phase boundary reactivity is often overlooked because molecules experience \"bulk\" reactivity. These systems are prevalent in biological processes, such as cell mitosis, biological sensor technology, organic synthesis, and pollution remediation.Recently, our group has developed different strategies of electrochemiluminescence (also called electrogenerated chemiluminescence, both shortened to ECL) microscopy and imaging to understand the unique properties and dynamics at electrified interfaces. ECL takes advantage of the reactivity between a luminophore that radically annihilates with a strong oxidizing or reducing reagent. If the enthalpy of annihilation is high enough, the luminophore will be left in an excited state and radiatively decay, producing light. Thus, ECL requires no incident light, and ECL microscopy has unique analytical figures of merit due to the light being emitted close to the electrified interface (1-10 μm), providing insight into reactivity within the electrode's proximity.This Account will detail our group's efforts in discovering ECL reactions in environments exhibiting native triphasic (liquid|liquid|electrode) interfaces and reactions where new phases are formed (e.g., bubble nucleation and electroprecipitation). We first began developing the tools necessary to image liquid|liquid interfaces and discovered that, when neighboring droplets fuse together, small pockets (inclusions) of the continuous phase existed inside the merged droplets. Studies of inclusion chemical reactivity have led to the interesting observation that small droplets on electrified interfaces can act as gas micropumps, protecting the electrode from gas buildup during electrocatalytic reactions.Even though a strength of ECL is that emission is confined directly to the surface, this can also be a significant weakness, considering interesting chemical phenomena can occur far away from the electrode surface. One recent thrust in the community is discovering new ways of using ECL far away from the electrode surface, a phenomenon termed \"Through-Space ECL\". Our group has used this technique to measure bubble forces at phase boundaries far from the electrode surface.By playing on the relative solubilities of ECL reactants and products, we showed that, if a radical ion can be generated and precipitates more quickly than its radical lifetime, radical salts can be formed. These radical salts are a way to fossilize highly energetic molecules. We have used this seemingly new chemical tenet to effectively bottle up ECL, fossilizing the reactants to be used elsewhere in space and time. Given our passion to teach the","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1856-1866"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214310","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":"","authors":"Leilei Zhang, Xiaofeng Yang, Jian Lin, Xuning Li, Xiaoyan Liu, Botao Qiao, Aiqin Wang* and Tao Zhang*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00140","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422772","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}