Chemphyschem最新文献

{"title":"Meta-Connected Oligo-Azobenzenes Outperform Their Para Counterparts.","authors":"Nils Oberhof, Leon Kambiz Paschai Darian, Andreas Dreuw","doi":"10.1002/cphc.202400799","DOIUrl":"10.1002/cphc.202400799","url":null,"abstract":"<p><p>Systems with multiple photoswitchable units in one molecule have attracted considerable attention in the past years as they are useful for a broad variety of possible applications. Especially, linked azobenzenes sharing one benzene ring are of high interest since their direct linkage introduces an additional photoswitchable unit at only small increase in molecular weight. In this spirit, linear oligo-azobenzenes had been synthesized, though their photochemical properties have only been investigated for short chain lengths. In this study, we use (time-dependent) density functional methodology for the evaluation of the excitations of meta- and para-connected oligo-azobenzenes to predict their switching ability. It becomes apparent, that the meta connection pattern enables each azobenzene subunit to act as an individual switchable unit, whereas they are strongly coupled and loose their individuality in para connection. Therefore, meta-oligo-azobenzenes are ideal candidates for future studies of azobenzene-based functional polymers, while para-oligo-azobenzenes are not.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400799"},"PeriodicalIF":2.3,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142590177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-Metal Bonding in Tri-Actinide Clusters: A DFT Study of [An₃Cl₆]^z (z=1-6) and [An₃Cl₆Cp₃]^z (z=-2-+3; An=Ac, Th, Pa, U, Np, Pu).","authors":"Josef Tomeček, Stephen T Liddle, Nikolas Kaltsoyannis","doi":"10.1002/cphc.202400816","DOIUrl":"10.1002/cphc.202400816","url":null,"abstract":"<p><p>The actinide-actinide bonding in tri-actinide clusters [An₃Cl₆]^z (An=Ac-Pu, z=1-6) and [An₃Cl₆Cp₃]^z (z=-2-+3; Cp=(η⁵-C₅H₅)) is studied using density functional theory. We find 3-centre bonding similar to the tri-thorium cluster [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃{K(THF)₂}₂]_∞, as we previously reported (Nature 2021, 598, 72-75). The population of 3-centre molecular orbitals (3c-MOs) by zero, one or two electrons correlates with shortening of the An-An bond lengths, which also decrease with increasing actinide atomic number, consistent with the contraction of the actinide valence atomic orbitals. Mulliken analyses indicate that these 3c-MOs predominantly involve An 6d and 5 f orbitals. Various methods evidence the presence of An-An bonding in most systems with populated 3c-MOs, including bond orders (Mayer and Wiberg), quantum theory of atoms in molecules metrics (ρ, ∇²ρ, -G/V, H, delocalization indices), electron localization function, and electron density assessments. Additionally, we explore the effect of Cp ligand substitution on uranium complexes, finding that bulkier Cp ligands can induce U-U bond distortions and result in slightly longer U-U bonds. Overall, this study advances our understanding of metal-metal bonding in tri-actinide clusters, highlighting its effects on geometric and electronic structures.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400816"},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142582303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cover Feature: Chlorine-Modified Soluble Melem-Based Graphitic Carbon Nitrite: Facile Synthesis, Catalytic Property and Ultrafast 2D IR Spectroscopic Characterization (ChemPhysChem 21/2024)","authors":"Yueting Zhao,&nbsp;Pengyun Yu,&nbsp;Jianping Wang","doi":"10.1002/cphc.202482103","DOIUrl":"https://doi.org/10.1002/cphc.202482103","url":null,"abstract":"<p><b>The Cover Feature</b> shows chlorine-modified soluble melem-based graphitic carbon nitrite (CNCl), which showed better photocatalytic performance than g-C₃N₄ in the decomposition of methyl orange. CNCl showed much improved dispersibility and solubility in water, DMSO and other solvents. Time-resolved two-dimensional infrared vibrational spectroscopy and other analytical methods were used to understand the photocatalytic performance of CNCl on a microscopic level. More information can be found in the Research Article by J. Wang and co-workers (DOI: 10.1002/cphc.202400356).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"25 21","pages":""},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202482103","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting the Exposed Surface Characteristics on the Stability and Photoelectric Properties of MAPbI₃.","authors":"Bingdong Zhang, Ruiyang Shi, Hongke Ma, Kai Ma, Zhengyang Gao, Hao Li","doi":"10.1002/cphc.202400897","DOIUrl":"10.1002/cphc.202400897","url":null,"abstract":"<p><p>CH₃NH₃PbI₃ (MAPbI₃), as a promising candidate of photovoltaic materials, has attracted extensive interests due to its excellent photoelectric properties and low preparation cost. However, the relationship between synthesis parameter and performance is still unclear due to the overlook of exposed surface characteristics, limiting the mass-production and commercialization of MAPbI₃. Therefore, it is necessary to clarify the stability and photoelectric properties of different exposed surfaces of MAPbI₃ under humid environment. In this work, the stability and photoelectric properties of the MAI-terminated and PbI₂-terminated of MAPbI₃ (001) were thoroughly investigated using density functional theory calculation. To study the stability of exposed surface, adsorption energy of water molecules, ab initio molecular dynamics (AIMD), mean square displacement (MSD) and X-ray diffraction (XRD) were calculated. MSD of PbI₂-terminated surface is greater by two orders of magnitude compared to MAI-terminated surface. For the photoelectric properties of MAPbI₃, the bandgap, absorption coefficients, joint density of states (JDOS) and dielectric constants were investigated. The inhibitory effect of water on the photoelectric performance for PbI₂-terminated surface is more significant than that of MAI-terminated surface. Although the photoelectric properties of water molecules adsorption on MAI-terminated surface is basically unchanged, the diffusion of water molecules reduces the photoelectric properties of MAPbI₃. Overall, the stability and photoelectric properties of MAI-terminated surface are superior to PbI₂-terminated surface. Therefore, we strongly advocate paying attention to the exposed surface of MAPbI₃ during the thin film production process and adjusting synthesis parameters to prepare MAI-terminated surface dominated thin film, which should substantially improve the performance of MAPbI₃ in the application.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400897"},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142582308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cover Feature: Combining Nitrogen Doping and Vacancies for Tunable Resonant States in Graphite (ChemPhysChem 21/2024)","authors":"Demba Demba,&nbsp;Abhishek Karn,&nbsp;Cyril Chacon,&nbsp;Yann Girard,&nbsp;Vincent Repain,&nbsp;Amandine Bellec,&nbsp;Hakim Amara,&nbsp;Philippe Lang,&nbsp;Jérôme Lagoute","doi":"10.1002/cphc.202482102","DOIUrl":"https://doi.org/10.1002/cphc.202482102","url":null,"abstract":"<p><b>The Cover Feature</b> shows a vacancy combined with nitrogen dopants on graphite. The two spectra correspond to the resonant state of a vacancy with (red) or without (yellow) nitrogen doping. In the presence of nitrogen, the vacancy state shifts from an unoccupied to an occupied energy level. More information can be found in the Research Article by J. Lagoute and co-workers (DOI: 10.1002/cphc.202400221).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"25 21","pages":""},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202482102","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Front Cover: Nonadiabatic Photodynamics of Amantadine and 1-Cyanoadamantane Cations (ChemPhysChem 21/2024)","authors":"Bonasree Roy,&nbsp;Evgenii Titov,&nbsp;Peter Saalfrank","doi":"10.1002/cphc.202482101","DOIUrl":"https://doi.org/10.1002/cphc.202482101","url":null,"abstract":"<p><b>The Front Cover</b> artistically illustrates different excited-state lifetimes of the cations of 1-cyanoadamantane and amantadine—nitrogen-containing derivatives of the adamantane cation. In their Research Article (DOI: 10.1002/cphc.202400331), B. Roy, E. Titov, and P. Saalfrank relate how the nonadiabatic dynamics and electronic spectra were studied by using surface-hopping molecular dynamics simulations and quantum chemical calculations.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"25 21","pages":""},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202482101","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Absence of the Third Linker Domain of ApcE Subunit in Phycobilisome from Synechocystis 6803 Reduces Rods-To-Core Excitation Energy Transfer.","authors":"Dariusz M Niedzwiedzki, Rupal Singh Tomar, Fatima Akram, Anna M Williams, Haijun Liu","doi":"10.1002/cphc.202400933","DOIUrl":"10.1002/cphc.202400933","url":null,"abstract":"<p><p>Phycobilisome (PBS) is a pigment-protein complex utilized by red algae and cyanobacteria in photosynthesis for light harvesting. A cyanobacterium Synechocystis sp. PCC 6803 contains PBS with a tricylindrical core built of allophycocyanin (APC) disks where six phycocyanin (PC) rods are attached. The top core cylinder is seemingly involved in attaching four PC rods and binding orange carotenoid protein (OCP) to quench excess of excitation energy. In this study, we have deleted the third linker domain (LD3) of ApcE subunit of PBS which assembles four APC discs into the top core cylinder. The mutation resulted in PBS with bicylindrical core, structurally comparable to the naturally existing PBS from Synechococcus 7942. Lack of LD3 and the top APC cylinder reduces the excitation energy transfer between PC and APC in the mutant. Moreover, these PBSs are more prone to light induced-photodamage and do not bind to the photoactivated orange carotenoid protein (OCP), a known PBS excitation quencher. These findings highlight the complex and elegant interplay between the PBS architecture and the functional efficiency, suggesting that in PBSs with naturally tri-cylindrical cores, the top cylinder has essential roles in recruiting the rods and proper binding of OCP.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400933"},"PeriodicalIF":2.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142582271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Na-Ion Electrochemical Performance through Cu Doping-Mediated Sb₂Se₃ Phase Transformation into CuSbSe₂ with Improved Kinetics.","authors":"Shah Jahan Ul Islam, Kowsar Majid, Malik Wahid","doi":"10.1002/cphc.202400793","DOIUrl":"10.1002/cphc.202400793","url":null,"abstract":"<p><p>This work investigates the influence of structural and electronic modification on the electrochemical performance of conversion and alloying materials. The CuSbSe₂, a promising 2D layered conversion, and alloying material is being investigated with references to parent pristine Sb₂Se₃ and a doped version of later Sn_0.2Sb_1.8Se₃ for their sodium-ion battery performance. The CuSbSe₂ with layered structure is well known to accommodate lattice distortions via inter-layer movement, potentially mitigating distortions brought about by the Alkali ion (Na in this case) insertion. In contrast, the parent conversion-cum-alloying material Sb₂Se₃ with its one-dimensional crystal structure leads to structural disintegration during battery operation. The Sn-doped analog, Sn_0.2Sb_1.8Se₃, comparatively exhibits enhanced kinetics owing to the reduced long-range order. The 2D layered, CuSbSe₂ despite exhibiting 2D long-range order exhibits superior electrochemical performance owing to the favorable electronic and structural features. The CuSbSe₂ exhibits a reversible capacity of 881 mAh g^-1 compared to 516 mAh g^-1 for Sn_0.2Sb_1.8Se₃ and 429 mAh g^-1 for Sb₂Se₃, with an improved Coulombic efficiency as well. The transient electrochemical investigations of Electrochemical Impedance Spectroscopy (EIS) and Galvanostatic intermittent titration techniques (GITT) reveal that better performance exhibited by CuSbSe₂ may well be attributed to kinetics owing to enhanced diffusion coefficients in the intercalation and conversion regime.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400793"},"PeriodicalIF":2.3,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142575112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Light-Induced Transformation of a Supramolecular Gel to a Stronger Covalent Polymeric Gel.","authors":"Sabith K Saleem, Thejus Pramod, Pruthvi Kuruva, Shyamkumar V Haridas, Anusha Shanmugam, Madhu Thalakulam, Kana M Sureshan","doi":"10.1002/cphc.202400861","DOIUrl":"10.1002/cphc.202400861","url":null,"abstract":"<p><p>A polymerizable diacetylene gelator, containing urea and urethane groups, that congeals various non-polar solvents was synthesized. The gelator molecules self-assemble forming non-covalent polymers through intermolecular hydrogen bonding, as evidenced from FT-IR and concentration-dependent ¹H NMR spectroscopy. The self-assembly positions the diyne units of adjacent molecules at proximity and in a geometry suitable for their topochemical polymerization. UV irradiation of the gel resulted in topochemical polymerization, transforming the non-covalent polymer to a covalent polymer, in situ, in the gel state. The polymerization was confirmed by characterizing the polydiacetylene (PDA) using UV-Vis and Raman spectroscopy. Time-dependent rheological studies revealed gradual strengthening of the gel with the duration of irradiation, suggesting that the degree of polymerization increases with the duration of irradiation. The PDA formed is a semiconductor, which might be useful for various applications.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400861"},"PeriodicalIF":2.3,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142567476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Investigation of the Structures of [(Glycine)(1-Methyluracil)]M⁺ Complexes (M=H, Li, Na, K) in the Gas Phase by IRMPD Spectroscopy and Theoretical Methods.","authors":"Samuel C Atkinson, Travis D Fridgen","doi":"10.1002/cphc.202400884","DOIUrl":"10.1002/cphc.202400884","url":null,"abstract":"<p><p>The presence of ions in the complexation of molecules can profoundly affect the structure, resulting in changes to functionality and stability. These non-covalent interactions drive many biological processes both necessary and inimical and require extensive research to understand and predict their effects. Protonated and alkali metalated complexes of glycine (Gly) and 1-methyluracil (1-mUra) were studied using infrared multiphoton dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations. The experimental and simulated vibrational spectra were compared to help elucidate the structure of each complex. The lowest energy structure for [(Gly)(1-mUra)]H⁺ consists of amine protonated Gly bound to O4 of canonical 1-mUra through a single ionic hydrogen bond with another, intraglycine ionic hydrogen bond between the protonated amine group and the carbonyl oxygen. For [(Gly)(1-mUra)]Li⁺, [(Gly)(1-mUra)]Na⁺ and [(Gly)(1-mUra)]K⁺, the experimental spectra are most consistent with the metal cations binding in a trigonal planar geometry with 1-mUra bound to the metal cation via the O4 carbonyl. In [(Gly)(1-mUra)]Li⁺ and [(Gly)(1-mUra)]Na⁺, the metal cation is bound to canonical Gly via the carbonyl oxygen and amine nitrogen, but in [(Gly)(1-mUra)]K⁺, Gly is bound through both oxygens and contains an intraglycine hydrogen bond from the hydroxyl to the amine nitrogen. It was found that the B3LYP/6-31+G(d,p) vibrational spectra are most consistent with the experimental spectra, but M062X was better than B3LYP at determining the lowest-energy structures.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400884"},"PeriodicalIF":2.3,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142567462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}