Chemphyschem最新文献_第6页

Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study. HOPG上双核铁（II）配合物的自旋交叉：x射线吸收光谱研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202401081

Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch

{"title":"Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study.","authors":"Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch","doi":"10.1002/cphc.202401081","DOIUrl":"10.1002/cphc.202401081","url":null,"abstract":"The spin-crossover (SCO) properties of the dinuclear complex <math> <semantics><mrow><mo>[</mo> <msub><mrow><mo>{</mo> <mtext>Fe</mtext> <msub> <mrow><mrow><mo>(</mo> <msub><mi>H</mi> <mn>2</mn></msub> <mi>B</mi> <msub><mrow><mo>(</mo> <mtext>pz</mtext> <mo>)</mo></mrow> <mn>2</mn></msub> <mo>)</mo></mrow> </mrow> <mn>2</mn></msub> <mo>}</mo></mrow> <mn>2</mn></msub> <mi>μ</mi> <mo>-</mo> <mo>(</mo> <msub><mrow><mtext>ac(bipy)</mtext></mrow> <mn>2</mn></msub> <mo>)</mo> <mo>]</mo></mrow> <annotation>$left[right. left{right. text{Fe} left(left(right. left(text{H}right)_{2} text{B} left(left(right. text{pz} left.right)right)_{2} left.right)right)_{2} left(left.right}right)_{2} mu - left(right. left(text{ac(bipy)}right)_{2} left.right) left]right.$</annotation></semantics> </math> are studied as (sub)-monolayer and thin film deposited by an ultrahigh vacuum liquid-jet deposition technique on highly oriented pyrolytic graphite (HOPG) by X-ray absorption spectroscopy. A comparison of the SCO properties of thin films and a dropcast sample indicates that the spin-switching probability of the thin films is limited due to substrate-molecule interactions. The maximum percentage of molecules in the low-spin (LS) state observed for 0.7 and 1.8 monolayers (ML) is ≈43% at a temperature of 80 K in comparison to the dropcast sample where ≈66% of the complex is in the LS state. The similar switching properties of the dropcast sample as of a bulk powder sample confirm that the SCO properties are not affected by the presence of solvent necessary for deposition. The soft-X-ray-induced excited spin-state trapping (SOXIESST) effect is pronounced in all samples, although the light-induced high-spin (HS) fraction of the dropcast and the thin-film samples on HOPG is higher as compared to the HS fraction attained by SOXIESST, which confirms the sensitivity of the complex to light.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401081"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794753","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}

引用次数: 0

Reactions of 1,4-Diborinine Derivatives with CO₂. 1,4-二硼碱衍生物与CO2的反应。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202401049

Maxime Ferrer, Ibon Alkorta, José Elguero, Israel Fernandéz

引用次数: 0

QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2'-Bipyridyl Rigid Core. 具有2,2'-联吡啶刚性核的[2]轮烷分子梭的QTAIM分析。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202500074

Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti

{"title":"QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2'-Bipyridyl Rigid Core.","authors":"Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti","doi":"10.1002/cphc.202500074","DOIUrl":"10.1002/cphc.202500074","url":null,"abstract":"Chemical contacts responsible for the supramolecular assembly of a rigid H-shaped [2]rotaxane molecular shuttle composed of a 24-crown-8(24C8) macrocycle on a molecular thread containing two benzimidazole (Bzi) recognition sites and a central 2,2'-bipyridyl (Bipy) rigid core are analytically addressed by combining the Quantum Theory of Atoms in Molecules (QTAIM) with density functional theory (DFT). In this respect, the available crystallographic structure-CCDC number 2248267-is taken as a reference condition for addressing the nature of the chemical interactions finely modulating the shuttling of the 24C8 between Bzi stations. Moreover, previous DFT computations (Chem. Sci., 2023, 14, 7215) are extended over a supercomputing environment to address the proposed ligand exchange mechanism involving DMF solvent molecules and promoting the observed shuttling process upon the addition of Zn(II) cations. To this end, converged DFT wavefunctions are fully analyzed by means of electron density ρ(r) and local electronic energy density-H(r)-descriptors; interestingly, the derived covalent versus noncovalent interaction patterns shed some light on the mutual position of the macrocycle along the axle following the coordination of Zn(II) ions in DMF solvent.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500074"},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771475","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}

引用次数: 0

Nonadditive CO₂ Uptake of Type II Porous Liquids Based on Imine Cages. 基于亚胺笼的II型多孔液体的非添加剂CO2吸收。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202400985

Lu Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S Sholl, Ryan P Lively

{"title":"Nonadditive CO2 Uptake of Type II Porous Liquids Based on Imine Cages.","authors":"Lu Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S Sholl, Ryan P Lively","doi":"10.1002/cphc.202400985","DOIUrl":"10.1002/cphc.202400985","url":null,"abstract":"Type II porous liquids can potentially exploit the fluidity of liquids and sorption properties of porous sorbents, yet CO2 uptake in porous liquids is still poorly understood. Molecular simulations and experiments are used to examine CO2 uptake by a prototypical porous liquid composed of porous organic cages (CC13) in 2'-hydroxyacetophenone (2'-HAP). The simulations are in reasonable agreement with experimental measurements of CO2 solubility and provide unambiguous information on the partitioning of CO2 within microenvironments in the liquid. Analysis of CO2 dynamics is performed using these simulations, including assessing the self-diffusivity of CO2 in both the neat solvent and porous liquid. This offers insights into the kinetics of CO2 uptake and transport in type II porous liquids based on imine cages. Experiments with type II porous liquids formed by dissolving CC13 in three different size-excluded solvents show nonadditive CO2 absorption relative to predictions based on ideal volume additivity. This nonadditive absorption behavior is also observed in simulations. Nonadditive CO2 uptake is also demonstrated in type II porous liquids based on another imine-based porous cage, CC19.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2400985"},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143779230","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}

引用次数: 0

Overcoming Challenges in Density Functional Theory-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals. 克服基于dft计算重杂原子自由基超精细耦合常数的挑战。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202400978

Maciej Witwicki

{"title":"Overcoming Challenges in Density Functional Theory-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals.","authors":"Maciej Witwicki","doi":"10.1002/cphc.202400978","DOIUrl":"10.1002/cphc.202400978","url":null,"abstract":"This study assesses density functional theory (DFT) methods for their accuracy in calculating hyperfine coupling constants (HFCCs) of heavy heteroatom radicals with heteroatoms including Sb, Bi, In, Tl, and Sn. Given the essential role of electron paramagnetic resonance spectroscopy in characterization of these species, it is crucial that theoretical models can predict HFCCs accurately for heavy elements. This work presents a computational approach that addresses crucial factors: selection of basis set, hybrid exchange-correlation functional, higher Hartree-Fock (HF) exchange, and the Gaussian description of nuclear charge. The relativistic effects are introduced using one-component linear response theory with the second-order Douglas-Kroll-Hess formalism and the fully relativistic four-component Dirac-Kohn-Sham method. The findings show that, while one-component DFT is accurate for the 4th-row elements, the four-component method is more precise for the 5th-row radicals and the one-component approach fails for the 6th-row congeners. Increasing HF exchange significantly improves HFCC predictions. The developed framework for accurate HFCC calculations will enhance the understanding of electronic and magnetic properties of heavy element radicals and can be used by computational chemists and experimentalists alike.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2400978"},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771474","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}

引用次数: 0

Front Cover: Revealing Mechanisms of Lithium-Mediated Nitrogen Reduction Reaction from First-Principles Simulations (ChemPhysChem 7/2025) 封面：从第一线原理模拟揭示锂介导的氮还原反应机制（chemphysichem 7/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-02 DOI: 10.1002/cphc.202580701

Chengyu Zhou, Qing Zhao

引用次数: 0

Cover Feature: Deciphering Mg-Surface Interactions with Unsaturated Hydrocarbons: An Integrated Experimental-Theoretical Study (ChemPhysChem 7/2025) 封面专题：破译mg -表面与不饱和烃的相互作用：一个综合的实验-理论研究（chemphysichem 7/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-02 DOI: 10.1002/cphc.202580702

Sourav Ghoshal, Nathaniel Carnegie, Chidozie Ezeakunne, Beni B. Dangi, Shyam Kattel

引用次数: 0

First-Principles Investigation of 2D o-Al₂C₂ Monolayer: A High-Performance Anode for Li/Na-Ion Batteries. 二维o-Al2C2单层：高性能锂/钠离子电池负极的第一性原理研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-28 DOI: 10.1002/cphc.202500025

Mohamed Agouri, Ayoub Benaddi, Nabil Khossossi, Said El Filali, Abderrahman Abbassi, Abdellatif Hasnaoui, Souad Taj, Bouzid Manaut

{"title":"First-Principles Investigation of 2D o-Al2C2 Monolayer: A High-Performance Anode for Li/Na-Ion Batteries.","authors":"Mohamed Agouri, Ayoub Benaddi, Nabil Khossossi, Said El Filali, Abderrahman Abbassi, Abdellatif Hasnaoui, Souad Taj, Bouzid Manaut","doi":"10.1002/cphc.202500025","DOIUrl":"10.1002/cphc.202500025","url":null,"abstract":"The development of novel anode materials with superior electrochemical performance is imperative for advancing next-generation high-performance rechargeable batteries beyond current limitations. In this study, it presents a 2D o-Al2C2 monolayer as a promising lightweight candidate for lithium and sodium-ion battery systems, based on the density functional theory investigations and ab initio molecular dynamics (AIMD) simulations. Our comprehensive investigation demonstrates that the o-Al2C2 monolayer exhibits remarkable stability with a cohesive energy of -5.30 eV atom-1 and maintains its structural integrity at room temperature during extended AIMD simulations. The o-Al2C2 monolayer demonstrates exceptional electrochemical characteristics for Li and Na storage: theoretical specific capacities of 3780.42 and 3436.75 mA h g-1, optimal average open circuit voltages of 0.81 and 0.67 V, and favorable diffusion barriers of 0.62 eV and 0.31 eV, respectively. These performance metrics significantly surpass those of conventional graphite (372 mA h g-1) and other recently reported 2D anode materials, establishing o-Al2C2 as an exceptionally promising candidate for next-generation energy storage applications. Hence, this current theoretical investigation suggests that the o-Al2C2 monolayer holds significant potential for future experimental studies in lithium and sodium storage applications for LIB and NIB systems.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500025"},"PeriodicalIF":2.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143729067","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}

引用次数: 0

Suppressing Halide Segregation in Wide-Bandgap Perovskite Absorbers by Transamination of Formamidinium. 甲酰胺转氨化抑制宽带隙钙钛矿吸收剂中的卤化物偏析。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-27 DOI: 10.1002/cphc.202500022

Georgios Loukeris, Clemens Baretzky, Dmitry Bogachuk, Audrey Elizabeth Gillen, Bowen Yang, Jiajia Suo, Waldemar Kaiser, Edoardo Mosconi, Filippo De Angelis, Gerrit Boschloo, Andreas Walter Bett, Uli Würfel, Markus Kohlstädt

{"title":"Suppressing Halide Segregation in Wide-Bandgap Perovskite Absorbers by Transamination of Formamidinium.","authors":"Georgios Loukeris, Clemens Baretzky, Dmitry Bogachuk, Audrey Elizabeth Gillen, Bowen Yang, Jiajia Suo, Waldemar Kaiser, Edoardo Mosconi, Filippo De Angelis, Gerrit Boschloo, Andreas Walter Bett, Uli Würfel, Markus Kohlstädt","doi":"10.1002/cphc.202500022","DOIUrl":"10.1002/cphc.202500022","url":null,"abstract":"All-perovskite tandem solar cells are emerging at a fast rate because of their potential to exceed efficiencies of Si-perovskite tandems, in combination with faster manufacturing, lower cost, and the ability to be processed on flexible substrates. Mixing halides is a key to achieve wide-bandgap absorbers, which however suffer from halide segregation under illumination, resulting in lowering of the bandgap. To tackle this problem, butylamine (BA) has been added to the perovskite precursor solution and is found to react with the formamidinium (FA) cation, producing N-butylformamidinium (BuFA+), which accumulates at the perovskite surface and grain boundaries. The creation of the BuFA cation results in suppressed halide segregation and improved crystallization. Density functional theory calculations propose the reduction of halide defect formation upon the addition of BA, being a key to stabilize mixed-halide perovskites. Lastly, we observe a more stable performance of single junction p-i-n perovskite solar cells with the addition of BA under constant illumination at 65 °C.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500022"},"PeriodicalIF":2.3,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718111","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}

引用次数: 0

N-Heterocyclic Carbenes: A Benchmark Study on their Singlet-Triplet Energy Gap as a Critical Molecular Descriptor. n -杂环碳烯：Βenchmark单重态-三重态能隙作为关键分子描述符的研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-27 DOI: 10.1002/cphc.202500012

Konstantinos P Zois, Andreas A Danopoulos, Demeter Tzeli

{"title":"N-Heterocyclic Carbenes: A Benchmark Study on their Singlet-Triplet Energy Gap as a Critical Molecular Descriptor.","authors":"Konstantinos P Zois, Andreas A Danopoulos, Demeter Tzeli","doi":"10.1002/cphc.202500012","DOIUrl":"10.1002/cphc.202500012","url":null,"abstract":"N-heterocyclic carbenes (NHCs) are used extensively in modern chemistry and materials science. The in-depth understanding of their electronic structure and their metal complexes remains an important topic of research and of experimental and theoretical interest. Herein, the adiabatic singlet-triplet gap as a superior, quantifiable critical descriptor, sensitive to the nature and the structural diversity of the NHCs, for a successful rationalization of experimental observations and computationally extracted trends is established. The choice is supported by a benchmark study on the electronic structures of NHCs, using high-level ab initio methods, that is, complete active space self-consistent field, n-electron valence second-order perturbation theory, multireference configuration interaction + singles + doubles, and domain-based local pair natural orbital-coupled cluster method with single-, double-, and perturbative triple excitations along with density functional theory methods such as BP86, M06, and M06-L, B3LYP, PBE0, TPSSh, CAM-B3LYP, and B2PLYP. In contrast to the adiabatic singlet-triplet (S-T) gap preferred as descriptor, the highest occupied molecular orbital-lowest unoccupied molecular orbital gap or the S-T vertical gap that has been used in the past occasionally leads to controversial results; some of these are critically discussed below. Extrapolation of these ideas to a group of copper-NHC complexes is also described.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500012"},"PeriodicalIF":2.3,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718109","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}

引用次数: 0