Structural Chemistry最新文献

{"title":"Atoms in molecules without boundaries: analyses via electrostatic potentials at nuclei","authors":"Jane S. Murray","doi":"10.1007/s11224-024-02369-3","DOIUrl":"https://doi.org/10.1007/s11224-024-02369-3","url":null,"abstract":"<p>This prefatory review begins with historical background relating to the emergence of the electrostatic potential into the field of chemistry and related fields, leading then into the major focus of this paper: electrostatic potentials at nuclei. The electrostatic potential at the nucleus of an atom, whether it be in the free state or in a neutral molecule or in an ionic molecular species, is qualitatively a characteristic property of the atom. It changes remarkably little from one molecular environment to another. As has been shown earlier by Politzer, the energies of atoms and molecules can be expressed both approximately and rigorously in terms of the electrostatic potentials at their nuclei. For example, molecular energies can be written entirely as summations over atomic contributions, with no explicit interatomic terms. This provides a basis for estimating the energy of an atom in a molecule and supports the validity of the atoms-in-molecules concept, however without the necessity of boundaries for the atoms. This has been further substantiated by a recent paper entitled “Atoms do exist in molecules: Analysis using electrostatic potentials at nuclei”, where the authors have shown that the electrostatic potential created by the electrons of all the other atoms at a particular nucleus in a molecular species, not including those associated with that particular atom itself, is almost identical in magnitude to the potential due to the other nuclei. The significance of this will be discussed, with an emphasis on atoms in molecules without boundaries.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142215645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nature of the chemical bonding and electronic structure of dicoordinated copper(I) complexes of alkenes, alkynes, and NHC ligands: a DFT overview","authors":"Nadjet Aimene, Abdallah Zaiter, Hacene Nemdili, Bachir Zouchoune","doi":"10.1007/s11224-024-02366-6","DOIUrl":"https://doi.org/10.1007/s11224-024-02366-6","url":null,"abstract":"<p>A DFT (density functional theory) investigation using the generalized gradient approximation BP86 and the hybrid B3LYP functionals and TZP basis set is dealing with the bonding, the electronic structure and the interaction types occurred within the XCuL’ and (LCuL’)⁺ (X = Cl, CH₃, CN, CF₃, L = CO, NH₃, PH₃, and L’ = C₂H₂, C₂H₄, C₄H₆, C₆H₆, and NHC) complexes. The optimized structures and energy decomposition analysis of XCuL’ and (LCuL’)⁺ complexes were employed to provide a relationship between the bond lengths, the X-Cu-L’ and L-Cu-L’ bond angles, the Wiberg indices, the Mayer bond orders, interaction energies, and the Cu-L’ bonding character. The energy decomposition analysis indicates that the interactions occurred for various L’ ligands are more electrostatically than covalently bonded to the Cu(I) center formally of + I oxidation state. The different contributions stemming from electrostatic and orbital interactions are significant, in relationship with the ionic and covalent characters, respectively. The contribution from σ-donation to the bonding energy was found more important for the NHC ligand than the alkene and alkynes ones. However, the contribution from π-back-donation was found to be comparable for all complexes. The σ-bonding contributes more than 50% into the total orbital interaction overtaking those of π type, in accordance with the population of the copper 4s orbital, particularly in the presence of C₆H₆ and NHC ligands. The interactions in all complexes exhibit comparable deformation densities and NOCV orbital shapes. Besides, it has been shown that the ΔE_prep contributes weakly in the deformation of the interacting fragments as well as the BSSE correction which impacts weakly or negligibly the interactions between the fragments composing different XCuL’ and (LCuL’)⁺ complexes.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142215644","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scandium and Titanium doped hexamine for remarkable nonlinear optical properties: a DFT study","authors":"Maria Mazhar, Areeba Asif, Nimra Maqsood, Haroon Ahmad, Naveed Hamid Nawaz Khan, Muhammad Nouman","doi":"10.1007/s11224-024-02365-7","DOIUrl":"https://doi.org/10.1007/s11224-024-02365-7","url":null,"abstract":"<p>This study explores the nonlinear optical (NLO) properties of hexamine (HMT) doped with transition metals scandium (Sc) and titanium (Ti), exhibiting enhanced NLO responses for advanced photonic devices. Employing ωB97XD functional for optimization and calculations, the study examines geometric parameters, electronic excitation, exciton binding energy (E_b), and vertical ionization energy (VIE) using DFT and TD-DFT. High VIE (3.25 to 4.52 eV) indicates enhanced stability in doped systems. The HOMO-LUMO gap decreases from 10.69 eV in pure HMT to 3.30 to 4.85 eV in the designed systems. These systems exhibit thermodynamic stability with binding energies 3.51 to 4.27 kcal/mol, and Ti-HMT-Ti being the most stable. A two-level approximation method is utilized to determine linear polarizability and nonlinear first and second hyperpolarizability (α_static, β_static, γ_static), which exhibits the highest γ_static (6546.63 au) value of Sc-HMT-Sc. Orbital transitions, charge distribution, electrophilicity, and nucleophilicity are examined using TDM, EDDM, and ESP, respectively. PDOS and TDOS provide insights into HOMO-LUMO gap reduction, NCI identifies the weak interactions and broadened and red-shifted UV absorption spectra, all are in the favour of NLO response of designed complexes. So, these materials show exceptional NLO properties and promising for optoelectronic applications.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141777896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The DFT study of the structural, hydrogen, electronic, mechanical, thermal, and optical properties of KXH3 (X = Ca, Sc, Ti, & Ni) perovskites for H2 storage applications","authors":"Muhammad Awais Rehman, Jawaria Fatima, Zia Ur Rehman, Suliman Yousef Alomar, Muhammad Sohiab, Abu Hamad","doi":"10.1007/s11224-024-02362-w","DOIUrl":"https://doi.org/10.1007/s11224-024-02362-w","url":null,"abstract":"<p>In this study, we employ density functional theory to investigate KXH₃ (X = Ca, Sc, Ti, &amp; Ni) hydride perovskites for H2 storage applications. Lattice parameters calculated using GGA-PBE are 4.482 Å, 4.154 Å, 3.974 Å, and 3.686 Å for KCaH₃, KScH₃, KTiH₃, and KNiH₃, respectively. Electronic structure analysis shows KScH₃, KTiH₃, and KNiH₃ are metallic, while KCaH₃ is a semiconductor. Strong bonding and long bond lengths indicate high hydrogen storage potential. The materials exhibit thermodynamic and mechanical stability, suggesting feasibility for experimental synthesis. Gravimetric analysis reveals promising hydrogen storage capacities: 3.646 wt% (KCaH₃), 3.452 wt% (KScH₃), 3.346 wt% (KTiH₃), and 3.005 wt% (KNiH₃). Calculated hydrogen desorption temperatures range from 442.40 K to 614.82 K, indicating suitability for practical hydrogen storage applications. These findings highlight the potential of KXH₃ (X = Ca, Sc, Ti, &amp; Ni) perovskites as effective hydrogen storage materials.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141777895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Geometrical and electronic properties of Sin (n = 6–15) clusters with rhodium impurity: a first-principles investigation","authors":"Zai-Fu Jiang, Hua-Long Jiang, Chang-Geng Luo, Shuai Zhang, Gen-Qquan Li","doi":"10.1007/s11224-024-02360-y","DOIUrl":"https://doi.org/10.1007/s11224-024-02360-y","url":null,"abstract":"<p>To delve into the microscopic property of the cluster RhSi_<i>n</i> (<i>n</i> = 6–15), this study employs the CALYPSO structure prediction program and density functional theory. The paper conducts a comprehensive theoretical analysis of the clusters, examining parameters such as structures, relative stabilities, charge transfer, vertical electron affinity, vertical ionization potential, chemical potential, chemical hardness, and infrared and Raman spectra. The optimization process reveals that the rhodium doping has clearly changed the structures of silicon clusters. The ground state geometries favor Rh-linked framework beginning from <i>n</i> = 6, and they favor Rh-encapsulated Si cages when <i>n</i> approach 10. RhSi₁₃ cluster is more stable than its neighbors. The charges transfer within the clusters always transfer from silicon atom to rhodium atom, and there is <i>spd</i> hybridization in RhSi_<i>n</i> cluster. The analyzed chemical potential and chemical hardness pointed out the RhSi₁₃ cluster has the stronger hardness than other clusters. At last, the infrared and Raman spectrum properties for RhSi₁₃ cluster are analyzed.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141742630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Template syntheses, molecular structures, and antimicrobial activities of two novel Schiff-base macrocyclic lanthanide complexes","authors":"Kun Zhang, Daoxin Wang, Shuangquan Wu, Chengeng Wang, Zhengguang Yu, Lei Zhang","doi":"10.1007/s11224-024-02361-x","DOIUrl":"https://doi.org/10.1007/s11224-024-02361-x","url":null,"abstract":"<p>Based on the template-assisted cyclocondensation procedure, two Schiff-base macrocyclic mononuclear lanthanide complexes (<b>Pr-2</b>_<b>l</b> and <b>Nd-2</b>_<b>l</b>) with the “lasso-type” architecture have been synthesized. According to X-ray structure analysis, the central ten-coordinate lanthanide ions (Pr³⁺ and Nd³⁺) in two complexes have distorted bicapped square antiprism geometry, and this geometry is completely encircled by two axial chelating nitrates on each side of the 23-membered macrocyclic plane and six donors in the macrocyclic skeleton. With the higher relatively inhibitory rates, the complex <b>Pr-2</b>_<b>l</b> can show significant antimicrobial activities against <i>C. albicans</i> and <i>MRSA</i> with lower MIC values (7.81 and 3.91 μg·mL⁻¹), while complex <b>Nd-2</b>_<b>l</b> exhibited good antimicrobial activities for <i>S. aureus</i>, <i>C. albicans</i>, and <i>MRSA</i> whose MIC values are 1.95, 7.81, and 3.91 μg·mL⁻¹. This current work is believed to provide another practical approach to further construct new antimicrobial materials by the use of Schiff-base and lanthanide antimicrobial fragments.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141742674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT exploration of anion accepting performance of perfluorocubane","authors":"Shomeys Bagheri, Morteza Rouhani, Javad Mokhtari Aliabad","doi":"10.1007/s11224-024-02363-9","DOIUrl":"https://doi.org/10.1007/s11224-024-02363-9","url":null,"abstract":"<p>Using the B3LYP-D3 functional and the 6-311++G(d,p) basis set, the fluoride (F⁻), chloride (Cl⁻), bromide (Br⁻), cyanide (CN⁻), nitrate (NO₃⁻), and sulfate (SO₄²⁻) affinities of perfluorocubane (PFC) was theoretically investigated. This anion receptor interacts to the selected anions by LP → σ* interactions. It was discovered that the charge distribution in a small radius and net charge value in anion have a significant impact on the anion affinities of PFC structure. The natural bond orbital (NBO) analysis was used for identifying the detailed characteristics of anion… PFC interactions. The ∆<i>H</i> value of anion affinity of PFC for F⁻, Cl⁻, Br⁻, CN⁻, NO₃⁻, and SO₄²⁻ was calculated as − 139.36, − 63.53, − 50.30, − 66.64, − 46.21, and − 151.28 kJ mol⁻¹, respectively. The obtained results show that the anion affinity of PFC for SO₄²⁻ and F⁻ are among the strong organic anion receptors.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141742646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural chemistry of mixed-ligand fluoride complexes of uranyl","authors":"Ruven L. Davidovich, Evgeny A. Goreshnik","doi":"10.1007/s11224-024-02322-4","DOIUrl":"https://doi.org/10.1007/s11224-024-02322-4","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.1,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141646649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure and luminescent properties of Nd(III) and Tb(III) coordination polymers with 2,4,6-pyridinetricarboxylate","authors":"Hongsheng Wang, Hui Li, Xinhua Chen","doi":"10.1007/s11224-024-02358-6","DOIUrl":"https://doi.org/10.1007/s11224-024-02358-6","url":null,"abstract":"<p>Two lanthanide coordination polymers (<b>CP</b>) of Nd(III) and Tb(III) with 2,4,6-pyridinetricarboxylate ligands were synthesized by reacting Nd(III) or Tb(III) chlorides with 2,4,6-pyridinetricarboxylic acid (H₃ptc) by hydrothermal method at 180 °C. Their chemical formulas were {[Nd(ptc)(H₂O)₂]·H₂O}_n (<b>CP-1</b>) and {[Tb(ptc)(H₂O)₃]·H₂O}_n (<b>CP-2</b>). Two compounds were characterized by IR spectra and element analyses. The crystal structures were determined by X-ray single crystal diffraction. <b>CP</b>-<b>1</b> formed three-dimensional (3D) structure by the connections of coordination bonds between Nd(III) and ptc ligands and <b>CP-2</b> formed two-dimensional (2D) layered structure. They could produce the characteristic f-f transition luminescence of Nd(III) or Tb(III) ion with the excitations of UV-rays. The lifetime for ⁵D₄ excited state of Tb(III) in <b>CP-2</b> was 741 μs. And the absolute quantum yield of photoluminescence for <b>CP-2</b> can reach 60% (<i>λ</i>_ex = 295 nm).</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141612197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, characterization, solvatochromic, and electrochemical investigation of novel 4-methyl coumarin fused azo dyes as an NLO material and their biological studies","authors":"Surendranaik. Y, Talavara Venkatesh, Eresha naik","doi":"10.1007/s11224-024-02359-5","DOIUrl":"https://doi.org/10.1007/s11224-024-02359-5","url":null,"abstract":"<p>Herein, we synthesized novel 4-methyl coumarin-incorporated heterocyclic azo dyes, and structures were confirmed by analytical and spectroscopic approaches. Computational studies were performed using the DFT method with a B3LYP/ 6–31 G (d, p) basis set used to explore the molecular geometry, Mullikan atomic charges, global reactive descriptors, MEP, and RDG. Nonlinear optical (NLO) analysis revealed that the first-order hyperpolarizability of 1d was 18 times greater than that of urea. Natural bond orbital (NBO) analysis showed that all the compounds had greater stability due to internal charge transfer. Solvatochromic behavior was analyzed using UV–Vis spectroscopy, and the absorbance was observed in the range of 380–445 nm. The electrochemical behavior was determined by cyclic voltammetry, which exhibited two reduction peaks and was used to calculate the energy of the molecules (E_HOMO-E_LUMO). The antimicrobial activity was studied against different pathogens Viz<i>., E. coli, S. aureus,</i> and <i>A. flavus</i>, and the results showed that the compounds had good antimicrobial efficacy. “Furthermore, in silico molecular docking results revealed that compounds 1b and 1a have good binding site energies against the target enzymes DNA gyrase and O-methyltransferase, respectively”.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}