Structural Chemistry最新文献_第9页

Size evolution and property study on PdAgn (n = 1–17) clusters from density functional theory 基于密度泛函理论的PdAgn （n = 1-17）簇尺寸演化与性质研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-21 DOI: 10.1007/s11224-025-02543-1

Zhimei Tian, Dongyang He, Jingzhe Sun, Chongfu Song

{"title":"Size evolution and property study on PdAgn (n = 1–17) clusters from density functional theory","authors":"Zhimei Tian, Dongyang He, Jingzhe Sun, Chongfu Song","doi":"10.1007/s11224-025-02543-1","DOIUrl":"10.1007/s11224-025-02543-1","url":null,"abstract":"<div>The combined method of genetic algorithm and density functional theory (GA-DFT) has been used to study the size evolution and property of PdAgn (n = 1–17) clusters. Benchmark calculations reveal that the TPSSH/def2-TZVP method is suitable. The structures of the clusters are planar or quasi-planar when n = 1–4, whereas they are three-dimensional when n = 5–17. The Pd atom favors to locate at the position with the highest coordination number. Moreover, the Pd atom likes to locate at the central position for PdAgn clusters. Average bond lengths of Pd–Ag and Ag–Ag of PdAgn (n = 1–17) clusters are recorded, which reveals that rAg-Ag and rPd-Ag increases as cluster size. The charge of Pd atom increases as cluster size. The average bond orders of Pd–Ag and Ag–Ag bonds decrease as cluster size increases. The peaks of the ultraviolet–visible spectra of the clusters increase as cluster size, and the peaks present odd–even oscillations as cluster size. The stability of PdAgn clusters displays odd–even oscillation based on harness analysis and second-order energy difference analysis. According to thermodynamic analysis, the formation reactions of PdAgn are spontaneous when the Ag atom adds to PdAgn-1 clusters.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"397 - 407"},"PeriodicalIF":2.2,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043342","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}

引用次数: 0

Synthesis, Spectral Properties, Crystal Structure and DFT Studies of 2-((1-Phenyl-1H-1,2,3-triazol-4-yl)methoxy)benzonitrile 2-（（1-苯基- 1h -1,2,3-三唑-4-基）甲氧基）苯腈的合成、光谱性质、晶体结构和DFT研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-19 DOI: 10.1007/s11224-025-02538-y

Yonas Belay, Alfred Muller, Cresten Moodley, Sage Singh, Adedapo S. Adeyinka

{"title":"Synthesis, Spectral Properties, Crystal Structure and DFT Studies of 2-((1-Phenyl-1H-1,2,3-triazol-4-yl)methoxy)benzonitrile","authors":"Yonas Belay, Alfred Muller, Cresten Moodley, Sage Singh, Adedapo S. Adeyinka","doi":"10.1007/s11224-025-02538-y","DOIUrl":"10.1007/s11224-025-02538-y","url":null,"abstract":"<div>2-((1-Phenyl-1H-1,2,3-triazol-4-yl)methoxy)benzonitrile (3), was synthesized by scaffold Schiff base condensation reaction of 1,2,3-triazole (1) and then followed by its dehydration. The title compound was characterized by typical spectroscopic techniques such as 1H-NMR, 13C-NMR and FTIR. The structure of the title compound 3 was also determined by single crystal X-ray diffraction analysis. The compound co-crystallizes with water molecules, which occupy a twofold axis special position, in the orthorhombic system with space group Pnna and a = 13.606(3) Å, b = 23.442(5) Å, c = 8.2412(16) Å. The crystal structure is stabilized by strong hydrogen bonds between the water molecules and the compound, along with weaker secondary interactions, including π-π stacking and C-H···N interactions. The geometry of 3 was optimized by the DFT method and the results were compared with the single crystal X-ray diffraction data. Frontier molecular orbitals of the title compound 3 were calculated by using the B3LYP/6–31 + g(d,p) method. MEP analysis and Mulliken charge density, Global reactivity and thermodynamic properties were also performed.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"373 - 383"},"PeriodicalIF":2.2,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02538-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Exploring uncommon cyclization: Synthesis and crystal structure of a morpholine-substituted 1,2-pyrazole from Coumarin 探索罕见的环化：香豆素取代的1,2-吡唑的合成和晶体结构

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-19 DOI: 10.1007/s11224-025-02546-y

Puthiyavalappil Rasin, Kailas Mahipal Malappuram, Nattamai Bhuvanesh

引用次数: 0

[Ti{η5-C9H7}Cl2(OR)] half-sandwich complexes: synthesis and theoretical studies on substituent effects on the HOMO − LUMO energy gap [Ti{η5-C9H7}Cl2(OR)]半夹层配合物的合成及取代基对HOMO - LUMO能隙影响的理论研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-18 DOI: 10.1007/s11224-025-02535-1

Deeb Taher, Sami Klaib, Khaleel I. Assaf, Zakariyya Ishtaiwi, Wissam Helal, Heinrich Lang

{"title":"[Ti{η5-C9H7}Cl2(OR)] half-sandwich complexes: synthesis and theoretical studies on substituent effects on the HOMO − LUMO energy gap","authors":"Deeb Taher, Sami Klaib, Khaleel I. Assaf, Zakariyya Ishtaiwi, Wissam Helal, Heinrich Lang","doi":"10.1007/s11224-025-02535-1","DOIUrl":"10.1007/s11224-025-02535-1","url":null,"abstract":"<div>The current work reports the facile synthesis and characterization of half-sandwich compounds [Ti(η5-C9H7)(Cl)2(OR)] (3) (R = iPr (3a); R = tBu (3b); R = 2,6-Ph2C6H3 (3c); CH2CH2(CC4H3S) (3d) (prepared via treatment of Ti(η5-C9H7)Cl3 (1) with LiOR (2a, R = iC3H7; 2b, R = tC4H9; 2c, R = 2,6-Ph2C6H3; 2d, R = CH2CH2(CC4H3S)) in a 1:1 molar ratio. Additionally, compounds 3a, 3b, and 3d were also obtained when compound 1 was reacted with HOR (2a, R = iC3H7; 2b, R = tC4H9; 2d, R = CH2CH2(CC4H3S)) under reflux in benzene. The half-sandwich titanium compounds 3a–d were characterized by elemental analyses, FT-IR, and 1H and 13C{1H}-NMR spectroscopy. Density functional theory (DFT) calculations at the B3LYP/6-31G(d) + LANL2DZ level of theory were carried out for 1 and 3a–d in order to better understand and rationalize the nature of bonding and thus demonstrate the effect of different substituents on the structural and electronic properties. The studies confirm a similar complexation pattern despite the different chemical nature of the substituents. However, the HOMO–LUMO frontier molecular orbitals analysis revealed ligand–metal charge transfer, and the calculations predicted smaller HOMO–LUMO energy gaps for 3c.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"343 - 353"},"PeriodicalIF":2.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043491","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}

引用次数: 0

Computational study of poly(ethylene terephthalate) glycolysis catalyzed by cyanamide 氰酰胺催化聚对苯二甲酸乙酯糖酵解的计算研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-14 DOI: 10.1007/s11224-025-02534-2

Varangkana Jitchum, Thana Maihom

{"title":"Computational study of poly(ethylene terephthalate) glycolysis catalyzed by cyanamide","authors":"Varangkana Jitchum, Thana Maihom","doi":"10.1007/s11224-025-02534-2","DOIUrl":"10.1007/s11224-025-02534-2","url":null,"abstract":"<div>We investigate the glycolysis of poly(ethylene terephthalate) or PET catalyzed by cyanamide using density functional theory. A PET dimer with C−O linkages is modeled as a representative active region. The reaction can proceed via two mechanisms based on the role of cyanamide: one involves forming a hydrogen bond with the PET dimer, while the other facilitates hydrogen transfer to promote C–O bond cleavage and O–H bond dissociation in ethylene glycol. Cyanamide stabilizes all species in the glycolysis reaction pathways by reducing their relative energies compared to the bare system. The intrinsic activation barriers for both mechanisms in the cyanamide-catalyzed system are found to be 40.6 and 36.3 kcal/mol, respectively, both lower than the barrier observed in the bare system (42.0 kcal/mol). We further investigate a mechanism in which cyanamide plays a dual role, simultaneously facilitating hydrogen transfer and forming hydrogen bonds with the dimer. The activation barrier is significantly reduced to 33.6 kcal/mol compared to the single cyanamide-catalyzed systems. Hence, we suggest that cyanamide serves a dual function, promoting both hydrogen transfer for C–O bond cleavage and hydrogen bond formation with the dimer. Moreover, the electron-donating substitution on the amino group of cyanamide further enhances catalytic activity by reducing the energy barrier compared to the unsubstituted form. Finally, in the presence of a water molecule, the barrier for the dual-role mechanism is reduced to 24.8 kcal/mol. Therefore, explicit water enhances the catalytic activity of cyanamide for PET glycolysis by acting as a medium to facilitate hydrogen transfer.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"333 - 342"},"PeriodicalIF":2.2,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043462","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}

引用次数: 0

Vertexane and related molecules: a computational exploration with contemporary quantum chemistry methods 顶点烷及相关分子：当代量子化学方法的计算探索

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-10 DOI: 10.1007/s11224-025-02524-4

Fabio Pichierri

引用次数: 0

Computational study of the bonding in η3-propargyl complexes of platinum and related species using MO, NBO, and QTAIM analysis 用MO， NBO和QTAIM分析计算了铂及其相关物质的η - 3-丙炔配合物的键合

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-10 DOI: 10.1007/s11224-025-02521-7

John P. Graham

{"title":"Computational study of the bonding in η3-propargyl complexes of platinum and related species using MO, NBO, and QTAIM analysis","authors":"John P. Graham","doi":"10.1007/s11224-025-02521-7","DOIUrl":"10.1007/s11224-025-02521-7","url":null,"abstract":"<div>Density functional theoretical calculations are used to investigate the nature of the metal–ligand bonding in the η3-propargyl complexes of Pt(II) and related species. Of particular interest are the interactions between the central propargyl C atom and the Pt centre. Experimental data has shown that the distance between Pt and the central C atom is the shortest Pt-C bond in the η3-propargyl complex [(η3-PhCCCH2)Pt(PPh3)2]+, suggesting a strong bonding interaction. However, approximate molecular orbital calculations have suggested that bonding between Pt and the propargyl ligand occurs primarily through the terminal propargyl C atoms. In this contribution, Pt-C interactions are analysed using molecular orbital theory, natural bonding orbital analysis, and the quantum theory of atoms in molecules (QTAIM). Calculated bond orders and delocalization indices suggest that there is a significant bonding interaction between the Pt centre and central carbon atom, but that this interaction is much weaker than the short bond distance would suggest. Energy decomposition using the interacting quantum atoms (IQA) approach further supports this conclusion. A comparison is made to the bonding in related model metallacyclobutene and η3-allyl complexes.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 5","pages":"1577 - 1584"},"PeriodicalIF":2.2,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02521-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145121713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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The Crystal and Molecular Structure of N-methylephedrinium 4-nitrobenzoate (I, II). Racemic Mimics Part 5 n -甲基麻黄碱4-硝基苯甲酸酯（I， II）的晶体和分子结构。外消旋模拟第5部分

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-10 DOI: 10.1007/s11224-025-02528-0

Ivan Bernal, Roger A. Lalancette

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Crystalline hydrogen peroxide adducts of triethylenediamine and triethylenediamine N,N′-dioxide nitrates 三乙二胺和三乙二胺N，N ' -二氧化氮的结晶过氧化氢加合物

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-06 DOI: 10.1007/s11224-025-02529-z

Alexander G. Medvedev, Elena A. Mel’nik, Petr V. Prikhodchenko

{"title":"Crystalline hydrogen peroxide adducts of triethylenediamine and triethylenediamine N,N′-dioxide nitrates","authors":"Alexander G. Medvedev, Elena A. Mel’nik, Petr V. Prikhodchenko","doi":"10.1007/s11224-025-02529-z","DOIUrl":"10.1007/s11224-025-02529-z","url":null,"abstract":"<div>Peroxosolvates are commonly employed as solid-state sources for hydrogen peroxide in various scientific and industrial applications. However, among the hydrogen peroxide adducts, nitrate peroxosolvates remain poorly studied. This study reports the synthesis and characterization of two crystalline peroxosolvates of triethylenediamine (DABCO) derivatives: H2DABCO dinitrate (C6H14N2)(NO3)2·H2O2 (1) and DABCO N,N′-dioxide mononitrate (C6H13N2O2)(NO3)·2H2O2 (2). The peroxosolvates were synthesized using 50 wt% aqueous hydrogen peroxide and characterized by permanganometry, CHN elemental analysis, powder X-ray diffraction, and differential thermal and thermogravimetric analyses. The crystal structure of peroxosolvates was determined by single-crystal X-ray diffraction analysis. Hydrogen peroxide acts only as a hydrogen bond donor to O atoms of nitrate anions and the N-O moiety. One of H2O2 hydrogen bonds in compound 1 is bifurcated, which is quite rare for peroxosolvates. The crystal structures of both compounds are stabilized by a rich network of hydrogen bonds.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"323 - 331"},"PeriodicalIF":2.2,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043460","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}

引用次数: 0

Bimetallic doping of benzocryptand with alkaline earth metals for outstanding nonlinear optical response; a DFT study 苯并氪与碱土金属的双金属掺杂具有优异的非线性光学响应DFT研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-06-05 DOI: 10.1007/s11224-025-02523-5

Hillia Fatima, Naima Rafique, Muhammad Nouman, Areeba Asif, Noman Akhtar

{"title":"Bimetallic doping of benzocryptand with alkaline earth metals for outstanding nonlinear optical response; a DFT study","authors":"Hillia Fatima, Naima Rafique, Muhammad Nouman, Areeba Asif, Noman Akhtar","doi":"10.1007/s11224-025-02523-5","DOIUrl":"10.1007/s11224-025-02523-5","url":null,"abstract":"<div>In this research, optical and nonlinear optical (NLO) properties of benzocryptand doped with alkaline earth metals (Be, Mg, Ca) both exohedrally and endohedrally were studied using DFT. Nine combinations of doped metals BzC, i.e., A-BzC-A* (A, A* = Be, Mg, Ca), were analyzed. Excess electron doping effects on optical and electronic properties for NLO response were also explored. Frontier molecular orbitals (FMOs), density of states (DOS), absorption maxima (λmax), and transition density matrix (TDM) analyses were conducted to investigate charge transfer phenomena. Parameters like dipole moment (μ), binding energy (Eb), interaction energy (Eint), electron affinity, excitation energy (ΔE), and natural bonding orbitals (NBO) were examined. Non-covalent interaction (NCI) and infrared (IR) analysis revealed weak interactions and vibrational frequencies. Enhanced λmax (536-3200 nm) and reduced band gap (0.34-2.71 eV) were observed. Among all, the Ca-Ca*-doped BzC complex demonstrated the highest NLO response, with endohedral and exohedral Ca doping resulting in the most remarkable enhancement in hyperpolarizability, confirming the effectiveness of bimetallic positioning in enhancing NLO properties. Bimetallic doping notably improved linear polarizability (αiso) and hyperpolarizability (βtl), indicating potential for novel NLO materials. DFT and TD-DFT for all compounds’ quantum chemical simulations were conducted using Gaussian 09 with molecular geometries and orbitals visualized in Gauss View 6.0. Furthermore, physical and chemical parameters, including bond lengths, dihedral angles, dipole moments, and charge densities, were analyzed. All the newly designed complexes were optimized at the B3LYP/6-31G (d′, p′) level of theory.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"283 - 306"},"PeriodicalIF":2.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043386","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}

引用次数: 0