Structural Chemistry最新文献

{"title":"In silico investigation of doped AlN nanotubes for artemether detection and adsorption: insights into electronic and non-covalent interaction mechanisms","authors":"Eban L. Kechi,&nbsp;Ohadoma Chika Selvesta,&nbsp;Lawal B. A. S,&nbsp;Blessing Imojara,&nbsp;Peter O. Ajala,&nbsp;Odey Kelvin Peter","doi":"10.1007/s11224-025-02514-6","DOIUrl":"10.1007/s11224-025-02514-6","url":null,"abstract":"<div><p>The disposal of artemether by pharmaceutical industries and its excretion into the environment disrupt ecological balance. Advanced materials, like aluminium nitride nanotubes (AlNNTs), offer promise for detecting and adsorbing these pollutants effectively due to their exceptional properties. This study explores the potential of doped AlNNT systems for the detection and adsorption of artemether from the environment. To achieve this, we employed the density functional theory (DFT) using the PBE1PBE functional and LANL2DZ basis set to assess the energy gap, dipole moment, adsorption energy, and the nature of interaction upon adsorption of AMT on doped AlNNT surfaces. From our result, we found that when AlNNT was doped with Bi, Ga, and Sn, a decline in energy gap was detected revealing that the presence of these dopants affects its electronic property. Also, the further decrease in energy gap upon interaction of the adsorbate shows increased electrical conductivity revealing that these materials yield an electronic signal at the presence of AMT and can be utilized as sensors. Also, the visual studies revealed that these complexes are dominated by the presence of non-covalent interactions characterized by the green patches observed between the adsorbate and adsorbent from the NCI analysis and the G(r)/V(r) ratio exceeding unity along with the positive values of ∇²ρ(r) observed in QTAIM studies. Furthermore, we found that AMT molecules can be chemisorbed on the surfaces due to the negative values of adsorption energy revealed for all the complexes with digits starting from − 1.459 to − 1.814 eV. Hence, this study reveals the ability of the investigated surfaces as a potential efficient sensor for AMT detection and adsorption.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"979 - 993"},"PeriodicalIF":2.2,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388617","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 arrangement and computational exploration of guanidinium-based hydrogen-bonded organic frameworks","authors":"Lina Jia,&nbsp;Qiang Ma,&nbsp;Yitong Deng,&nbsp;Shixian Wang,&nbsp;Guoying Zhao,&nbsp;Changyu Sun","doi":"10.1007/s11224-025-02614-3","DOIUrl":"10.1007/s11224-025-02614-3","url":null,"abstract":"<div><p>The directional modulation of hydrogen-bonding networks serves as a pivotal strategy for optimizing the thermal stability of crystalline materials. In this study, four guanidinium-based hydrogen-bonded organic frameworks (HOFs)—guanidinium hydroquinone ([GUA][HYD]), guanidinium phloroglucinol ([GUA][PHL]), guanidinium terephthalic acid ([GUA][TER]), and guanidinium trimesic acid ([GUA][TRI])—were designed and synthesized by tailoring the acidic strength and substituent topology of anionic ligands, systematically investigating the hydrogen-bonding network’s impact on their crystal structures and properties. Single-crystal X-ray diffraction combined with Hirshfeld surface analysis revealed that N-H···O hydrogen bonds dominate the assembly of all HOFs, yielding two distinct topologies: a periodically layered framework ([GUA][HYD]) and a highly symmetric octameric cage-like architecture ([GUA][TRI]). In contrast, [GUA][PHL] and [GUA][TER] formed guest-incorporated configurations due to disordered hydrogen-bond directionality. Thermogravimetric analysis and density functional theory (DFT, B3LYP/6-311++G(d,p)) demonstrated that hydrogen-bond strength, density, and network symmetry critically govern thermal stability. Carboxylate-substituted systems ([GUA][TER]/[GUA][TRI]) exhibited better stability over phenolic hydroxyl analogs ([GUA][HYD]/[GUA][PHL]), attributed to enhanced hydrogen-bond interactions and three-dimensional ionic synergy. Furthermore, high-symmetry frameworks ([GUA][HYD] and [GUA][TRI]) outperformed their counterparts ([GUA][PHL] and [GUA][TER], respectively) in stability due to their highly ordered packing modes. This work reveals the inherent correlation between hydrogen-bond coordination, topological configuration, and thermodynamic behavior, probably providing theoretical support for the rational design of HOFs and advancing their applications in energy storage, catalysis, and controlled drug delivery.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"963 - 978"},"PeriodicalIF":2.2,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334258","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":"Dual-atom catalysts based on PN-co-doped graphene: a comparative study of iron, cobalt, and nickel for ORR","authors":"Pegah Ghafouri Mirsaraei,&nbsp;Maryam Anafcheh,&nbsp;Elaheh Ahmadi","doi":"10.1007/s11224-025-02617-0","DOIUrl":"10.1007/s11224-025-02617-0","url":null,"abstract":"<div><p>In this DFT study, we systematically investigated PN-co-doped graphene-supported dual-atom catalysts (DACs) comprising homonuclear and heteronuclear pairs of Fe, Co, and Ni for enhancing the kinetics of the four-electron oxygen reduction reaction (ORR). Binding and formation energy analyses confirm the thermodynamic stability of all M1M2@NPxC configurations, indicating strong resistance to metal atom diffusion and aggregation. The adsorption geometries and energies of key ORR intermediates (*O₂, *OOH, *O, and *OH) were examined alongside free energy changes for the four elementary steps, revealing that P-doping in M1M2@NC systems enhances O₂ activation and optimizes intermediate reduction. Electron transfer was found to play a crucial role in chemisorption and activation, with O₂ predominantly binding in a side-on configuration to the metal dimers. Theoretical overpotentials (η_ORR), calculated via the Limiting potential method, ranged from 0.345 to 1.217 V. Ni-based DACs, particularly NiNi@NP₅C (<i>η</i> = 0.345 V), exhibit the most favorable free energy profiles and the highest predicted catalytic activity. Heterodimeric systems such as FeCo@NP_xC, FeNi@NP_xC, and CoNi@NP_xC also demonstrate promising performance. Strong linear correlations are observed between Δ<i>G</i>*_OOH and Δ<i>G</i>*_OH (<i>R</i>² = 0.86), consistent with their similar binding modes via a single oxygen atom, whereas correlations with Δ<i>G</i>*_O are weaker. These findings highlight the synergistic benefits of P-doping and dual-metal active sites in designing efficient, platinum-free ORR electrocatalysts for fuel cell applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"949 - 961"},"PeriodicalIF":2.2,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388547","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 structures and electronic properties of Al-doped Agn (n = 1–18) clusters: a computational study","authors":"Gen Liu,&nbsp;Kai Wang","doi":"10.1007/s11224-025-02619-y","DOIUrl":"10.1007/s11224-025-02619-y","url":null,"abstract":"<div><p>The structural evolution and electronic properties of Al-doped Ag_<i>n</i> (<i>n</i> = 1–18) clusters were investigated through a hybrid global optimization algorithm and density functional theory (DFT) calculations. The results show that in clusters with <i>n</i> ≤ 13, the Al atom preferentially occupies surface sites, whereas in larger clusters (<i>n</i> ≥ 14), it prefers to be encapsulated by Ag atoms to form endohedral structures, except for AlAg₁₅ with a cage structure. In all studied clusters, the Al atom consistently functions as an electron acceptor, receiving electrons donated by the silver framework. The average binding energy per atom in these clusters increases with cluster size, suggesting greater thermodynamic stability that favors the formation of larger clusters. The HOMO–LUMO gap and second-order difference of energy exhibit similar even–odd oscillation trends, indicating that electronic structure governs cluster stability. AlAg₅, AlAg₁₅, and AlAg₁₇ clusters are confirmed as superatoms with closed electronic configurations of (1S)²(1P)⁶, (1S)²(1P)⁶(1D)¹⁰, and (1S)²(1P)⁶(1D)¹⁰(2S)², respectively.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"941 - 948"},"PeriodicalIF":2.2,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388555","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":"Density functional theory calculations on the interaction between adsorption redox intermediates and typical Ni porphyrin derivatives","authors":"Shu-qi Yang,&nbsp;Hao-bo Zhai,&nbsp;Zhi Li","doi":"10.1007/s11224-025-02609-0","DOIUrl":"10.1007/s11224-025-02609-0","url":null,"abstract":"<div><p>Ni porphyrins possess exceptional catalytic versatility due to their electronically active metal coordination centers. To evaluate the effects of peripheral substituents on the catalytic efficacy of Ni porphyrins, the oxidative catalytic performance of Ni porphyrin derivatives has been investigated using density functional theory (DFT). The results reveal that the O-2p in H₂O + O* is strongly hybridized with Ni-d, which promotes oxygen activation. The carboxylic acid group stabilizes the charged intermediates (OH*/OOH*). For TPTBP, the polybenzene ring enhances the stability of OOH*/HOOH*. The electron-withdrawing effect of TCPP synergizes with structural flexibility to achieve dissociation pathways with low energy barriers. TPYP-O is the only efficient 2e-ORR catalyst. TPTBP has a strong adsorption-conjugation synergy effect, and path 1 (O₂ → OOH* → H₂O + O* → H₂O + OH*) has no energy barriers of adsorption. It will provide theoretical references for the application of Ni-based metalloporphyrins as catalysts.\u0000</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"923 - 940"},"PeriodicalIF":2.2,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388681","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 crystal chemistry and topology of modular structures. I. Selenites of rare-earth elements","authors":"Sergey M. Aksenov","doi":"10.1007/s11224-025-02586-4","DOIUrl":"10.1007/s11224-025-02586-4","url":null,"abstract":"<div><p>Selenites and hydroselenites exhibit a wide structural diversity and are considered as functional materials with a broad spectrum of potential physical properties. The complex crystal chemistry of these compounds is predominantly determined by the peculiarities of chemical bonds between SeO₃ triangles and other polyhedra, as well as the stereochemical activity of the lone electron pair, which makes this family similar in structure to sulfates and sulfites, as well as tellurites. The presence of stable modules in the structures of rare-earth selenites allows for the identification of modular series of crystal structures. This fact enables the classification of known structural types as well as the prediction of new ones using the formalism of modular crystal chemistry. This review highlights the breadth of research on the crystal structures of rare-earth selenites and aims to provide new insights for their more detailed analysis.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"47 - 80"},"PeriodicalIF":2.2,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043454","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":"Polymorphism and weak noncovalent interactions with unique halogen bonding in the supramolecular assemblies of (Z)-3-[(4-bromophenyl)amino]-2-cyanoprop-2-enoate","authors":"Perumal Venkatesan,&nbsp;Thirumani Logalakshmi,&nbsp;M. Judith Percino,&nbsp;Olivier Blacque,&nbsp;Subbiah Thamotharan","doi":"10.1007/s11224-025-02583-7","DOIUrl":"10.1007/s11224-025-02583-7","url":null,"abstract":"<div><p>A new polymorphic form of (<i>Z</i>)-3-[(4-bromophenyl)amino]-2-cyanoprop-2-enoate was obtained from an ethanolic solution. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the compound crystallizes in the monoclinic system with space group <i>P</i>2₁/c, <i>Z</i> = 8, and an asymmetric unit comprising two crystallographically independent molecules (<i>Z</i>′ = 2). An intramolecular N–H···O hydrogen bond forms an <i>S</i>(6) ring motif. The intramolecular and intermolecular interactions, as well as the supramolecular architecture of this new polymorph (<b>form II</b>), are compared with the previously reported polymorph (<b>form I</b>). Topological analysis indicates that the intramolecular N–H···O hydrogen bond in both <b>forms I</b> and <b>II</b> exhibits closed-shell character. Intermolecular interaction energies for dimers in both forms were quantified using the Coulomb-London–Pauli-PIXEL (CLP-PIXEL) and density functional theory (DFT) methods. The nature and strength of various intermolecular interactions were further analyzed and quantified using Bader’s quantum theory of atoms in molecules (QTAIM) approach. The crystal structure of <b>form II</b> is stabilized by weak intermolecular C–H···N, C–H···O, and C–H···Br and molecular stacking interactions. Unique halogen bonds are observed in polymorphic <b>forms I</b> (Br···N) and <b>II</b> (Br···Br) and were examined using molecular electrostatic potential (MESP) surface maps and deformation electron density maps. These halogen bonds significantly influence the crystal packing of their respective polymorphs. Hirshfeld surface (HS) analysis indicated that H···H, H···N, H···Br, C···H, and O···H contacts make substantial contributions to the overall packing.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"905 - 921"},"PeriodicalIF":2.2,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388616","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":"Investigating the physicochemical properties of anthranol, emodin, and aloe-emodin: DFT and TD-DFT analysis of undoped and lithium/potassium-doped molecules in gas phase and solution","authors":"Magloire Benjamin Osse,&nbsp;Martin Thierry Ottou Abe,&nbsp;Yannick Tadjouteu Assatse,&nbsp;Ariel Teyou Ngoupo,&nbsp;Jean-Marie Bienvenu Ndjaka","doi":"10.1007/s11224-025-02605-4","DOIUrl":"10.1007/s11224-025-02605-4","url":null,"abstract":"<div><p>This study explores the thermodynamic, electronic, nonlinear optical, and spectroscopic (IR, UV–Vis, Raman) of dihydroxyanthraquinone (aloe-emodin), trihydroxyanthraquinone (emodin), and anthranol, using Density Functional Theory (DFT) with the B3LYP, B3PW91, and CAM-B3LYP methods via Gaussian 09 software with the 6-311G(d,p) basis set. Analysis of the thermodynamic properties shows that the three molecules are stable in their ground state. The energy gaps, as revealed by the B3LYP and B3PW91 functionals, indicate that the three molecules are good semiconductors, with a significant improvement in the energy gap upon doping with potassium or lithium. Lithium doping reduces the energy gap more markedly than potassium doping, while all three molecules possess antioxidant characteristics. The nonlinear optical properties indicate that the first-order static hyperpolarizability values for the molecules, both doped and undoped, are higher than those of urea, suggesting their potential in the development of nonlinear materials. Analysis of the reactivity descriptors reveals that all three compounds are considered hard, as their hardness values are greater than their softness values (η &gt; S), with aloe-emodin proving to be more reactive and electrophilic than emodin and anthranol. The UV–Vis spectra indicate that both doped and undoped molecules absorb in the visible range.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"883 - 904"},"PeriodicalIF":2.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388613","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":"Elucidating the impact of photo-isomeric dithienylcyclopentene-based molecular switches for efficient nonlinear optics","authors":"Muhammad Hammad Ali,&nbsp;Falak Chaudhry,&nbsp;Umar Farooq,&nbsp;Muhammad Salman,&nbsp;Riaz Hussain,&nbsp;Muhammad Adnan","doi":"10.1007/s11224-025-02608-1","DOIUrl":"10.1007/s11224-025-02608-1","url":null,"abstract":"<div><p>Nonlinear optical (NLO) materials have gained significant scientific attention in the modern era due to their extensive applications in electronics, optics, and telecommunications. In this study, a theoretical NLO investigation was conducted on four photo-isomeric forms of a dithienylcyclopentene (DTECP)-based molecular switch using the DFT approach. The ring closure in the DTECP subunits modulated the electronic structure, resulting in a significant reduction in HOMO–LUMO energy gap to 0.85 eV, which in turn enhanced the NLO response due to increase π-electron delocalization and charge transfer. Among the studied forms, the molecular switch with three closed rings (MS3C) exhibited the highest first-order static hyperpolarizability (9.24 × 10^–28 esu) and switch ratio β_ratio ~ 3.15 with corresponding three open-ring form because of the better delocalization of the π-electron system, the greater degree of charge transfer and the smaller transition energy in the closed-ring. The highest β_o value suggests strong electronic polarization in response to an external electric field which is essential for efficient NLO materials. Additionally, TD-DFT calculations revealed a redshift upon ring closure, further validating the molecular switch's excellent photo-switching NLO properties. Thus, this molecular switch, in its different photo-isomeric forms demonstrates strong potential for the fabrication of optoelectronic and sensing devices due to its superior photo-switching NLO response.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"865 - 881"},"PeriodicalIF":2.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388600","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 mechanisms of some transitions between Ices IV, XII, VI, VII(VIII) and Ic","authors":"Ekaterina A. Zheligovskaya","doi":"10.1007/s11224-025-02606-3","DOIUrl":"10.1007/s11224-025-02606-3","url":null,"abstract":"<div><p>The structural mechanisms of the transitions VI–VII(VIII), IV → VIII, IV → VI, XII → VIII, XII → VI, and XII → Ic are studied. It is shown that the transitions between more dense crystal ices IV, VI, VII(VIII), and XII usually proceed by small shifts of molecules with rearrangement of more than a half of the initial hydrogen bonds. In this case, only finite fragments of the initial phase are retained, which consist of a few molecules. At the same time, as was shown previously, the transitions between less dense crystal ices can proceed by retaining all hydrogen bonds in large (i.e., infinite at least in one dimension) fragments of the initial structure, with a possible change of the bond lengths and angles inside these fragments and rearrangement of hydrogen bonds only between these fragments. In this case, a large fraction (more than a half) of the initial bonds is retained. The difference in the structural mechanisms of transitions between more dense ices or between less dense ices is related to the degree of space filling in the ice structures. The structural mechanisms of the transitions IV → Ic and XII → Ic are very close to those of the transitions IV → VIII and XII → VIII, respectively, because the structures of ices IV and XII are intermediate between those of ices Ic and VII(VIII).\u0000</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 6","pages":"2037 - 2048"},"PeriodicalIF":2.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665989","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}