Structural Chemistry最新文献

{"title":"Effects of substituents on the charge transport properties and nonlinear optical responses of TMCz-BO","authors":"Tran Huynh Hoang Loc,&nbsp;Nguyen Nhan,&nbsp;Ngo Phuong Thuy,&nbsp;Hoang Nguyen Bao Ngoc,&nbsp;Dang T. Nguyen,&nbsp;Pham Vu Nhat","doi":"10.1007/s11224-025-02709-x","DOIUrl":"10.1007/s11224-025-02709-x","url":null,"abstract":"<div><p>A set of donor and acceptor substituted derivatives of the thermally activated delayed fluorescence (TADF) emitter TMCz-BO was explored through density functional theory (DFT) and time-dependent TD-DFT calculations. The influence of chemical substitution on molecular structure, electronic arrangement, charge transfer dynamics, and nonlinear optical (NLO) response was examined in detail. Each optimized geometry was confirmed to be a true minimum without imaginary frequencies, validating the structural stability of all investigated species. Variations in the substitution pattern were found to modulate the HOMO–LUMO separation, ionization and electron affinity levels, and optical absorption behavior. Donor–acceptor modification enhances intramolecular charge transfer and leads to pronounced increases in both polarizability and first hyper-polarizability. Among the studied molecules, the NH₂-functionalized derivative possesses the smallest energy gap, the highest softness, and the largest β value, while fluorinated analogues exhibit wider gaps and more localized orbitals because of their inductive character. Overall, the findings demonstrate that rational substituent control effectively tunes charge transport efficiency and optical nonlinearity in TMCz-BO, offering quantitative insight for designing advanced TADF and photonic materials.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2765 - 2778"},"PeriodicalIF":2.3,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950526","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":"New acenaphthene-based heterocycles: synthesis, crystal structure, and spectroelectrochemistry","authors":"Vera V. Khrizanforova,&nbsp;Robert R. Fayzullin,&nbsp;Evgeniya B. Krasovskaya,&nbsp;Artem S. Agarkov,&nbsp;Dilyara O. Mingazhetdinova,&nbsp;Tatiana P. Gerasimova,&nbsp;Vladimir I. Morozov,&nbsp;Yulia H. Budnikova","doi":"10.1007/s11224-025-02690-5","DOIUrl":"10.1007/s11224-025-02690-5","url":null,"abstract":"<div><p>New acenaphthene-based heterocyclic compounds were obtained as a result of the reaction between acenaphthenequinone and NH₂−CH₂−R (where R=Py or thiophene) in the presence of ZnCl₂ as a template. Depending on the type of primary alkyl-amine used, the reaction resulted in the formation of pyrrole, pyrazine or pyrrolidine rings. All compounds were characterized using spectroscopic methods and their structures were confirmed via X-ray diffraction analysis. The electrochemical properties of the new heterocyclic compounds were studied using cyclic voltammetry and electron paramagnetic resonance spectroelectrochemistry. It was demonstrated that these new acenaphthene-based heterocycles exhibit multi-acceptor properties, rendering them promising candidates for use as redox-active ligands in coordination chemistry.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2481 - 2490"},"PeriodicalIF":2.3,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950527","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":"Unveiling the impact of end-capped acceptor moieties on second and third nonlinear optical response of naphtho[1,2-b:5,6-b′]dithiophene-based derivatives","authors":"Saba Abid,&nbsp;Aiman Jabbar,&nbsp;Zubaria Saeed,&nbsp;Sadia Jamal,&nbsp;Muhammad Haroon,&nbsp;Saifullah Bullo,&nbsp;Tansir Ahamad","doi":"10.1007/s11224-025-02645-w","DOIUrl":"10.1007/s11224-025-02645-w","url":null,"abstract":"<div><p> Herein, the novel D–π–A compounds (NDTD1-NDTD8) based on naphtho[1,2-b:5,6-b′]dithiophene were designed by modifying the donor and acceptor groups of NDTR reference. Density functional theory (DFT) and time-dependent DFT (TD-DFT) methods were employed to analyze the geometrical, optoelectronic, and nonlinear optical (NLO) properties of these chromophores. After the structure optimization, various analyses were performed, such as the frontier molecular orbitals (FMOs), density of states (DOS), natural bond orbitals (NBOs), UV–Visible, transition density matrix (TDM), and non-linear optical (NLO) properties at the M06/6-311G(d,p) functional. The results showed that due to the presence of extended conjugation in the D–π–A derivatives, their energy gap (<i>E</i>_gap) values were lowered as compared to the NDTR. The decreasing order of <i>E</i>_gap for the studied compounds was obtained as: NDTR (2.659) &gt; NDTD8 (2.232) &gt; NDTD2 (2.184) &gt; NDTD1 (2.097) &gt; NDTD7 (2.061) &gt; NDTD3 (2.002) &gt; NDTD6 (1.928) &gt; NDTD4 (1.901) &gt; NDTD5 (1.811) in <i>eV</i>. The global reactivity parameters (GRPs) were calculated utilizing the <i>E</i>_gap of these chromophores, showing their high chemical reactivity and stability. Moreover, the presence of hyper-conjugation and intramolecular attractions were demonstrated via the NBOs findings. Nevertheless, prominent charge transfer was observed in the studied chromophores displayed via their DOS and TDM plots. Interestingly, NDTD5 showed the minimal energy gap (1.811 eV) and highest bathochromic shift (λ_max = 817.730 nm). From the NLO insights, all the studied compounds showed promising results, especially the NDTD5, which exhibited the highest average linear polarizability (⟨<i>α</i>⟩ = 3.809 × 10⁻²² <i>esu</i>), first hyper-polarizability (<i>β</i>_tot = 3.414 × 10⁻²⁷ <i>esu</i>), and second hyper-polarizability (<i>γ</i>_tot = 5.895 × 10⁻³² <i>esu</i>). Furthermore, it showed significant values for the simple harmonic generation (SHG) and electro-optic Pockel’s effect (EOPE) at 1907.21 nm, i.e., 4.21 × 10⁻²⁷ and 10.4 × 10⁻²⁷ <i>esu</i>, respectively. These outcomes showed that by utilizing strong donor and acceptor moieties in these D–π–A compounds, vital NLO materials are obtained for promising NLO applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2725 - 2748"},"PeriodicalIF":2.3,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950522","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":"Therapeutic potential of O4-coordinated copper(II) complexes: a synergy of DFT insights, SOD activity, and enhanced antibacterial action","authors":"Saeed S. Samman,&nbsp;Munirah M. Al-Rooqi,&nbsp;P. K. Vishwakarma,&nbsp;Abdulrahman A. Alsimaree,&nbsp;Jan Mohammad Mir,&nbsp;Sultan I. Alkubaysi,&nbsp;Rabab S. Jassas,&nbsp;Saleh A. Ahmed","doi":"10.1007/s11224-025-02699-w","DOIUrl":"10.1007/s11224-025-02699-w","url":null,"abstract":"<div><p>Novel mixed-ligand copper(II) complexes, [Cu(chrys)(macac)] (1) and [Cu(chrys)(dbm)] (2) (where chrysH = chrysin, macacH = methyl acetoacetate, dbmH = dibenzoylmethane), were synthesized and characterized as potent multifunctional agents. The structural evidences were gathered from a suite of techniques: infrared (IR) spectroscopy identified key functional groups and binding modes, magnetic susceptibility measurements confirmed the mononuclear copper(II) center, and mass spectrometry confirmed the molecular ion. Additional insights were derived from electronic absorption spectra, electron spin resonance (ESR) spectroscopy, and thermogravimetric analysis (TGA). The collective results confirmed a distorted square planar geometry, which was further validated by Density Functional Theory (DFT) calculations. Theoretical calculations over molecular geometry, charge distribution, molecular orbital descriptions FMOs, absolute electronegativity (χ_abs), and total hardness (η) of the complex, namely [Cu(chrys)(dbm)] (1), using density functional theory were also investigated. The complexes exhibit significant superoxide dismutase (SOD) mimetic activity and demonstrate potent, dose-dependent antibacterial efficacy against pathogens like <i>E. coli</i> and <i>Citrobacter</i>, outperforming standard antibiotics at higher concentrations. This combined experimental and theoretical study highlights the potential of these complexes as promising scaffolds for developing new metallodrugs with dual antioxidant and antibacterial properties.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2709 - 2723"},"PeriodicalIF":2.3,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950521","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":"How are valence electrons distributed in hyperlithiated carbon clusters? an answer from the electron localization function topology","authors":"Bruno Madebène,&nbsp;Julien Pilmé,&nbsp;Peter Reinhardt,&nbsp;Mohammad Esmaïl Alikhani","doi":"10.1007/s11224-025-02703-3","DOIUrl":"10.1007/s11224-025-02703-3","url":null,"abstract":"<div><p>We reinvestigated some archetypical hyperlithiated mono-carbon clusters within the electron localization function (ELF) topology. We show that despite the high coordination number, the central atom (C) always obeys the octet rule. In the Li₆C cluster, two delocalized electrons can be localized by adding one or two lithium atoms. For clusters larger than Li₈C, the coordination number increases from six to seven, with a first coordination sphere formed by lithium cations, while those in the second sphere are lithium anions. Indeed, we found no disynaptic attractor (related to the standard di-center-di-electron covalent bond) nor any trisynaptic attractor (related to the three-center-di-electron bond) within the hyperlithiated Li_nC compounds.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1805 - 1813"},"PeriodicalIF":2.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148614890","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":"Quantitative analysis of weak interactions in the solid state structures of fluorinated (E)-N-benzylbut-2-enamides","authors":"Dhananjay Dey,&nbsp;Arsheen Aijaz,&nbsp;Avantika Hasija,&nbsp;Deepak Chopra","doi":"10.1007/s11224-025-02696-z","DOIUrl":"10.1007/s11224-025-02696-z","url":null,"abstract":"<div><p>The role of weak intermolecular interactions in directing the molecular assembly and solid-state architecture is crucial in the design of functional organic materials. In this study, two fluorinated (<i>E</i>)-<i>N</i>-benzylbut-2-enamide derivatives were synthesized, and their solid-state structures were investigated using single-crystal X-ray diffraction. Furthermore, these two compounds were also characterized using powder X-ray diffraction, NMR spectroscopy, and Differential Scanning Calorimetry (DSC). The crystal packing investigation demonstrates that both the crystal structures form one-dimensional N–H···O hydrogen-bonded chains, further stabilised by weak C–H···F and C–H···O intermolecular interactions, which collectively support the three-dimensional supramolecular architecture in molecular solids. The interaction energy calculations using PIXEL provide quantitative insights to identify and evaluate the nature and strength of non-covalent interactions, including C–H···F, C–H···O, C-H···π, and non-specific close contacts. Additionally, the contributions of different interatomic contacts are elucidated through Hirshfeld surface analysis and associated two-dimensional fingerprint plots, while the electrostatic potential (ESP) mapping provides insights into the charge distribution on molecular surfaces and reveals potential hydrogen bond acceptor regions. Overall, the analysis shows that the position of fluorine substituents significantly influences the interaction landscape and overall crystal architecture.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2675 - 2687"},"PeriodicalIF":2.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950525","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 insights into the role of thiophene π-spacers and end-capped acceptors on the photovoltaic performance of dimethoxyterephthalaldehyde-derived chromophores","authors":"Iqra Shafiq,&nbsp;Sania Mureed,&nbsp;Khansa Gull,&nbsp;Muqadas Javed,&nbsp;Noor Fatima,&nbsp;Muhammad Imran,&nbsp;Faiz Rasool","doi":"10.1007/s11224-025-02702-4","DOIUrl":"10.1007/s11224-025-02702-4","url":null,"abstract":"<div><p>Organic photovoltaic (OPV) cells have emerged as promising alternatives to traditional inorganic solar cells due to the structural versatility and tunable optoelectronic properties of organic materials. In this context, a series of organic chromophore (<b>CPR</b> and <b>CPD1–CPD6</b>) was rationally designed through molecular engineering at terminal acceptor units to evaluate their potential as efficient OPV materials. The influence of these end-capped acceptors on the photovoltaic properties was investigated using quantum chemical calculations. The electronic structures were optimized using density functional theory (DFT) at the B3LYP/6-311G(d, p) level, while the optical properties were explored through time-dependent DFT (TD-DFT) simulations utilizing same functional. The <b>CPR</b> and <b>CPD1</b>–<b>CPD6</b> exhibited bathochromic shifts (617–723 <i>nm</i>) with reduced HOMO–LUMO gaps (1.967–2.274 <i>eV</i>), indicating enhanced electronic conjugation and charge transfer. An efficient charge transferred from the core toward the terminal acceptor units was investigated in entitled chromophores. Among all designed compounds, <b>CPD3</b> exhibited the promising optoelectronic characteristics, including the lowest exciton binding energy (0.251 <i>eV</i>), the highest absorption maximum (722.65 <i>nm</i>), and the smallest energy gap (1.967 <i>eV</i>), attributed to the presence of a strong electron-withdrawing substituent on acceptors. Furthermore, the donor–acceptor interactions between the designed chromophores and the PBDB-T polymer demonstrated favorable open-circuit voltages (0.685–1.052 <i>V</i>). Overall, these findings highlight the designed chromophores particularly <b>CPD3</b> as reasonable candidates for next-generation organic photovoltaic applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2689 - 2707"},"PeriodicalIF":2.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950520","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":"Investigation of the impact of DMSO and H2O solvents on the electronic and photovoltaic properties of graphene-oxide nanostructures: A DFT study","authors":"Hayder M. Abduljalil,&nbsp;Noor Al-Huda S. Hadi,&nbsp;Hussein Hakim Abed","doi":"10.1007/s11224-025-02700-6","DOIUrl":"10.1007/s11224-025-02700-6","url":null,"abstract":"<div><p>In the present study, the geometric, electronic, and optical properties of three nanostructured systems graphene oxide (GO), iron-doped graphene oxide (GO–FeO), and GO–FeO linked with polymethyl methacrylate (PMMA) (GO–FeO–PMMA) were investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The effects of two solvents, water (H₂O) and dimethyl sulfoxide DMSO ( C₂H₆OS) on the properties of these nanostructures were also examined. Photovoltaic parameters, including light harvesting efficiency (LHE), oscillator strength (f), free energy of electron injection and regeneration, and open-circuit voltage (V_oc), were evaluated. The results revealed that iron doping reduced the energy gap and enhanced the optical absorption of GO, while the incorporation of PMMA improved the overall stability of the system. Moreover, theoretical predictions indicated that DMSO solvent caused a reduction in energy gap for all systems and stronger light absorption compared to H₂O, thereby improving the electronic and optical performance of the GO-based systems for potential photovoltaic and sensor applications. In contrast, dissolving the GO–FeO nanostructure in H₂O enhanced its electronic properties and induced a blue shift in the UV–visible spectrum, leading to improved photovoltaic characteristics and a greater potential for application in dye sensitizer solar cell devices.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2663 - 2673"},"PeriodicalIF":2.3,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950494","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":"Substituent effects on the optoelectronic properties of conjugated polymers for high-efficiency organic solar cells: a theoretical investigation","authors":"Paulo Henrique de Sousa Paulino,&nbsp;Luciana Guimarães,&nbsp;Clebio Soares Nascimento Jr.","doi":"10.1007/s11224-025-02694-1","DOIUrl":"10.1007/s11224-025-02694-1","url":null,"abstract":"<div><p>This work investigates the enhancement of organic solar cells (OSCs) through structural modifications to electron-donor polymers. Using density functional theory (DFT) calculations, oligomers of polythiophene, polyselenophene, and polytellurophene were studied with the addition of electron-donating and -withdrawing substituent groups (a push-pull system). The results show that this strategy consistently improves the materials’ properties, leading to a reduced band gap, increased visible light absorption, and decreased exciton binding energy. These improvements facilitate charge separation, a crucial step for device efficiency. The reliability of the study is validated by its agreement with existing literature data. Among the derivatives, the TPhA–CNPhNO₂ push-pull system stood out, exhibiting the most favorable energy alignment with the TY acceptor. This makes it a highly promising candidate for the development of future high-efficiency OSCs.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2651 - 2662"},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950499","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":"Quantifying superacidity with density-based reactivity theory","authors":"Yaqin Zheng,&nbsp;Xinyue Zhao,&nbsp;Lei Zeng,&nbsp;Chunying Rong,&nbsp;Shubin Liu","doi":"10.1007/s11224-025-02695-0","DOIUrl":"10.1007/s11224-025-02695-0","url":null,"abstract":"<div><p>Superacids, defined as compounds exhibiting acidities stronger than sulfuric acid, are essential in catalysis, synthesis, and material chemistry. Yet the quantitative understanding of their <i>intrinsic</i> acidity remains challenging due to the complex interplay of charge delocalization, resonance, and solvation effects. In this work, we employ density-based reactivity theory to describe and predict the equilibrium acidities of two major families of superacids— comprising four representative series of nitrogen-centered and carbon-centered species—each comprising multiple molecular series with experimentally measured pKₐ values available in 1,2-dichloroethane. Descriptors derived from conceptual density functional theory, information-theoretic approach, and topological analysis at bond critical points were systematically evaluated. Strong linear correlations between calculated descriptors and experimental pKₐ values were observed for N-centered superacids, confirming the robustness of density-based quantities in capturing intrinsic acidity. In contrast, weaker correlations for C-centered analogues reveal the multifaceted origins of their superacidity. Multi-descriptor regression further improves quantitative agreement across all systems. These findings demonstrate that superacidity is an emergent, electron density associated phenomenon that can be rationalized and predicted within the density-based reactivity framework.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1837 - 1850"},"PeriodicalIF":2.3,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613040","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}