Structural Chemistry最新文献

{"title":"A modern “Skeptical chemist”: How Angelo Gavezzotti contributed to our understanding of molecular crystals","authors":"Leonardo Lo Presti","doi":"10.1007/s11224-026-02767-9","DOIUrl":"10.1007/s11224-026-02767-9","url":null,"abstract":"<div>\u0000 \u0000 <p>Prof. Angelo Gavezzotti is an Italian physical chemist who spent most of his career at the Università degli Studi di Milano. If one were to identify a common thread throughout his scientific work, it would undoubtedly be the study of molecular recognition in its broadest sense, with the goal of understanding how and why molecular symmetry emerges from disorder during crystallization. In recognition of his lifelong contributions, Structural Chemistry is pleased to honor Angelo with a dedicated special collection. This introductory note outlines the motivations and aims of the project while offering a guided overview of the most significant scientific contributions that both longtime colleagues and newer collaborators have contributed to celebrate Angelo’s distinguished career.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1045 - 1047"},"PeriodicalIF":2.2,"publicationDate":"2026-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-026-02767-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147938386","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}

{"title":"Exploration of the eigenvectors of the localization delocalization matrices for rutile TiO2 finite unit cells and solids: from resonance to QTAIM","authors":"Guadalupe Ureiro-Cueto,&nbsp;James S. M. Anderson","doi":"10.1007/s11224-026-02726-4","DOIUrl":"10.1007/s11224-026-02726-4","url":null,"abstract":"<div><p>The newly introduced eigenvectors of the localization-delocalization matrices (LDM) are used to characterize the distinct functional groups in the TiO₂ rutile solid material. The 1 × 1 × 1 finite unit cell and the 1 × 1 × 1 finite unit cell with the appropriate edge and corner atoms due to periodicity are included, which are neglected in a standard unit cell, as well as the solid (periodic) material are examined. The LDMs are constructed using all atoms in the two finite unit cells (for the periodic cases the corresponding atoms are used, and all other atoms are neglected). The eigenvectors and the corresponding localization/delocalization modes are used to indicate the functional groups and the resonance structures.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1763 - 1773"},"PeriodicalIF":2.3,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-026-02726-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148614530","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}

{"title":"Delocalization and geometries in the P-function of thiophosphinic derivatives: tautomerism and supramolecular interactions","authors":"Mátyás Czugler,&nbsp;Zoltán Mucsi,&nbsp;Józef Drabowicz,&nbsp;György Keglevich","doi":"10.1007/s11224-025-02596-2","DOIUrl":"10.1007/s11224-025-02596-2","url":null,"abstract":"<div><p>Model series of thiophosphinic acid derivatives were scrutinized at the B3LYP/6–311 + + G(2d,2p) level of theory, and the resulting geometries were compared with experimental crystal structure data obtained from the Cambridge Structure Database (CSD). Typical bond length and bond angle values were selected for a series of similar fragments from CSD, and mean dimensions were also calculated from the experimental data accumulated. Linking the results of theoretical calculations and the evidences of data mining allowed the reconsideration of a few past experimental models with (thio)phosphinate-anion-(thio)phosphinic acid-type associations. It seems also from this survey that thiophosphinic acid derivatives may be suitable vehicles for transgressing boundaries from a single molecule to supramolecular relations and vice versa. The study shows that a few intramolecular distances such as the P-O bond lengths both in the anionic and in the neutral forms may significantly depend on intermolecular contacts as well. The tautomerism involving the thionic acid and thiolic acid forms was studied by theoretical methods at the B3LYP/6–311 + + G(2d,2p) level of theory assuming monomolecular and different bimolecular mechanisms. The shift toward the thionic actor was supported by the kinetic and thermodynamic energetics.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1609 - 1620"},"PeriodicalIF":2.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02596-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147938686","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}

{"title":"Anatomy and formation of Br···O=C halogen and nonclassical hydrogen bonds and (pi)···(pi) stacking: insights from the conservative electronic force fields in the molecular crystal and the supermolecule of 1-(5-bromopyridin-2-yl)ethan-1-one","authors":"Alina F. Saifina,&nbsp;Sergey V. Kartashov,&nbsp;Robert R. Fayzullin","doi":"10.1007/s11224-025-02711-3","DOIUrl":"10.1007/s11224-025-02711-3","url":null,"abstract":"<div><p>Herein, a combined experimental–theoretical investigation of the subatomic structure of 1-(5-bromopyridin-2-yl)ethan-1-one in the crystal, the isolated molecule, and its dimer is presented. The use of novel structural descriptors—most of which are based on the conservative electronic force fields—provides an exceptional framework for elucidating chemical interactions in these systems within the conceptual contexts of Lewis acidity–basicity, interatomic electron transfer, and the concomitant manifestations of Fermi electron correlation in real space. The analysis of the vector fields relies extensively on the superposition of trajectory maps. The electron density gradient <span>(nabla rho (mathbf{r}))</span>, the electrostatic force field <span>(mathbf{F}_{mathrm{es}}(mathbf{r}))</span>, and the total static force field <span>(mathcal{F}(mathbf{r}))</span> in the crystal, together with the distributions of the bosonic, fermionic, and total static potentials—<span>(varphi_{mathrm{W}}(mathbf{r}))</span>, <span>(varphi_{mathrm{f}}(mathbf{r}))</span>, and <span>(varphi_{mathrm{em}}(mathbf{r}))</span>—are derived from the high-resolution single-crystal X-ray diffraction data and compared with theoretical results. Particular attention is devoted to the characterization of halogen bonding, nonclassical hydrogen bonding, and <span>(pi)</span>···<span>(pi)</span> stacking in the crystal. To analyze the molecular association mediated by the Br···O=C halogen bond, in addition to the aforementioned properties, the exchange force field <span>(mathbf{F}_{x}(mathbf{r}))</span>, its component projection <span>(left[mathbf{F}_{x}(mathbf{r}) cdot mathcal{F}(mathbf{r})right]/|mathcal{F}(mathbf{r})|)</span>, and the exchange charge density <span>(nabla cdot mathbf{F}_{x}(mathbf{r})/(4pi))</span> are employed as principal diagnostics. Importantly, for the Br···O=C halogen bond studied herein, the charge transfer is directed from the bromine atom acting as the Lewis acid to the oxygen atom acting as the Lewis base, rather than <i>vice versa</i>. </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":"1951 - 1968"},"PeriodicalIF":2.3,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613653","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":"Local spin of atoms in molecules: relation to electron localization and delocalization","authors":"Ángel Martín Pendás,&nbsp;Evelio Francisco,&nbsp;Aldo J. Mortera-Carbonell,&nbsp;Jesús Jara-Cortés,&nbsp;Jesús Hernández-Trujillo","doi":"10.1007/s11224-026-02732-6","DOIUrl":"10.1007/s11224-026-02732-6","url":null,"abstract":"<div>\u0000 \u0000 <p>Following the approach of Clark and Davidson, we partition the total squared spin of a molecule, <span>(langle hat{varvec{S}}^{varvec{2}}rangle )</span>, into atomic, <span>(langle hat{varvec{S}}_{varvec{A}}^{varvec{2}}rangle )</span>, and interatomic, <span>(langle hat{varvec{S}}_{varvec{A}}cdot hat{varvec{S}}_{varvec{B}}rangle )</span>, components within the framework of the Quantum Theory of Atoms in Molecules (QTAIM) and algebraically establish, and numerically analyze the relationship of these contributions to standard QTAIM measures of electron localization and delocalization for a set of molecules described at various levels of theory. Although this relationship is already known, it remains underutilized in QTAIM, warranting a dedicated examination in this work. Furthermore, we subdivide the atomic (or local) and bonding (or interatomic) spin terms into finer contributions, each associated with a specific electron population of an arbitrary atom or fragment of the molecule. This finer partition is achieved by using the theory of open quantum systems (OQSs). Our results reinforce our confidence in the proposed partitioning scheme for <span>(langle hat{varvec{S}}^{varvec{2}}rangle )</span>, since it preserves the physical meaning of the components without resorting to mathematically equivalent but physically ambiguous transformations that have been frequently used in the literature. Several examples in simple molecular systems are also examined.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1689 - 1701"},"PeriodicalIF":2.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-026-02732-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613092","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}

{"title":"Avogadro constant and molecular crystals","authors":"Fabio Pichierri","doi":"10.1007/s11224-026-02734-4","DOIUrl":"10.1007/s11224-026-02734-4","url":null,"abstract":"<div><p>In this study we set out to calculate the Avogadro number (N_mx) for a set of 22 molecular crystals of known experimental density. Crystals comprise cubic, orthorhombic, and monoclinic unit cells whose lattice parameters are available in the Cambridge Structural Database (CSD). The computed N_mx values are then compared to the modern value of the Avogadro constant (N_A), which is taken as reference. The crystals that yield the N_mx values closest to N_A are characterized by extended networks of hydrogen bonds which are likely responsible for high values of the packing coefficient (PC &gt; 0.7). Thus, crystals with dense packings are likely to produce values of N_mx that converge towards N_A. However, there are exceptions to this trend since some crystals with low PC values (PC &lt; 0.7) yield N_mx values which also are close to N_A. Another surprising result is that concerning a group of tightly packed crystals which produce values of N_mx that are significantly higher than N_A. This result could arise from the low accuracy of the experimental densities utilized herein or from the presence of impurities incorporated into molecular solids during the crystallization process. Thus, the need to perform accurate measurements of the experimental density done at the same temperature as that of the X-ray data collection would be important for assessing the factors that contribute to the deviation from Avogadro constant.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1133 - 1148"},"PeriodicalIF":2.2,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147937999","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":"Darleane C. Hoffman centennial: A life for nuclear chemistry","authors":"Magdolna Hargittai","doi":"10.1007/s11224-026-02751-3","DOIUrl":"10.1007/s11224-026-02751-3","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1621 - 1625"},"PeriodicalIF":2.2,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147937830","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":"Exploring the impact of terminal and central positions of polycyclic aromatic cores on aromaticity and NLO properties: a systematic computational analysis under various solvation methods","authors":"Shabbir Muhammad,&nbsp;Adan Ahmad,&nbsp;Faleh Zafer Alqahtany,&nbsp;Shamsa Bibi,&nbsp;Shafiq urRehman,&nbsp;Abdullah G. Al-Sehemi","doi":"10.1007/s11224-026-02763-z","DOIUrl":"10.1007/s11224-026-02763-z","url":null,"abstract":"<div>\u0000 \u0000 <p>Polycyclic aromatic compounds (PACs) are setting a higher benchmark for next-generation optoelectronics and nonlinear optical (NLO) materials, owing to their unparalleled π-conjugation and aromatic stability. In this study, we designed two tailored molecular sets, <b>P1-A</b> to <b>P3-A</b> and <b>P1-D</b> to <b>P3-D</b>, by blending diverse polycyclic aromatic cores with donor or acceptor terminals. We quantified the aromaticity of our designed compounds by using the harmonic oscillator model aromaticity (HOMA) and the nucleus independent chemical shift (NICS) to assess the extent of aromatic character and distinguish between aromatic and non-aromatic behavior. Strikingly, the terminal rings in compounds <b>P1-A</b> and <b>P1-D</b> exhibit nearly ideal structural aromaticity (HOMA = ~ 0.98 to ~ 0.99), yet show positive NICS(1)_zz values (1.7 to 2 ppm), revealing a pronounced disconnect between geometric and magnetic aromaticity. Building on the aromaticity findings, we proceed to explore the NLO responses of the studied compounds. This evaluation demonstrates how their electronic and structural characteristics modulate NLO behavior. Our density functional theory (DFT) calculations indicate that <b>P3-A</b> and <b>P3-D</b> emerge as standout candidates with the highest level of third-order NLO polarizability (γ) of 160 × 10^− 36 esu and 124.1 × 10^− 36 esu, outshining their counterparts. Furthermore, unit spherical representation (USR) analysis confirms the superior performance of compound <b>P3-A</b>, providing strong evidence of its remarkable NLO behavior. Solvent effects, analyzed through integral equation formalism polarizable continuum model (IEFPCM), conductor-like screening model (COSMO), and the explicit model, present a promising trend, with α_iso values increasing by approximately ⁓1.1 to ⁓1.2 times in methanol compared to the gas phase. In dynamic NLO, both the electro-optic Pockels effect (EOPE, γ (-ω; ω,0,0)) and the second-harmonic generation (SHG) process γ (-2ω; ω, ω,0) show significantly enhanced values (537.9 × 10^− 36 esu and 11599.2 × 10^− 36 esu) of NLO at 543 nm. TD-DFT studies underscore the significant excitation properties of <b>P3-A</b> and <b>P3-D</b>, with solid oscillator strength values (0.9080 and 0.8696). Meanwhile, UV-Visible results demonstrate a noticeable red shift for <b>P1-D</b> at 356 nm. Hence, these PAC-based derivatives are promising candidates with the potential to advance next-generation NLO technologies.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"2023 - 2045"},"PeriodicalIF":2.3,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613368","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 role of π–π, C–H⋯halogen, and halogen⋯π interactions in the crystal packing of 9-aminoacridinium 3-halobenzoate salts: an experimental and theoretical investigation","authors":"Patryk Nowak,&nbsp;Artur Sikorski,&nbsp;Artur Mirocki","doi":"10.1007/s11224-026-02758-w","DOIUrl":"10.1007/s11224-026-02758-w","url":null,"abstract":"<div>\u0000 \u0000 <p>The crystal structures of 9-aminoacridinium 3-halobenzoate salts (X = Cl, Br, I) were compared in terms of molecular packing and intermolecular interactions. All three compounds crystallize in the monoclinic <i>P</i>2₁/<i>c</i> space group, are isomorphous, and exhibit a high degree of structural similarity with closely related packing motifs. Analysis of geometric parameters confirms proton transfer from the carboxylic group of the acid to the endocyclic nitrogen atom of 9-aminoacridine, consistent with Δp<i>K</i>a predictions indicating salt formation. Analysis of intermolecular interactions shows that the crystal packing is stabilized by a network of N–H⋯O and C–H⋯O hydrogen bonds, as well as π–π stacking, C–H⋯halogen, and halogen⋯π interactions. Geometric analysis of the halogen⋯π contacts indicates that these interactions can be classified as weak n–π* interactions. Energy framework calculations demonstrate that the energetic stability of the crystals increases with halogen size (I &gt; Br &gt; Cl), in agreement with the observed melting points, and highlight the dominant role of dispersion forces in stabilizing the supramolecular architecture across all three structures.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1191 - 1202"},"PeriodicalIF":2.2,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147938132","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":"Comprehensive quantum-chemical, spectroscopic, topological, and molecular docking investigation of 4FCA and 4MCA as potential anticancer agents targeting human estrogen receptor alpha","authors":"Remya Punnyamurthy,&nbsp;Nekaa Nithya Sre Karuppanan Ayyappan Venkatachalapathy,&nbsp;Jayavarthanan Toulasy,&nbsp;Sivaranjani Tamilmani,&nbsp;Kumaran Manogaran","doi":"10.1007/s11224-026-02736-2","DOIUrl":"10.1007/s11224-026-02736-2","url":null,"abstract":"<div><p>A comprehensive structural, thermodynamic, vibrational, and electronic investigation of the <i>s-cis</i> and <i>s-trans</i> conformers of 4-fluorocinnamic acid (4FCA) and 4-methoxycinnamic acid (4MCA) has been carried out using the DFT/B3LYP method in conjunction with FTIR, FT–Raman, FTNMR, and natural bond orbital (NBO) analyses. Conformational stability follows the order I &lt; II &lt; III for both molecules. Bond length comparison reveals shorter C–F bonds in 4FCA conformers compared to fluorobenzene, while 4MCA exhibits characteristic C–OCH₃ and O–CH₃ bond lengths consistent with its structural features. Electron density and electrostatic potential mapping highlight distinct charge distributions in the conformers, while dipole moment calculations confirm higher polarity in 4MCA relative to 4FCA. Frontier molecular orbital analysis shows a larger HOMO–LUMO gap for 4FCA, indicating its greater hardness compared to 4MCA. Strong intramolecular charge transfer interactions, particularly <i>n</i>O → π*CO stabilizations, are evident in both molecules with stabilization energies exceeding 32 kcal mol⁻¹. NMR chemical shifts further support delocalization effects, especially in = C–H protons. Fukui function–based reactivity descriptors reveal site selectivity for nucleophilic and electrophilic attacks, with C1 emerging as the most reactive site in both compounds. These combined experimental and theoretical results provide valuable insights into the structural preferences, electronic features, and reactivity patterns of 4FCA and 4MCA conformers. The simulations performed by the Protein-Ligand Interaction Analysis indicated successful binding capabilities of 4FCA and 4MCA to Human Estrogen Receptor Alpha, and it might be used as an anticancer agent. Its pharmacokinetic and drug-likeness were also supported by ADMET predictions. The findings highlight the therapeutic importance of 4FCA and 4MCA present a basis on which the drug will be used in pharmaceutical methods in the future.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"2219 - 2246"},"PeriodicalIF":2.3,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613204","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}