Polyhedron最新文献

{"title":"Synthesis and structural investigation of an 8-Hydroxyquinoline–fluoride adduct","authors":"Priyanka R. Angarkhe ,&nbsp;Satyajit Sahoo ,&nbsp;Umakanta Pradhan ,&nbsp;Kuldeep Mahiya ,&nbsp;Jagnyaseni Tripathy ,&nbsp;Swagat K. Mohapatra","doi":"10.1016/j.poly.2025.117720","DOIUrl":"10.1016/j.poly.2025.117720","url":null,"abstract":"<div><div>An adduct of 8-hydroxyquinoline and fluoride was synthesized, and its structure was determined through single-crystal X-ray and elemental analysis. The fluoride ion forms weak bonds with three 8-hydroxyquinoline molecules, arranged in a distorted triangular geometry. Given the complexity of the structure, we have found a reasonably good model that fits the structure well. The fluoride adduct crystallizes in the monoclinic C2/c space group with Z = 4 and Z' = ½. The asymmetric unit consists of a half-occupied tetrabutylammonium ion, where the N-atom is positioned on a two-fold axis. Additionally, one 8-hydroxy quinoline (HQ) molecule in the asymmetric unit is disordered about a two-fold axis, and the second HQ molecule is located at the inversion center. The fluorine atom appears ordered and is assigned one-half occupancy to maintain charge balance.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"281 ","pages":"Article 117720"},"PeriodicalIF":2.6,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144830176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical CO2 capture by quinone-functionalized ruthenium polypyridine complexes","authors":"Sebastián Pizarro,&nbsp;Constanza Angel,&nbsp;Raul Cañas-Sarazua,&nbsp;Alvaro Delgadillo","doi":"10.1016/j.poly.2025.117719","DOIUrl":"10.1016/j.poly.2025.117719","url":null,"abstract":"<div><div>Carbon dioxide emissions have reached critical levels, making it necessary to develop efficient capture and storage strategies to mitigate its environmental impact. Electrochemical methods employing redox-active carriers offer a promising alternative to traditional technologies. In this study, we explore the potential of ruthenium(II) polypyridyl complexes with quinone functionalized ligands (Q), specifically [Ru(bpy)₂(phendione)]²⁺ and [Ru(bpy)₂(NQphen)]²⁺ (where phendione is 1,10-phenanthroline-5,6-dione; NQphen is benzo[<em>i</em>]dipyrido[3,2-a:2′,3′-c]phenazine-10,15-dione, and bpy is 2,2′-bipyridine) with regard to their electrochemical behavior towards CO₂ capture. The electrochemical properties of these complexes were analyzed using cyclic voltammetry, focusing on the potentials associated with the formation of radical anions (Q/Q^•-) and dianions (Q^•−/Q²⁻), with the latter species being responsible for CO₂ capture. The reduction potentials of the quinone units were determined to be −0.17 V and − 0.81 V vs Ag/AgCl for [Ru(bpy)₂(phendione)]²⁺ and − 0.46 V and − 0.97 V vs Ag/AgCl for [Ru(bpy)₂(NQphen)]²⁺. In the presence of CO₂, average cathodic shifts of 220 mV were observed, indicating the formation of reversible adducts. Additionally, the CO₂ binding constants (log K) for the adducts were determined, yielding values of 5.8 for [Ru(bpy)₂(phendione)]²⁺ and 7.2 for [Ru(bpy)₂(NQphen)]²⁺, suggesting that the CO₂ affinity can be tuned through ligand modification. These results indicate that ruthenium(II) polypyridyl complexes functionalized with quinones possess favorable electrochemical well-defined electrochemical characteristics, including reversible redox processes and significant CO₂ binding ability. for CO₂ capture. This study highlights the potential of such systems to contribute to the development of efficient and reusable molecular technologies aimed at advancing sustainable carbon management.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"281 ","pages":"Article 117719"},"PeriodicalIF":2.6,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144830175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure, XAS and magnetism of copper(II) and nickel(II) heterometallic complexes based on the [Cr(NCS)6]3− and [Cr(NCS)4(NH3)2]− units","authors":"Natalia Tereba ,&nbsp;Tadeusz M. Muzioł ,&nbsp;Robert Podgajny ,&nbsp;Alina Bieńko ,&nbsp;Maciej Witwicki ,&nbsp;Jedrzej Kobylarczyk ,&nbsp;Joanna Wiśniewska","doi":"10.1016/j.poly.2025.117714","DOIUrl":"10.1016/j.poly.2025.117714","url":null,"abstract":"<div><div>The new heterometallic compounds, {[Ni(tren)(H₂O)]₂(μ_1,3-NCS)}[Cr(NCS)₆] (<strong>1</strong>), {[Cu(tren)(H₂O)]₂(μ_1,3-NCS)}[Cr(NCS)₆] (<strong>2</strong>) and [Ni(tren)(H₂O)(NCS)][Cr(NCS)₄(NH₃)₂] (<strong>3</strong>) (tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. The compounds <strong>1</strong> and <strong>2</strong> were isomorphous and crystallized in the monoclinic P2₁/c space group. These compounds consisted of a homometallic Ni<img>Ni and Cu<img>Cu dimers in <strong>1</strong> and <strong>2</strong>, respectively, in which metal ions were coordinated by a single thiocyanate μ_1,3-NCS⁻ bridge, and the [Cr(NCS)₆]³⁻ unit as the counterion. Crystal lattice of compound <strong>3</strong> had an orthorhombic Pbca symmetry. Single monomeric nickel ions and [Cr(NCS)₄(NH₃)₂]⁻ ions were arranged in the form of columns composed of alternately arranged complex cations and anions stabilised by hydrogen bonding. The XAS spectra on the selected 3d metals (Ni, Cu, Cr) L-edge and the N and O K-edge were intended to enable the determination of the spin state and configuration of Ni, Cu, Cr and to relate this information to other properties of materials, such as local symmetry of central atoms, charge state, covalency of unoccupied valence orbitals. The K-edge and L-edge XAS spectra confirmed the elemental composition and local geometry of transition metals occurring in newly synthesized molecular materials. Similarities in topology, local symmetry and structure enabled significant simplification of the magnetic properties modelling by assuming magnetic coupling inside {Ni^IINi^II} or {Cu^IICu^II} binuclear units separated by paramagnetic [Cr(NCS)₆]³⁻ units in <strong>1</strong> and <strong>2</strong>. The obtained results indicated dominant antiferromagnetic interactions between metal ions in the dimers, which was confirmed by theoretical DFT and <em>ab initio</em> CASSCF/NEVPT2 calculations.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117714"},"PeriodicalIF":2.6,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144780175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The rise of agents: Computational chemistry is ready for (R)evolution","authors":"Alán Aspuru-Guzik ,&nbsp;Varinia Bernales","doi":"10.1016/j.poly.2025.117707","DOIUrl":"10.1016/j.poly.2025.117707","url":null,"abstract":"<div><div>In this perspective, we take a historical view of the development of modern quantum chemistry from the 1950s to the present. We argue that we are at a crossroads where artificial intelligence will further democratize our discipline. Historically, the computational chemistry tasks that a chemist could conceive and execute were inherently bound to the computational capabilities of the period. We focus on the second half of this decade, from 2025 to 2030, where we believe the artificial intelligence revolution will enable us to rethink how quantum chemistry is conducted. In particular, we will review the recent development of our agentic quantum chemistry, discuss what we believe are its implications for the capabilities and future of the chemical profession in general, and explore what it may mean to be a computational chemist in the future.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"281 ","pages":"Article 117707"},"PeriodicalIF":2.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A new approach to density functional energy evaluation","authors":"Peter M.W. Gill,&nbsp;Kosta D. Tsoukalas,&nbsp;Martin Mrovec","doi":"10.1016/j.poly.2025.117681","DOIUrl":"10.1016/j.poly.2025.117681","url":null,"abstract":"<div><div>We describe a method for computing density functional energies and test it on a variety of organic and inorganic molecules. Instead of avoiding double-counting by introducing Becke weights at each point in space, we use a Hirshfeld partition of the electron density and then apply the Inclusion-Exclusion Principle to expand the energy <span><math><mi>E</mi></math></span> in a series. We find that the first term <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> contributes 95%–100% of <span><math><mi>E</mi></math></span> and that <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> delivers most of the remainder. The higher terms, <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> and <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>4</mn></mrow></msub></math></span>, are generally much smaller although, in highly crowded systems such as cubane, their contribution can approach 1% of <span><math><mi>E</mi></math></span>. We propose an efficient Double Exponential + Lebedev quadrature scheme for calculating <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> and a less optimized product scheme for calculating <span><math><msub><mrow><mi>E</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> in prolate spheroidal coordinates.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117681"},"PeriodicalIF":2.6,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144780173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploration of electronic and nonlinear optical properties of excess electrons system (alkaline earthides) based on 18-aza-crown complexant","authors":"Jabir Hussain ,&nbsp;Riaz Hussain ,&nbsp;Ajaz Hussain ,&nbsp;Muhammad Arshad ,&nbsp;Muhammad Durair Sajjad Haider ,&nbsp;Khaled Fahmi Fawy ,&nbsp;Rao Shahab Ahmed ,&nbsp;Masooma Zahra ,&nbsp;Khurshid Ayub","doi":"10.1016/j.poly.2025.117711","DOIUrl":"10.1016/j.poly.2025.117711","url":null,"abstract":"<div><div>A class of alkaline earthides based on aza-18-crown-6 complexant, containing nine complexes, is designed by intercalating alkali metals, Li – K (AMs) inside and alkaline earth metals, Be – Ca (AEMs) outside the complexant. The DFT calculations are performed by using WB97XD/ 6-31 + G (d,p) level of theory to explore electronic and nonlinear optical (NLO) properties of complexes. The alkaline earthides are electronically and thermally stable, as indicated by their vertical ionization potentials and interaction energies. The nature of the earthides is confirmed through natural bond orbital and frontier molecular orbital analyses, which show negative charges and the position of the HOMO on AEMs. The complexes exhibit notable nonlinear optical responses, with first hyperpolarizability (β₀) values reaching up to 3.40 × 10⁴ a.u. The higher β₀ values are attributed to excess electrons on AEMs in the complexes. Additionally, applying an external electric field (EEF) further enhances their hyperpolarizability. A remarkable 10-fold increase in hyperpolarizability, from 9.81 × 10³ a.u. to 2.88 × 10⁴ a.u., is observed for the <strong>K</strong>^{<strong>+</strong>}<strong>(aza-18-crown-6)Be</strong>^{<strong>−</strong>} complex when an EEF of 0.01 a.u. strength is applied. These findings supported the better NLO responses of the designed complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117711"},"PeriodicalIF":2.6,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144757160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, characterization and antiviral efficacy of new Pd(II) and Cu(II) complexes with imines-based bidentate ligands","authors":"Simranjeet Singh,&nbsp;Mukesh Choudhary","doi":"10.1016/j.poly.2025.117710","DOIUrl":"10.1016/j.poly.2025.117710","url":null,"abstract":"<div><div>This work reports the design, synthesis and antiviral studies of two new Pd(II) and Cu(II) complexes <em>viz.</em> [Pd(L¹)₂].DMF <strong>1</strong> and [Cu(L²)₂] <strong>2</strong> with imine-based bidentate ligands (HL¹ = (<em>E</em>)-2-(2,3-dichlorobenzylidene)-<em>N</em>-phenylhydrazine-1-carbothioamide and HL² = (<em>E</em>)-(2-((5-bromo-2-hydroxybenzylidene)amino)-5-chlorophenyl)(phenyl)methanone). Single-crystal X-ray crystallography study reveals that complexes <strong>1</strong> and <strong>2</strong> crystallized in a monoclinic and triclinic crystal system with <em>P2</em>_<em>1/c</em> and <em>P</em>_<em>−</em>_<em>1</em> space groups, respectively. Both metal complexes <strong>1</strong> and <strong>2</strong> exhibit a distorted square planar geometry around the Pd(II) and Cu(II) ions coordinated through the NS and NO donor atoms from their respective two deprotonated ligands HL¹ and HL². Density functional theory (DFT) calculations were performed to validate the experimental geometries and confirm the electronic structures. Further insights into the crystal packing and intermolecular interactions were obtained through Hirshfeld surface analysis and 2D-fingerprint plots, providing a detailed understanding of non-covalent interactions in the solid state. We further explored the nucleotide/protein binding interaction ability of <strong>1</strong> and <strong>2</strong> with CT-DNA/BSA using a UV–visible and Fluorescence study. Absorption titration studies of the complexes <strong>1</strong> and <strong>2</strong> revealed that they strongly interact with CT-DNA and BSA. The <em>K</em>_<em>b</em> values found can be considered strong when compared with typical DNA intercalators such as ethidium bromide. To explore the superior biological activity (anticancer efficacy) of <strong>1</strong> and <strong>2</strong> <em>in-vitro</em> cytotoxicity assays were conducted against human cell lines: breast cancer (MCF-7), cervical cancer (HeLa) and lung cancer (A549) and the results are compared with the human normal kidney epithelial (NKE) cell line to get insights into the side effect on normal cells. Moreover, <strong>1</strong> and <strong>2</strong> were tested for <em>in-vitro</em> antibacterial activity and the results showed that <strong>1</strong> proved more potent activity than <strong>2</strong>. Additionally, molecular docking calculations were employed to explore the antiviral potential of complexes <strong>1</strong> and <strong>2</strong> against the SARS-CoV-2 (PDB ID:<span><span>8K67</span><svg><path></path></svg></span>), Omicron (PDB ID: <span><span>7ZFF</span><svg><path></path></svg></span>) and HIV-1 (PDB ID: <span><span>6PTP</span><svg><path></path></svg></span>) viral proteins. <strong>1</strong> and <strong>2</strong> showed good inhibition performance with the intended drug targets of t","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117710"},"PeriodicalIF":2.6,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144738540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The high stable dielectric response with tailored structural and spectral properties of Sm3+ substituted cu-ferrites","authors":"Muhammad Junaid ,&nbsp;Muhammad Adnan Mehmood ,&nbsp;Alina Manzoor ,&nbsp;Yosef Jazaa ,&nbsp;Syeda Rabia Ejaz ,&nbsp;Abdul Majeed ,&nbsp;Muhammad Azhar Khan ,&nbsp;Majid Niaz Akhtar","doi":"10.1016/j.poly.2025.117712","DOIUrl":"10.1016/j.poly.2025.117712","url":null,"abstract":"<div><div>The structural, spectral, and dielectric study of Sm³⁺ incorporated copper (Cu) nano ferrites CuSm_xFe_2-xO₄ (where x = 0.00, 0.04, 0.08, 0.12, and 0.16) were studied, and samples were synthesized by sol-gel route in the nanoscale. X-ray diffraction patterns revealed the formation of spinel structure in the nano-regime. The FTIR spectra indicated the presence of specific bands reflecting the stretching vibrations of metal oxygen bonds in tetrahedral and octahedral configurations in the range of 400 to 600 cm⁻¹. The dielectric losses ε” and tanδ were found to decline as the frequency increased. The study of M′ and M′′ versus frequency indicated that the real part of the modulus increased in the low-frequency region, remained steady in the moderate-frequency region, and showed resonance peaks at higher frequencies. The increase in samarium concentration decreases grain size and increases aggregation. The synthesized materials may have potential in the fabrication of magnetic and microwave devices.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117712"},"PeriodicalIF":2.6,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144757159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co-crystals of manganese(II) 1,10-phenanthroline-based complexes with 4-hydroxybenzoic acid and hippuric acid: synthesis, crystal structure and antibacterial activity","authors":"Rodi Laishram ,&nbsp;Atom Rajiv Singh ,&nbsp;Sapam Saya Devi ,&nbsp;Nameirakpam Thomson ,&nbsp;Wahengbam Pusparani Chanu ,&nbsp;Lesław Sieroń ,&nbsp;Waldemar Maniukiewicz ,&nbsp;Rajkumari Lonibala","doi":"10.1016/j.poly.2025.117682","DOIUrl":"10.1016/j.poly.2025.117682","url":null,"abstract":"<div><div>Two metal–organic co-crystal complexes with Mn(II) centre, [Mn(phen)₂Cl₂][4-hbaH] (<strong>1</strong>) and [Mn(phen)₂(H₂O)Cl]⁺[hip]⁻Cl⁻.H₃O⁺.2H₂O (<strong>2</strong>) where phen = 1,10-phenanthroline; 4-hbaH = 4-hydroxybenzoic acid; hip⁻ = hippuric acid ion, were successfully synthesized by conventional reflux method and characterized using single crystal X-ray diffraction, spectroscopic, magnetic susceptibility, thermal and EDAX analysis data. SC-XRD analysis for <strong>1</strong> and <strong>2</strong> revealed the presence of distorted octahedral Mn(II) centre complex unit where the formation of metal–organic co-crystal complexes were confirmed from the dominant supramolecular non-covalent interactions such as halogen-bonding in <strong>1</strong> and hydrogen-bonding in <strong>2</strong>. We explored the use of potential auxiliary ligands which embroidered through non-covalent interactions between organic and metal-organic moieties resulting in the formation of co-crystal with Mn(II) based supramolecular motif such as 4-hbaH in <strong>1</strong> and hip in <strong>2</strong>. The complexes were screened for their activities and showed significant antibacterial properties against bacteria pathogens.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117682"},"PeriodicalIF":2.6,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144738527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical insights into exchange coupling interactions in two biomimetic mixed-valence manganese complexes: A density matrix renormalization group study","authors":"Cheng Peng ,&nbsp;Ke Niu ,&nbsp;Yinxuan Song ,&nbsp;Haibo Ma","doi":"10.1016/j.poly.2025.117664","DOIUrl":"10.1016/j.poly.2025.117664","url":null,"abstract":"<div><div>Manganese complexes exhibiting magnetic interactions play a pivotal role in single-molecule magnetism and photosynthetic water oxidation. These systems often possess dense spin manifolds with energy gaps smaller than the threshold of chemical accuracy (1 kcal/mol), making the accurate theoretical description of their electronic structures and magnetic properties a significant challenge due to strong electron correlation effects. In this work, we employ state-of-the-art multi-configurational calculations with an extensive active space encompassing 31 electrons in 26 orbitals to investigate the electronic structures of two mixed-valence manganese dimers: <span><math><msup><mrow><mrow><mo>[</mo><msub><mrow><mtext>Mn</mtext></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>O</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>OAc</mtext><mo>)</mo></mrow><msub><mrow><mrow><mo>(</mo><mtext>tacn</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mo>]</mo></mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></math></span> and <span><math><msup><mrow><mrow><mo>[</mo><msub><mrow><mtext>Mn</mtext></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>O</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>OAc</mtext><mo>)</mo></mrow><msub><mrow><mrow><mo>(</mo><mtext>bpea</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mo>]</mo></mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></math></span> using the density matrix renormalization group (DMRG) method. The results demonstrate that DMRG provides superior accuracy over the widely used broken-symmetry density functional theory (BS-DFT) in predicting magnetic exchange coupling constants (<span><math><msub><mrow><mi>J</mi></mrow><mrow><mi>i</mi><mi>j</mi></mrow></msub></math></span>). Furthermore, orbital entanglement analysis, grounded in quantum information theory, reveals that the antiferromagnetic coupling in these dimers stems from superexchange interactions between the Mn centers mediated by the oxo and acetate bridging ligands. Notably, the pathway through the bridging oxygen dominates over the longer O-C-O route. In addition, we find that <span><math><msup><mrow><mrow><mo>[</mo><msub><mrow><mtext>Mn</mtext></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>O</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mrow><mo>(</mo><mi>μ</mi><mo>−</mo><mtext>OAc</mtext><mo>)</mo></mrow><msub><mrow><mrow><mo>(</mo><mtext>bpea</mtext><mo>)</mo></mrow></mrow><mrow><mn>2</mn></mrow></msub><mo>]</mo></mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></math></span> exhibits stronger exchange coupling than its <span><math><msup><mrow><mrow><mo>[</mo><msub><mrow><mtext>Mn</mtext></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mrow><mo>(</mo><mi>μ</","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117664"},"PeriodicalIF":2.6,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}