Pub Date : 2026-03-16Epub Date: 2026-03-02DOI: 10.1021/acs.inorgchem.5c06053
Yan-Juan Wang, Ye Du, Xiao-Yu Zhang, Yan-Ran Weng, Yan Qin, Lin Zhou, Yuan-Yuan Tang
Multifunctional materials with multiple physical channel responses are extensively used in various high-tech fields due to their superordinary electrical, magnetic, optical, thermal, acoustic, and other functions. Despite significant progress in functional materials, the ones with multiphysical channel switching responses have long been a great challenge. Herein, we present a thermochromic organic-inorganic hybrid ferroelastic semiconductor [PPY]2[CuCl4] (PPY = 4-pyrrolidinopyridine) with three physical channel switching responses in thermal/electrical/optical properties. [PPY]2[CuCl4] undergoes a ferroelastic phase transition at 317 K, characterized by the Aizu notation mmmF2/m, accompanied by the emergence and disappearance of ferroelastic domains during the phase transition. It also exhibits continuous and stable switching between high- and low-dielectric states in the vicinity of 417 K. Moreover, it exhibits intriguing thermochromism (green ↔ chartreuse) and possesses potential semiconductor characteristics with a band gap of 2.31 eV. This study contributes to the advancement of ferroelastic materials and devices capable of multiphysical channel responses.
{"title":"Thermochromic Hybrid Ferroelastic Semiconductor with Thermal/Electrical/Optical Switching Responses.","authors":"Yan-Juan Wang, Ye Du, Xiao-Yu Zhang, Yan-Ran Weng, Yan Qin, Lin Zhou, Yuan-Yuan Tang","doi":"10.1021/acs.inorgchem.5c06053","DOIUrl":"10.1021/acs.inorgchem.5c06053","url":null,"abstract":"<p><p>Multifunctional materials with multiple physical channel responses are extensively used in various high-tech fields due to their superordinary electrical, magnetic, optical, thermal, acoustic, and other functions. Despite significant progress in functional materials, the ones with multiphysical channel switching responses have long been a great challenge. Herein, we present a thermochromic organic-inorganic hybrid ferroelastic semiconductor [PPY]<sub>2</sub>[CuCl<sub>4</sub>] (PPY = 4-pyrrolidinopyridine) with three physical channel switching responses in thermal/electrical/optical properties. [PPY]<sub>2</sub>[CuCl<sub>4</sub>] undergoes a ferroelastic phase transition at 317 K, characterized by the Aizu notation <i>mmm</i>F2/<i>m</i>, accompanied by the emergence and disappearance of ferroelastic domains during the phase transition. It also exhibits continuous and stable switching between high- and low-dielectric states in the vicinity of 417 K. Moreover, it exhibits intriguing thermochromism (green ↔ chartreuse) and possesses potential semiconductor characteristics with a band gap of 2.31 eV. This study contributes to the advancement of ferroelastic materials and devices capable of multiphysical channel responses.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"5724-5730"},"PeriodicalIF":4.7,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147324030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A quantum-chemical investigation of nitroxide and nitronyl nitroxide diradicals with a 2,7-naphthalene coupling unit (bis-tert-butylnitroxide DR4, bis-nitronyl nitroxide DR6, and mixed tert-butylnitroxide/nitronyl nitroxide DR5) was carried out to predict conformation-dependent values of the intramolecular interactions. The coupling constants J are positive for symmetrical diradicals with tert-butyl-nitroxide or nitronyl nitroxide moieties (B3LYP/Def2-TZVPP: ∼440 and 60 K, respectively, for the most stable conformations), but it is negative for the mixed DR5 (∼−160 K). The triplet diradical DR4 was allowed to react with Mn(hfac)2 to give a polymer complex [Mn(hfac)2(DR4)]n exhibiting non-linear field dependencies of magnetization at low temperatures due to short-range ordering within the polymer chains. Attempts to synthesize the mixed diradical DR5 revealed that the tert-butyl-nitroxide moiety is not stable and undergoes a previously unobserved degradation pathway to give the corresponding α-carbonyl nitrone. At the same time, diradical DR6 was successfully prepared by using the palladium-catalyzed reaction of 2,7-dibromonaphthalene with a (nitronyl nitroxide-2-ide)(triphenylphosphine)gold complex. Magnetic susceptibility studies proved that the diradical DR6 has the triplet ground state with the energy gap ΔEST = ∼24 and ∼10–18 K in frozen (glassy) solution and solid state, respectively. Surprisingly, naphthalene-2,7-diyl is comparable as a ferromagnetic coupler with m-phenylene, which provides the singlet-triplet energy gap of value ΔEST = ∼46 K.
{"title":"Synthesis and Characterization of Free and Coordinated Nitroxide and Nitronyl Nitroxide Diradicals with a 2,7-Naphthalene Coupling Unit","authors":"Mikhail Zlokazov,Igor Zayakin,Galina Romanenko,Artem Bogomyakov,Kristina Smirnova,Konstantin Zaitsev,Matvey Fedin,Andrey Starikov,Pavel Shangin,Mikhail Syroeshkin,Darina Nasyrova,Evgeny Tretyakov","doi":"10.1021/acs.inorgchem.5c05421","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05421","url":null,"abstract":"A quantum-chemical investigation of nitroxide and nitronyl nitroxide diradicals with a 2,7-naphthalene coupling unit (bis-tert-butylnitroxide DR4, bis-nitronyl nitroxide DR6, and mixed tert-butylnitroxide/nitronyl nitroxide DR5) was carried out to predict conformation-dependent values of the intramolecular interactions. The coupling constants J are positive for symmetrical diradicals with tert-butyl-nitroxide or nitronyl nitroxide moieties (B3LYP/Def2-TZVPP: ∼440 and 60 K, respectively, for the most stable conformations), but it is negative for the mixed DR5 (∼−160 K). The triplet diradical DR4 was allowed to react with Mn(hfac)2 to give a polymer complex [Mn(hfac)2(DR4)]n exhibiting non-linear field dependencies of magnetization at low temperatures due to short-range ordering within the polymer chains. Attempts to synthesize the mixed diradical DR5 revealed that the tert-butyl-nitroxide moiety is not stable and undergoes a previously unobserved degradation pathway to give the corresponding α-carbonyl nitrone. At the same time, diradical DR6 was successfully prepared by using the palladium-catalyzed reaction of 2,7-dibromonaphthalene with a (nitronyl nitroxide-2-ide)(triphenylphosphine)gold complex. Magnetic susceptibility studies proved that the diradical DR6 has the triplet ground state with the energy gap ΔEST = ∼24 and ∼10–18 K in frozen (glassy) solution and solid state, respectively. Surprisingly, naphthalene-2,7-diyl is comparable as a ferromagnetic coupler with m-phenylene, which provides the singlet-triplet energy gap of value ΔEST = ∼46 K.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16Epub Date: 2026-02-27DOI: 10.1021/acs.inorgchem.6c00397
Chong Zhao, Shu Zhang, Chuanhao Li, Pan Li, Yixin Tang, Keyan Linghu, Jingwen Tang, Xue Li, Lei Tang
Although fullerenes are well-recognized for their exceptional radical-quenching abilities, the molecular-level mechanisms governing their interactions with free radicals remain unclear. Herein, the interactions between C60/C70 and 16 representative radicals were systematically investigated using density functional theory (DFT). The calculated binding energies (-10.21 to -51.26 kcal·mol-1) indicate strong and thermodynamically favorable radical-fullerene associations. Frontier orbital and spin-density analyses reveal that fullerenes act as electron acceptors, facilitating electron transfer from radicals and stabilizing their electronic states. Ab initio molecular dynamics (AIMD) simulations of five typical radicals (•OH, •OOH, CH3OO•, Ph3C•, and DPPH) further uncover time-resolved quenching behavior, where spin populations at radical sites rapidly decrease to nearly zero, confirming single-electron transfer as the dominant quenching pathway. Mayer bond-order analysis shows the transient formation of weak covalent bonds enabling reversible radical capture. Complementary electron paramagnetic resonance (EPR) spin-trapping experiments validate these theoretical findings, demonstrating that C60 effectively quenches hydroxyl radicals generated from H2O2 photolysis. Moreover, transition-state calculations reveal that C60 catalytically promotes H2O2 decomposition by reducing the reaction barrier while maintaining structural integrity. These combined results establish a dual-function mechanism of electron-transfer-driven radical quenching and catalytic ROS decomposition, providing a theoretical foundation for designing fullerene-based antioxidant materials.
{"title":"Study on the Quenching Mechanism of Radicals by Fullerenes (C<sub>60</sub> and C<sub>70</sub>).","authors":"Chong Zhao, Shu Zhang, Chuanhao Li, Pan Li, Yixin Tang, Keyan Linghu, Jingwen Tang, Xue Li, Lei Tang","doi":"10.1021/acs.inorgchem.6c00397","DOIUrl":"10.1021/acs.inorgchem.6c00397","url":null,"abstract":"<p><p>Although fullerenes are well-recognized for their exceptional radical-quenching abilities, the molecular-level mechanisms governing their interactions with free radicals remain unclear. Herein, the interactions between C<sub>60</sub>/C<sub>70</sub> and 16 representative radicals were systematically investigated using density functional theory (DFT). The calculated binding energies (-10.21 to -51.26 kcal·mol<sup>-1</sup>) indicate strong and thermodynamically favorable radical-fullerene associations. Frontier orbital and spin-density analyses reveal that fullerenes act as electron acceptors, facilitating electron transfer from radicals and stabilizing their electronic states. Ab initio molecular dynamics (AIMD) simulations of five typical radicals (<sup>•</sup>OH, <sup>•</sup>OOH, CH<sub>3</sub>OO<sup>•</sup>, Ph<sub>3</sub>C<sup>•</sup>, and DPPH) further uncover time-resolved quenching behavior, where spin populations at radical sites rapidly decrease to nearly zero, confirming single-electron transfer as the dominant quenching pathway. Mayer bond-order analysis shows the transient formation of weak covalent bonds enabling reversible radical capture. Complementary electron paramagnetic resonance (EPR) spin-trapping experiments validate these theoretical findings, demonstrating that C<sub>60</sub> effectively quenches hydroxyl radicals generated from H<sub>2</sub>O<sub>2</sub> photolysis. Moreover, transition-state calculations reveal that C<sub>60</sub> catalytically promotes H<sub>2</sub>O<sub>2</sub> decomposition by reducing the reaction barrier while maintaining structural integrity. These combined results establish a dual-function mechanism of electron-transfer-driven radical quenching and catalytic ROS decomposition, providing a theoretical foundation for designing fullerene-based antioxidant materials.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"5839-5849"},"PeriodicalIF":4.7,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147315827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ce-based polar materials are promising NLO candidates due to their unique electronic configuration of [Xe] 4f15d16s2 and diverse coordination modes. Ce4+ compounds are highly desired candidates for advanced nonlinear optical materials, yet the development of trivalent cerium-based NLO materials exhibiting a high second-harmonic-generation (SHG) response (above 3.0 × KDP) remains a great challenge. Herein, a new cerium iodate, Ce2(IO3)6(H2O), crystallized in the polar space group Pn (No. 7), was discovered by introducing rare-earth cations into iodates with a hydrothermal method, where corner-shared distorted [CeO9] polyhedra and [IO3]- groups alternately connect to assemble a three-dimensional (3D) framework. Optical studies showed that Ce2(IO3)6(H2O) exhibits strong SHG intensities (3 × KDP), a large band gap of 2.83 eV in the trivalent Ce-based NLO materials, indicating its potential application in frequency conversion. First-principles simulations of Ce2(IO3)6(H2O) were conducted to investigate the molecular structure and optical properties. First-principles calculations, informed by structural analysis, indicate that the two kinds of polarizable cerium-centered polyhedra ([Ce(1)O9] and [Ce(2)O8(H2O)]) constitute the primary contribution to the SHG coefficients.
{"title":"A Polar Cerium Iodate Ce2(IO3)6(H2O) with a Strong Second-Harmonic Generation Response in Trivalent Ce-Based Materials.","authors":"Jiahang Liu,Miao Zhang,Shizheng Li,Ziyang Wang,Yang Zhao,Nianrui Qu,Weiwei Cao,Jianmin Gu,Tianhui Wu","doi":"10.1021/acs.inorgchem.5c05490","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05490","url":null,"abstract":"Ce-based polar materials are promising NLO candidates due to their unique electronic configuration of [Xe] 4f15d16s2 and diverse coordination modes. Ce4+ compounds are highly desired candidates for advanced nonlinear optical materials, yet the development of trivalent cerium-based NLO materials exhibiting a high second-harmonic-generation (SHG) response (above 3.0 × KDP) remains a great challenge. Herein, a new cerium iodate, Ce2(IO3)6(H2O), crystallized in the polar space group Pn (No. 7), was discovered by introducing rare-earth cations into iodates with a hydrothermal method, where corner-shared distorted [CeO9] polyhedra and [IO3]- groups alternately connect to assemble a three-dimensional (3D) framework. Optical studies showed that Ce2(IO3)6(H2O) exhibits strong SHG intensities (3 × KDP), a large band gap of 2.83 eV in the trivalent Ce-based NLO materials, indicating its potential application in frequency conversion. First-principles simulations of Ce2(IO3)6(H2O) were conducted to investigate the molecular structure and optical properties. First-principles calculations, informed by structural analysis, indicate that the two kinds of polarizable cerium-centered polyhedra ([Ce(1)O9] and [Ce(2)O8(H2O)]) constitute the primary contribution to the SHG coefficients.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elucidating proton transfer dynamics in water represents one of the most challenging problems in water splitting reactions due to the presence of multiple proton donors, which complicates the overall reaction kinetics. This study examines the impact of buffer pKa and its concentration on catalytic performance for hydrogen evolution catalyzed by a CoIII complex (1). The results demonstrate that buffer increases the catalytic rate of the hydrogen evolution reaction. This enhanced activity is supported by the number of buffer acids possessing varying pKa values, with 2-(N-morpholino)ethanesulfonic acid yielding the maximum catalytic current. A linear free energy relationship, a characteristic of a Brønsted-type mechanism, is observed between the buffer’s pKa and catalytic rate constants. This substantiates that the rate-limiting step is controlled by the proton delivery mediated by the buffer acids. Moreover, the observed inhibition in catalytic activity at a higher concentration of buffer reveals the possible binding interaction between buffer and the cobalt center, thereby impeding substrate access. These findings underscore the critical role of buffer identity and its concentration in optimizing the proton-dependent catalytic reactions in water.
{"title":"Buffer-Induced Electrocatalytic Hydrogen Evolution by a Cobalt Pentadentate Complex in Water","authors":"Pankaj Kumar, Santanu Pattanayak, Anagha Raghavendrachar Bidarahalli, Munmun Ghosh","doi":"10.1021/acs.inorgchem.5c05524","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05524","url":null,"abstract":"Elucidating proton transfer dynamics in water represents one of the most challenging problems in water splitting reactions due to the presence of multiple proton donors, which complicates the overall reaction kinetics. This study examines the impact of buffer p<i>K</i><sub>a</sub> and its concentration on catalytic performance for hydrogen evolution catalyzed by a Co<sup>III</sup> complex (<b>1</b>). The results demonstrate that buffer increases the catalytic rate of the hydrogen evolution reaction. This enhanced activity is supported by the number of buffer acids possessing varying p<i>K</i><sub>a</sub> values, with 2-(<i>N</i>-morpholino)ethanesulfonic acid yielding the maximum catalytic current. A linear free energy relationship, a characteristic of a Brønsted-type mechanism, is observed between the buffer’s p<i>K</i><sub>a</sub> and catalytic rate constants. This substantiates that the rate-limiting step is controlled by the proton delivery mediated by the buffer acids. Moreover, the observed inhibition in catalytic activity at a higher concentration of buffer reveals the possible binding interaction between buffer and the cobalt center, thereby impeding substrate access. These findings underscore the critical role of buffer identity and its concentration in optimizing the proton-dependent catalytic reactions in water.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single-ion magnets, particularly low-coordinate Co(II) complexes, are promising for high-density data storage; however, achieving large effective energy barriers while retaining strong magnetic anisotropy remains an unresolved challenge. In this work, we systematically extracted three-coordinate Co(II) complexes from reported X-ray crystal structures and subsequently expanded this set to 1053 complexes, thereby capturing a broad chemical diversity that spans homoleptic {CoX3} species (X = C, N, O, S) and heteroleptic motifs such as {CoX2Y} and {CoCClX} (X, Y = C, N, O, S, Cl, Br, I). The D values in this data set range from +95 to -222 cm-1, with E/D ratios from 0 to 0.32, capturing diverse magnetic behavior. We have developed a machine learning (ML) model using geometric parameters such as bond lengths, angles, and deviations from ideal C3V geometry, etc. that predicts D, E/D, and g-factors with over 95% accuracy, with a mean absolute error of ∼12 cm-1 and aligns well with both CASSCF results and available experimental data. Remarkably, our models also uncovered over 40 new Co(II) complexes with large negative D values (>180 cm-1) and low E/D ratios (0.01-0.07), demonstrating the capability of the ML-driven approach to accelerate the discovery of next-generation ambiently stable SIMs.
{"title":"Uncovering Giant Magnetic Anisotropy in Co(II) Single-Ion Magnets via Combined Ab Initio and Machine-Learning Approaches.","authors":"Rajanikanta Rana,Abinash Swain,Garima Bangar,Gopalan Rajaraman","doi":"10.1021/acs.inorgchem.6c01031","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01031","url":null,"abstract":"Single-ion magnets, particularly low-coordinate Co(II) complexes, are promising for high-density data storage; however, achieving large effective energy barriers while retaining strong magnetic anisotropy remains an unresolved challenge. In this work, we systematically extracted three-coordinate Co(II) complexes from reported X-ray crystal structures and subsequently expanded this set to 1053 complexes, thereby capturing a broad chemical diversity that spans homoleptic {CoX3} species (X = C, N, O, S) and heteroleptic motifs such as {CoX2Y} and {CoCClX} (X, Y = C, N, O, S, Cl, Br, I). The D values in this data set range from +95 to -222 cm-1, with E/D ratios from 0 to 0.32, capturing diverse magnetic behavior. We have developed a machine learning (ML) model using geometric parameters such as bond lengths, angles, and deviations from ideal C3V geometry, etc. that predicts D, E/D, and g-factors with over 95% accuracy, with a mean absolute error of ∼12 cm-1 and aligns well with both CASSCF results and available experimental data. Remarkably, our models also uncovered over 40 new Co(II) complexes with large negative D values (>180 cm-1) and low E/D ratios (0.01-0.07), demonstrating the capability of the ML-driven approach to accelerate the discovery of next-generation ambiently stable SIMs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15DOI: 10.1021/acs.inorgchem.6c00707
Jin-Wang Liu,Zhe-Kun Xu,Tian Gan,Zhong-Xia Wang
Organic-inorganic hybrid ABX3-type ferroelectric materials with their structural versatility hold broad application prospects in optoelectronics, data storage, sensing, and other advanced fields. Despite chemical strategies targeting organic motifs that have proven effective for the rational design of novel hybrid molecular ferroelectrics, studies on halogen substitution receiving dual regulation of structure and symmetry in an edge-shared ABX3 hybrid ferroelectrics remain scarce. Herein, we synthesized a new one-dimensional ABX3 hybrid ferroelectric DMEIM-CdCl3 (DMEIM = N-(iodomethyl)-N,N-dimethylethylamine) by employing a halogen substitution strategy. This approach precisely tuned the crystal space group of the parent compound (centrosymmetric Pbca) to the ferroelectric Cc space group. Structurally, DMEIM-CdCl3 features one-dimensional [CdCl5]-n pyramidal chains composed of edge-shared CdCl5 hexahedra, deviating from the conventional ABX3 framework built from face- or corner-sharing polyhedra. DMEIM-CdCl3 undergoes a characteristic ferroelectric phase transition above room temperature (Tc = 379 K) with an Aizu notation of 2/mFm. This work offers insights into expanding the family of hybrid ferroelectric materials through rational chemical design.
{"title":"Halogen Substitution Dual Regulation of Structure and Symmetry in an Edge-Shared ABX3 Hybrid Ferroelectric.","authors":"Jin-Wang Liu,Zhe-Kun Xu,Tian Gan,Zhong-Xia Wang","doi":"10.1021/acs.inorgchem.6c00707","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00707","url":null,"abstract":"Organic-inorganic hybrid ABX3-type ferroelectric materials with their structural versatility hold broad application prospects in optoelectronics, data storage, sensing, and other advanced fields. Despite chemical strategies targeting organic motifs that have proven effective for the rational design of novel hybrid molecular ferroelectrics, studies on halogen substitution receiving dual regulation of structure and symmetry in an edge-shared ABX3 hybrid ferroelectrics remain scarce. Herein, we synthesized a new one-dimensional ABX3 hybrid ferroelectric DMEIM-CdCl3 (DMEIM = N-(iodomethyl)-N,N-dimethylethylamine) by employing a halogen substitution strategy. This approach precisely tuned the crystal space group of the parent compound (centrosymmetric Pbca) to the ferroelectric Cc space group. Structurally, DMEIM-CdCl3 features one-dimensional [CdCl5]-n pyramidal chains composed of edge-shared CdCl5 hexahedra, deviating from the conventional ABX3 framework built from face- or corner-sharing polyhedra. DMEIM-CdCl3 undergoes a characteristic ferroelectric phase transition above room temperature (Tc = 379 K) with an Aizu notation of 2/mFm. This work offers insights into expanding the family of hybrid ferroelectric materials through rational chemical design.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wide-bandgap molecular ferroelectric semiconductors are emerging as critical candidates for next-generation multifunctional optoelectronics, yet integrating robust ferroelectricity with a wide optical bandgap remains a formidable challenge. Herein, we report a zero-dimensional organic–inorganic hybrid ferroelectric semiconductor, [FMeQ]2ZnI4 (FMeQ = N-fluoromethyl-quinuclidine), constructed via a targeted cation fluorination strategy. This compound crystallizes in the polar orthorhombic space group Pna21 and exhibits a wide indirect bandgap of approximately 3.65 eV, comparable to traditional inorganic semiconductors like GaN. Remarkably, [FMeQ]2ZnI4 undergoes two sequential reversible order–disorder phase transitions at 306 and 336 K, endowing the material with a unique two-step switchable second harmonic generation (SHG) response over a wide temperature range. Electronic structure analysis reveals an effective decoupling mechanism where the inorganic [ZnI4]2– anion dominates the wide bandgap, while the dynamic organic cation dictates the ferroelectricity. This discovery provides an alternative approach to explore wide-bandgap molecular ferroelectrics, especially ferroelectric semiconductors with high-performance multistate optical switching capabilities.
宽带隙分子铁电半导体正成为下一代多功能光电子学的关键候选者，然而将强大的铁电性与宽光带隙集成仍然是一个艰巨的挑战。在此，我们报道了一种零维有机-无机杂化铁电半导体，[FMeQ]2ZnI4 （FMeQ = n -氟甲基-喹啉），通过靶向阳离子氟化策略构建。该化合物在极性正交空间群Pna21中结晶，具有约3.65 eV的宽间接带隙，可与GaN等传统无机半导体相媲美。值得注意的是，[FMeQ]2ZnI4在306 K和336 K下经历了两次连续可逆的有序-无序相变，使材料在宽温度范围内具有独特的两步可切换二次谐波产生（SHG）响应。电子结构分析揭示了一种有效的解耦机制，其中无机[ZnI4]2 -阴离子主导宽带隙，而动态有机阳离子支配铁电性。这一发现为探索宽带隙分子铁电体，特别是具有高性能多态光开关能力的铁电半导体提供了另一种方法。
{"title":"A Wide-Bandgap Molecular Ferroelectric Semiconductor with a Two-Step Wide-Temperature Second Harmonic Generation Response: [FMeQ]2ZnI4","authors":"Wen-He Zhong, Cheng-Fang Zhang, Rui-Si Yu, Lin-Na Tian, Zheng-Xuan Ni, Jia-Jia Zhao, Li-Zhuang Chen","doi":"10.1021/acs.inorgchem.6c00486","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00486","url":null,"abstract":"Wide-bandgap molecular ferroelectric semiconductors are emerging as critical candidates for next-generation multifunctional optoelectronics, yet integrating robust ferroelectricity with a wide optical bandgap remains a formidable challenge. Herein, we report a zero-dimensional organic–inorganic hybrid ferroelectric semiconductor, [FMeQ]<sub>2</sub>ZnI<sub>4</sub> (FMeQ = <i>N</i>-fluoromethyl-quinuclidine), constructed via a targeted cation fluorination strategy. This compound crystallizes in the polar orthorhombic space group <i>Pna</i>2<sub>1</sub> and exhibits a wide indirect bandgap of approximately 3.65 eV, comparable to traditional inorganic semiconductors like GaN. Remarkably, [FMeQ]<sub>2</sub>ZnI<sub>4</sub> undergoes two sequential reversible order–disorder phase transitions at 306 and 336 K, endowing the material with a unique two-step switchable second harmonic generation (SHG) response over a wide temperature range. Electronic structure analysis reveals an effective decoupling mechanism where the inorganic [ZnI<sub>4</sub>]<sup>2–</sup> anion dominates the wide bandgap, while the dynamic organic cation dictates the ferroelectricity. This discovery provides an alternative approach to explore wide-bandgap molecular ferroelectrics, especially ferroelectric semiconductors with high-performance multistate optical switching capabilities.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"212 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147454665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-14DOI: 10.1021/acs.inorgchem.5c05201
Deepika Mohapatra, Pratikshya Das Pattanayak, Werner Kaminsky, Maddalena Paolillo, Gabriella Tito, Giarita Ferraro, Antonello Merlino, Rupam Dinda
Three new water-stable aqueous dioxidovanadium(V) complexes, [(VVO2L1–3)M(H2O)n] (1–3), incorporating hydrazone ligands with different alkali metals (Na+/K+) as counterions were synthesized and characterized by various physicochemical approaches, including single-crystal X-ray diffraction (SCXRD). Time-dependent spectroscopic/spectrometric techniques were used to determine their aqueous-phase stabilities. Blood compatibility studies were employed to investigate their efficacy and stability with human red blood cells. Lipophilicity and calf thymus (CT)–DNA interaction of 1–3 were investigated using conventional techniques. High-resolution molecular structures of the adduct formed between 1 and hen egg white lysozyme (HEWL) were determined by SCXRD. The structural analysis reveals that the compound self-assembles within protein crystals, forming a dimeric structure that non-covalently interacts with the protein surface. The binding of 1 to HEWL was also evaluated through different spectroscopic methods. Fluorescence data indicate that 1 can also bind the physiologically relevant protein human serum albumin at pH 7.4. Furthermore, the cytotoxicity of 1–3 was evaluated against the lung (A549) and human breast adenocarcinoma (MCF-7) cancer cell lines, as well as an human embryonic kidney cell line (HEK-293) noncancerous cell line. 1 (IC50 value of 9.2 ± 0.1 μM) is more effective than the other two complexes. It induces cell death via apoptosis.
{"title":"Binding of Aqueous-Stable, Lipophilic, Hemocompatible Anticancer VVO2 Metallodrugs with Biological Molecules: X-ray Structures of the Adduct of the VV–hydrazonato Complex with Hen Egg White Lysozyme","authors":"Deepika Mohapatra, Pratikshya Das Pattanayak, Werner Kaminsky, Maddalena Paolillo, Gabriella Tito, Giarita Ferraro, Antonello Merlino, Rupam Dinda","doi":"10.1021/acs.inorgchem.5c05201","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05201","url":null,"abstract":"Three new water-stable aqueous dioxidovanadium(V) complexes, [(V<sup>V</sup>O<sub>2</sub>L<sup>1–3</sup>)M(H<sub>2</sub>O)<sub>n</sub>] (<b>1</b>–<b>3</b>), incorporating hydrazone ligands with different alkali metals (Na<sup>+</sup>/K<sup>+</sup>) as counterions were synthesized and characterized by various physicochemical approaches, including single-crystal X-ray diffraction (SCXRD). Time-dependent spectroscopic/spectrometric techniques were used to determine their aqueous-phase stabilities. Blood compatibility studies were employed to investigate their efficacy and stability with human red blood cells. Lipophilicity and calf thymus (CT)–DNA interaction of <b>1</b>–<b>3</b> were investigated using conventional techniques. High-resolution molecular structures of the adduct formed between <b>1</b> and hen egg white lysozyme (HEWL) were determined by SCXRD. The structural analysis reveals that the compound self-assembles within protein crystals, forming a dimeric structure that non-covalently interacts with the protein surface. The binding of <b>1</b> to HEWL was also evaluated through different spectroscopic methods. Fluorescence data indicate that <b>1</b> can also bind the physiologically relevant protein human serum albumin at pH 7.4. Furthermore, the cytotoxicity of <b>1</b>–<b>3</b> was evaluated against the lung (A549) and human breast adenocarcinoma (MCF-7) cancer cell lines, as well as an human embryonic kidney cell line (HEK-293) noncancerous cell line. <b>1</b> (IC<sub>50</sub> value of 9.2 ± 0.1 μM) is more effective than the other two complexes. It induces cell death via apoptosis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"212 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147447855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chiral organic-inorganic hybrid metal halides (OIMHs) have emerged as promising materials for applications in circularly polarized luminescence (CPL), yet achieving high luminescence dissymmetry factor (glum) remains challenging. Herein, we report a pair of zero-dimensional chiral indium chloride enantiomers, (R/S-2-MPH2)[InCl4(bp2do)]2 (R/S-1; R/S-2-MP = R/S-2-methylpiperazine, bp2do = 2,2'-bipyridyl-1,1'-dioxide), which feature chiral cations and ligand-modified anionic units. The bp2do ligand adopts a noncoplanar conformation due to the steric hindrance from its oxygen atoms. The In3+ center, leveraging its high coordination affinity, binds to this ligand along with halide ions. This coordination yields the structurally asymmetric anion [InCl4(bp2do)]-. Crucially, the chiral cations induce distinct M or P-helical arrangements of these anions along the crystallographic b-axis, mediated by synergistic hydrogen-bonding and anion···π interactions. Effective chirality transfer is thereby accomplished. The study demonstrates that the bp2do ligand's incorporation is indispensable, endowing the otherwise nonemissive and CPL-inactive systems such as (R/S-2-MPH2)2[InCl6]Cl with luminescence and substantial CPL activity (|glum| ∼ 10-2). This work demonstrates the effectiveness of anion engineering strategy for achieving high-performance metal halide CPL materials and opens a new avenue in chiral optoelectronics.
{"title":"Achieving Circularly Polarized Luminescence in Chiral N,O-Ligand-Modified Indium Chlorides.","authors":"Xin-Ping Guo,Hao-Wei Lin,Abdusalam Ablez,Sheng-Mao Zhang,Jia-Hua Luo,Guo-Yang Chen,Yu-Wei Ren,Ke-Zhao Du,Xiao-Ying Huang","doi":"10.1021/acs.inorgchem.6c00179","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00179","url":null,"abstract":"Chiral organic-inorganic hybrid metal halides (OIMHs) have emerged as promising materials for applications in circularly polarized luminescence (CPL), yet achieving high luminescence dissymmetry factor (glum) remains challenging. Herein, we report a pair of zero-dimensional chiral indium chloride enantiomers, (R/S-2-MPH2)[InCl4(bp2do)]2 (R/S-1; R/S-2-MP = R/S-2-methylpiperazine, bp2do = 2,2'-bipyridyl-1,1'-dioxide), which feature chiral cations and ligand-modified anionic units. The bp2do ligand adopts a noncoplanar conformation due to the steric hindrance from its oxygen atoms. The In3+ center, leveraging its high coordination affinity, binds to this ligand along with halide ions. This coordination yields the structurally asymmetric anion [InCl4(bp2do)]-. Crucially, the chiral cations induce distinct M or P-helical arrangements of these anions along the crystallographic b-axis, mediated by synergistic hydrogen-bonding and anion···π interactions. Effective chirality transfer is thereby accomplished. The study demonstrates that the bp2do ligand's incorporation is indispensable, endowing the otherwise nonemissive and CPL-inactive systems such as (R/S-2-MPH2)2[InCl6]Cl with luminescence and substantial CPL activity (|glum| ∼ 10-2). This work demonstrates the effectiveness of anion engineering strategy for achieving high-performance metal halide CPL materials and opens a new avenue in chiral optoelectronics.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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