Pub Date : 2025-12-27DOI: 10.1016/j.ica.2025.123044
Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang
Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO3)(H2O)]n (1) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm2(OH-bdc)2(H2O)10]·OH-bdc·H2O}n (2) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound 1 features a three dimensional (3D) pillared layer network containing [Tm2(NO3)2]4+ units and 2,5-dtc2− ligands. Compound 2 exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm2(bdc)2(H2O)10]2+ to uncoordinated OH-bdc2− ligands via π···π stacking interactions. The striking feature of compounds 1 and 2 is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds 1 and 2 display antiferromagnetic coupling in the solid state at room temperature.
{"title":"Near-infrared (NIR) luminescence of two Tm(III)-based dicarboxylate coordination polymers","authors":"Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang","doi":"10.1016/j.ica.2025.123044","DOIUrl":"10.1016/j.ica.2025.123044","url":null,"abstract":"<div><div>Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO<sub>3</sub>)(H<sub>2</sub>O)]<sub><em>n</em></sub> (<strong>1</strong>) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm<sub>2</sub>(OH-bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]·OH-bdc·H<sub>2</sub>O}<sub><em>n</em></sub> (<strong>2</strong>) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound <strong>1</strong> features a three dimensional (3D) pillared layer network containing [Tm<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>]<sup>4+</sup> units and 2,5-dtc<sup>2−</sup> ligands. Compound <strong>2</strong> exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm<sub>2</sub>(bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]<sup>2+</sup> to uncoordinated OH-bdc<sup>2−</sup> ligands via <em>π···π</em> stacking interactions. The striking feature of compounds <strong>1</strong> and <strong>2</strong> is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds <strong>1</strong> and <strong>2</strong> display antiferromagnetic coupling in the solid state at room temperature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123044"},"PeriodicalIF":3.2,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939886","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}
Pub Date : 2025-12-27DOI: 10.1016/j.ica.2025.123046
Nawishta Jabeen , Ali Yaqoob , Ahmad Hussain , Aseel Smerat , Mohamed A. Nassan , Nidhal Ben Khedher
DFT based simulations have been performed to investigate the structural, optoelectronics, thermodynamics and mechanical properties of double anionic structured (alkaline selenite oxo-fluoro) compounds (XSeO3F where X = Y, Sc, La and Lu), which can present their potentials for the green energy applications. The choice of metallic cationic replacements within these structures is greatly influenced their dynamics stability and the ionic character. Among these compounds, SeO3 counterpart is responsible for enhanced optical characteristics. All these compounds have presented wide indirect band gaps from 3.31 eV to 3.93 eV, followed by high values of optical properties like absorption (105 cm−1), optical conductivity (3 fs−1–5 fs−1). Moreover, no transparency is observed for the incident radiations range from 0 eV to 10 eV, which is confirmed by the values ε1(ω) > 0, and n(ω) > 1. Reflectivity remains as low as 10 % within the visible region of incident light which is followed by low loss of dissipated energy within the compounds. Lower value of zero-point energy 0.767 eV for LuSeO3F shows less vibrational frequencies indicating more stability as compared to other compounds. The convergence of heat capacity near the Dulong-Petit limit (74.9 cal/cell. K) reveals the thermal resistance showing potentials for high temperature electronics devices. Ductile nature has been confirmed for XSeO3F (X = Y, Sc, and Lu) compounds by Poisson's and Pugh's ratios, but LaSeO3F compound has demonstrated the more unique auxetic nature. These results suggest that alkaline selenite based oxo-fluoro compounds possess promising potential for next generation green technologies such as optoelectronic, tendon cells, and sustainable energy conversion devices.
{"title":"Multifunctional behavior of alkaline selenite oxo-fluoro compounds, investigated by DFT for green tech applications","authors":"Nawishta Jabeen , Ali Yaqoob , Ahmad Hussain , Aseel Smerat , Mohamed A. Nassan , Nidhal Ben Khedher","doi":"10.1016/j.ica.2025.123046","DOIUrl":"10.1016/j.ica.2025.123046","url":null,"abstract":"<div><div>DFT based simulations have been performed to investigate the structural, optoelectronics, thermodynamics and mechanical properties of double anionic structured (alkaline selenite oxo-fluoro) compounds (XSeO<sub>3</sub>F where X = Y, Sc, La and Lu), which can present their potentials for the green energy applications. The choice of metallic cationic replacements within these structures is greatly influenced their dynamics stability and the ionic character. Among these compounds, SeO<sub>3</sub> counterpart is responsible for enhanced optical characteristics. All these compounds have presented wide indirect band gaps from 3.31 eV to 3.93 eV, followed by high values of optical properties like absorption (10<sup>5</sup> cm<sup>−1</sup>), optical conductivity (3 fs<sup>−1</sup>–5 fs<sup>−1</sup>). Moreover, no transparency is observed for the incident radiations range from 0 eV to 10 eV, which is confirmed by the values ε<sub>1</sub>(ω) > 0, and n(ω) > 1. Reflectivity remains as low as 10 % within the visible region of incident light which is followed by low loss of dissipated energy within the compounds. Lower value of zero-point energy 0.767 eV for LuSeO<sub>3</sub>F shows less vibrational frequencies indicating more stability as compared to other compounds. The convergence of heat capacity near the Dulong-Petit limit (74.9 cal/cell. K) reveals the thermal resistance showing potentials for high temperature electronics devices. Ductile nature has been confirmed for XSeO<sub>3</sub>F (X = Y, Sc, and Lu) compounds by Poisson's and Pugh's ratios, but LaSeO<sub>3</sub>F compound has demonstrated the more unique auxetic nature. These results suggest that alkaline selenite based oxo-fluoro compounds possess promising potential for next generation green technologies such as optoelectronic, tendon cells, and sustainable energy conversion devices.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123046"},"PeriodicalIF":3.2,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882483","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}
A Schiff base ligand, [4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol], shortly Diformyl Amino Pyridine (DAP), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg2+ binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 108 M−1 and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe DAP was converted into a heterogeneous solid-state material, ZnAl2O4 (ZA) conjugated DAP (ZDAP), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to DAP's quenching, ZDAP exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg2+ binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (ZDAP), causing a bathochromic shift in emission. The observed fluorescence quenching of DAP upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, ZDAP demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.
希夫碱配体[4-甲基-2,6-双(（E)-（（2-（吡啶-2-基）乙基）亚氨基）甲基）苯酚]，简称二甲酰氨基吡啶（DAP），是一种均相探针，并通过不同的光谱技术进行了表征。它的荧光被Hg2+结合猝灭，这一过程受多种非辐射途径的控制，包括光诱导电子转移（PET）和重原子效应，Stern-Volmer常数为8.83 × 108 M−1，检测限为1.35 μM。为了解决可重复使用性和样品基质分离等限制，通过将亚胺配体锚定在ZA尖晶石上，将均相探针DAP转化为非均相固态材料ZnAl2O4 （ZA）共轭DAP （ZDAP）。令人惊讶的是，这种改变从根本上改变了感知机制。与DAP的猝灭相反，ZDAP通过聚集诱导发射（AIE）表现出“开启”反应，其中Hg2+结合限制了分子内运动并增强了荧光。该方法的检出限为1.01 nM。ICP-MS分析证实，使用该传感器处理后，汞几乎完全去除，汞去除率高达98.46%。这两个系统的传感机制已经通过DFT计算和实验技术，如斯特恩-沃尔默分析和时间分辨荧光光谱得到证实。理论计算结果与实验结果非常吻合，能隙从2.28 eV （ZA）减小到2.15 eV (ZDAP)，引起发射的深色偏移。所观察到的DAP锚定在ZA上的荧光猝灭是由强配-金属相互作用、电荷转移诱导的非辐射衰变、结构硬化和表面缺陷捕获引起的，与实验（2.93 eV）带隙一致。至关重要的是，ZDAP具有出色的可重复使用性，在螯合剂再生后至少可以保持其传感效率和结构完整性5个循环。这项工作展示了单个希夫基平台如何设计为提供两种互补的传感模式，为汞检测和去除提供敏感，选择性和可持续的解决方案。
{"title":"Concurrent detection and removal of Hg2+ from potable water using ZnAl2O4 modified end off Schiff base ligand: Experimental and theoretical investigation","authors":"Sneha Biswas , Jaydeep Adhikary , Rama Rathi , Sreejeeb Ganguly , Ennio Zangrando , Abhijit Kumar Das","doi":"10.1016/j.ica.2025.123045","DOIUrl":"10.1016/j.ica.2025.123045","url":null,"abstract":"<div><div>A Schiff base ligand, <em>[4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol]</em>, shortly Diformyl Amino Pyridine (<strong>DAP</strong>), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg<sup>2+</sup> binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 10<sup>8</sup> M<sup>−1</sup> and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe <strong>DAP</strong> was converted into a heterogeneous solid-state material, ZnAl<sub>2</sub>O<sub>4</sub> (<strong>ZA</strong>) conjugated <strong>DAP</strong> (<strong>ZDAP</strong>), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to <strong>DAP</strong>'s quenching, <strong>ZDAP</strong> exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg<sup>2+</sup> binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (<strong>ZDAP</strong>), causing a bathochromic shift in emission. The observed fluorescence quenching of <strong>DAP</strong> upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, <strong>ZDAP</strong> demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123045"},"PeriodicalIF":3.2,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839361","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}
Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg2+, Cu2+, Zn2+, Ag+, Al3+, Pb2+,Fe3+,Cd2+, Au3+, Pd2+, Ni2+, Cr3+, Ga3+, Zr4+ as well as anions including I−, F− and CN−. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.
{"title":"Thiophene based chemosensors: a comprehensive review on synthesis and detection of cations and anions","authors":"Zuverya Zareen , Aram Rahman , Anzar Jahan , Salahuddin Syed , Mohammad Arifuddin","doi":"10.1016/j.ica.2025.123042","DOIUrl":"10.1016/j.ica.2025.123042","url":null,"abstract":"<div><div>Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ag<sup>+</sup>, Al<sup>3+</sup>, Pb<sup>2+</sup>,Fe<sup>3+</sup>,Cd<sup>2+</sup>, Au<sup>3+</sup>, Pd<sup>2+</sup>, Ni<sup>2+</sup>, Cr<sup>3+</sup>, Ga<sup>3+</sup>, Zr<sup>4+</sup> as well as anions including I<sup>−</sup>, F<sup>−</sup> and CN<sup>−</sup>. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123042"},"PeriodicalIF":3.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882482","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}
Pub Date : 2025-12-18DOI: 10.1016/j.ica.2025.123043
Madeline R. Handel , Samuel J. Lenze , Lucas G. Fuller , Theodore A. Corcovilos , Michael J. van Stipdonk
Interest in Main Group metal hydrides remains high because of their potential use as hydrogen storage materials and as green catalysts. However, the high reactivity of metal hydrides along with the solvent effects and complex equilibria of condensed phase studies makes study of their intrinsic chemistry a challenge. In principle, the challenge can be overcome by using ion preparation methods such as collision-induced dissociation to synthesize species within the relatively inert gas-phase environment of ion-trapping mass spectrometers. In this study, preparative (ion trap) tandem mass spectrometry (PTMSn) was used to generate a series of binary, gas-phase metal hydride cations. In particular, we show that the relatively inert environment of a quadrupole ion trap permits (a) the synthesis of discrete, group II metal hydride cations, [MetH]+ (Met = Ca, Sr, Ba) and (b) allows for monitoring of intrinsic reactions with neutral species such as H2O and CH2Cl2. When exposed to H2O, the [MetH]+ cations undergo a hydrolysis reaction to form the respective cationic, metal hydroxides. When allowed to react with CH2Cl2, two reaction pathways are observed, one leading to formation of [Met(CHCl2)]+ (with elimination of neutral H2) and the other producing [MetCl]+ (by elimination of CH3Cl). The reactions to generate the [MetH]+ cations, and the ion-molecule reactions with H2O and CH2Cl2, were modeled using density functional theory (DFT) and 2nd – order Moller-Plesset (MP2) calculations to provide optimized structures of reactants, intermediates, products and transition states. In general, the computed enthalpies and free energies for the reactions are in good qualitative agreement with the experimental outcomes.
由于其作为储氢材料和绿色催化剂的潜在用途，人们对主族金属氢化物的兴趣仍然很高。然而，金属氢化物的高反应活性、溶剂效应和复杂的缩合相平衡研究给其内在化学的研究带来了挑战。原则上，可以通过使用离子制备方法，如碰撞诱导解离，在离子捕获质谱仪的相对惰性气相环境中合成物种来克服这一挑战。本研究采用制备（离子阱）串联质谱法（PTMSn）生成了一系列二元气相金属氢化物阳离子。特别是，我们证明了相对惰性的四极离子阱环境允许(a)合成离散的，II族金属氢化物阳离子，[甲基]+ (Met = Ca, Sr, Ba)和(b)允许监测与中性物质如H2O和CH2Cl2的固有反应。当暴露于H2O时，[甲基]+阳离子发生水解反应，形成各自的阳离子金属氢氧化物。当允许与CH2Cl2反应时，观察到两个反应途径，一个导致形成[Met(CHCl2)]+（消除中性H2），另一个产生[MetCl]+（消除CH3Cl）。利用密度泛函理论（DFT）和二阶Moller-Plesset （MP2）计算，对生成[甲基]+阳离子的反应以及H2O和CH2Cl2的离子-分子反应进行了建模，以优化反应物、中间体、产物和过渡态的结构。总的来说，计算出的反应焓和自由能与实验结果在定性上是一致的。
{"title":"Synthesis of gas-phase, group II metal hydride cations using preparative tandem mass spectrometry","authors":"Madeline R. Handel , Samuel J. Lenze , Lucas G. Fuller , Theodore A. Corcovilos , Michael J. van Stipdonk","doi":"10.1016/j.ica.2025.123043","DOIUrl":"10.1016/j.ica.2025.123043","url":null,"abstract":"<div><div>Interest in Main Group metal hydrides remains high because of their potential use as hydrogen storage materials and as green catalysts. However, the high reactivity of metal hydrides along with the solvent effects and complex equilibria of condensed phase studies makes study of their intrinsic chemistry a challenge. In principle, the challenge can be overcome by using ion preparation methods such as collision-induced dissociation to synthesize species within the relatively inert gas-phase environment of ion-trapping mass spectrometers. In this study, preparative (ion trap) tandem mass spectrometry (PTMS<sup>n</sup>) was used to generate a series of binary, gas-phase metal hydride cations. In particular, we show that the relatively inert environment of a quadrupole ion trap permits (a) the synthesis of discrete, group II metal hydride cations, [MetH]<sup>+</sup> (Met = Ca, Sr, Ba) and (b) allows for monitoring of intrinsic reactions with neutral species such as H<sub>2</sub>O and CH<sub>2</sub>Cl<sub>2</sub>. When exposed to H<sub>2</sub>O, the [MetH]<sup>+</sup> cations undergo a hydrolysis reaction to form the respective cationic, metal hydroxides. When allowed to react with CH<sub>2</sub>Cl<sub>2</sub>, two reaction pathways are observed, one leading to formation of [Met(CHCl<sub>2</sub>)]<sup>+</sup> (with elimination of neutral H<sub>2</sub>) and the other producing [MetCl]<sup>+</sup> (by elimination of CH<sub>3</sub>Cl). The reactions to generate the [MetH]<sup>+</sup> cations, and the ion-molecule reactions with H<sub>2</sub>O and CH<sub>2</sub>Cl<sub>2</sub>, were modeled using density functional theory (DFT) and 2nd – order Moller-Plesset (MP2) calculations to provide optimized structures of reactants, intermediates, products and transition states. In general, the computed enthalpies and free energies for the reactions are in good qualitative agreement with the experimental outcomes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123043"},"PeriodicalIF":3.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837297","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}
Pub Date : 2025-12-16DOI: 10.1016/j.ica.2025.123041
Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang
Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with D- and L-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(D-val)] and Λ-[Ir(dfppy)₂(L-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(D-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by 1H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.
{"title":"Synthesis, structure and photooxidative dehydrogenation of chiral Ir(III) valine complexes based on precursor [Λ-Ir(dfppy)2(MeCN)2](PF6)","authors":"Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang","doi":"10.1016/j.ica.2025.123041","DOIUrl":"10.1016/j.ica.2025.123041","url":null,"abstract":"<div><div>Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with <em>D</em>- and <em>L</em>-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(<em>D</em>-val)] and Λ-[Ir(dfppy)₂(<em>L</em>-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(<em>D</em>-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by <sup>1</sup>H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123041"},"PeriodicalIF":3.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882485","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}
Pub Date : 2025-12-14DOI: 10.1016/j.ica.2025.123040
Barış Seçkin Arslan , Nagihan Öztürk , Mehmet Nebioğlu , İlkay Şişman
This study focuses on the synthesis of novel zinc phthalocyanines containing tetra-((6,7,8-trimethoxytetrazolo[1,5-a]quinolin-4-yl)methoxy) and tetra-((2,5,6,7-tetramethoxyquinolin-3-yl)methoxy) substituents and the investigation of their photodynamic therapy (PDT) properties. Two novel phthalonitrile derivatives bearing trimethoxytetrazolo (5a) and tetramethoxy (5b) quinoline moieties and their corresponding peripherally substituted zinc(II) phthalocyanine complexes (BIM8 and BIM9) were synthesized. The molecular structures of these compounds were verified by FT-IR, NMR, UV–Vis spectroscopy, and mass spectrometry. The photophysical, photochemical, and electrochemical properties of the zinc phthalocyanines were systematically investigated to evaluate their potential application in PDT. Compared to BIM8, BIM9 exhibited superior photochemical performance, including a high singlet oxygen quantum yield (ɸΔ = 0.89), negligible aggregation tendency, sufficient fluorescence emission for imaging purposes, and notable photostability. These results demonstrate that BIM9 is a promising photosensitizer candidate for PDT.
{"title":"Synthesis, photophysicochemical and electrochemical properties of new peripheral tetra-substituted Zn(II) phthalocyanines bearing quinoline groups","authors":"Barış Seçkin Arslan , Nagihan Öztürk , Mehmet Nebioğlu , İlkay Şişman","doi":"10.1016/j.ica.2025.123040","DOIUrl":"10.1016/j.ica.2025.123040","url":null,"abstract":"<div><div>This study focuses on the synthesis of novel zinc phthalocyanines containing tetra-((6,7,8-trimethoxytetrazolo[1,5-<em>a</em>]quinolin-4-yl)methoxy) and tetra-((2,5,6,7-tetramethoxyquinolin-3-yl)methoxy) substituents and the investigation of their photodynamic therapy (PDT) properties. Two novel phthalonitrile derivatives bearing trimethoxytetrazolo (<strong>5a</strong>) and tetramethoxy (<strong>5b</strong>) quinoline moieties and their corresponding peripherally substituted zinc(II) phthalocyanine complexes (<strong>BIM8</strong> and <strong>BIM9</strong>) were synthesized. The molecular structures of these compounds were verified by FT-IR, NMR, UV–Vis spectroscopy, and mass spectrometry. The photophysical, photochemical, and electrochemical properties of the zinc phthalocyanines were systematically investigated to evaluate their potential application in PDT. Compared to <strong>BIM8</strong>, <strong>BIM9</strong> exhibited superior photochemical performance, including a high singlet oxygen quantum yield (ɸ<sub>Δ</sub> = 0.89), negligible aggregation tendency, sufficient fluorescence emission for imaging purposes, and notable photostability. These results demonstrate that <strong>BIM9</strong> is a promising photosensitizer candidate for PDT.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123040"},"PeriodicalIF":3.2,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787879","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}
Transition metal complexes bearing redox-active ligands often exhibit multiple accessible oxidation states resulting from the electronic interplay between the metal center and the coordinated ligand framework. This study focused on the synthesis and characterization of two mononuclear copper (II) complexes incorporating redox active ligands, 3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one(LwOx) and 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (LwOx-Me), the ligands differ structurally by the substitution of hydrogen atom with a methyl group in the ligand oxime backbone, this small change affects the ability of the ligand to form intramolecular hydrogen bonds within metal complexes. Remarkably, both metal complexes display multiple redox events attributed to the combined redox-active nature of quinoneoxime-based ligands and the copper(II) center. Furthermore, both complexes were evaluated as catalysts in the oxidation of alcohols. [Cu(LwOx)2] exhibited excellent catalytic activity, whereas [Cu(LwOx-Me)2] showed negligible activity; DFT studies suggest the crucial role of intramolecular hydrogen bonding in modulating the catalytic activity of Cu(II) complexes.
{"title":"Ligand design and catalytic performance of Quinone-oxime copper complexes: role of intramolecular hydrogen bonding","authors":"Vivek Mokashi , Sourav Datta , Swapan Patra , Priyabrata Banerjee , Sunita Salunke-Gawali","doi":"10.1016/j.ica.2025.123039","DOIUrl":"10.1016/j.ica.2025.123039","url":null,"abstract":"<div><div>Transition metal complexes bearing redox-active ligands often exhibit multiple accessible oxidation states resulting from the electronic interplay between the metal center and the coordinated ligand framework. This study focused on the synthesis and characterization of two mononuclear copper (II) complexes incorporating redox active ligands, 3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one(<strong>LwOx</strong>) and 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (<strong>LwOx-Me</strong>), the ligands differ structurally by the substitution of hydrogen atom with a methyl group in the ligand oxime backbone, this small change affects the ability of the ligand to form intramolecular hydrogen bonds within metal complexes. Remarkably, both metal complexes display multiple redox events attributed to the combined redox-active nature of quinoneoxime-based ligands and the copper(II) center. Furthermore, both complexes were evaluated as catalysts in the oxidation of alcohols. <strong>[Cu(LwOx)</strong><sub><strong>2</strong></sub><strong>]</strong> exhibited excellent catalytic activity, whereas <strong>[Cu(LwOx-Me)</strong><sub><strong>2</strong></sub><strong>]</strong> showed negligible activity; DFT studies suggest the crucial role of intramolecular hydrogen bonding in modulating the catalytic activity of Cu(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123039"},"PeriodicalIF":3.2,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787876","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}
Cadmium(II) complexes with salen- and salpn-type Schiff base ligands have gained increasing attention for their structural versatility, diverse coordination geometries, and notable biological potential. This review summarizes recent advances in their synthesis, spectral and structural characterization, and bioactivity. The flexible coordination of Cd(II) and the chelating nature of Schiff bases promote the formation of di- and polynuclear architectures, often stabilized by bridging ligands. Structural insights from X-ray studies and their correlation with antimicrobial, antifungal, anticancer, and enzyme-inhibitory activities are discussed. Despite cadmium's inherent toxicity, rational ligand design has yielded complexes with enhanced bioactivity and reduced cytotoxicity. Key challenges and prospects for developing Cd(II) Schiff base complexes as therapeutic and functional materials are also highlighted.
{"title":"Synthetic strategy, structural aspects and biological applications of multinuclear cadmium complexes using salen type N2O2 donor ligands and N2O2O2′ donor compartmental ligands: A review","authors":"Puspendu Middya , Siddhartha Majhi , Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.123029","DOIUrl":"10.1016/j.ica.2025.123029","url":null,"abstract":"<div><div>Cadmium(II) complexes with salen- and salpn-type Schiff base ligands have gained increasing attention for their structural versatility, diverse coordination geometries, and notable biological potential. This review summarizes recent advances in their synthesis, spectral and structural characterization, and bioactivity. The flexible coordination of Cd(II) and the chelating nature of Schiff bases promote the formation of di- and polynuclear architectures, often stabilized by bridging ligands. Structural insights from X-ray studies and their correlation with antimicrobial, antifungal, anticancer, and enzyme-inhibitory activities are discussed. Despite cadmium's inherent toxicity, rational ligand design has yielded complexes with enhanced bioactivity and reduced cytotoxicity. Key challenges and prospects for developing Cd(II) Schiff base complexes as therapeutic and functional materials are also highlighted.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123029"},"PeriodicalIF":3.2,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837298","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}
Pub Date : 2025-12-11DOI: 10.1016/j.ica.2025.123038
Souvik Naskar, Ishita Naskar, Karan Kumar Gupta, Chung-Hsin Lu
A simple hydrothermal and calcination procedure was used to synthesize 2D‑vanadium-doped MoSe₂ nanosheets (V-MoSe₂ NSs) with good control over shape and crystallinity in this study. Se removal from the VMo structure was assessed by p-XRD, FE-SEM, EDAX, and FE-TEM. The findings demonstrate that the crystal phase and textural characteristics alter as a result of physical parameter adjustment. The V-MoSe₂ in the two-electrode system was found to have a specific capacitance of 369 F g−1, which is higher than that of the pristine MoSe₂ (P-MoSe₂) electrode. The assembled lithium-ion supercapacitor (LISC) also exhibits impressive electrochemical performance, possessing an energy density of 479 Wh kg−1 and a power density of 8.7 kW kg−1, with good cycling stability and 88 % capacitance retention after 5000 cycles. The novelty of this work lies in the rational incorporation of vanadium into the MoSe₂ lattice to engineer its electronic structure and surface properties, which effectively enhances charge storage capability and ion diffusion kinetics. The increase in the electrochemical performance of V-MoSe₂ was due to its distinctive nanosheet-like morphology, which features a high specific surface area, low charge transfer resistance, and reduced ion diffusion resistance. This study displays a practical scheme for a combination of electrodes made of the metallic element vanadium and selenide.
本研究采用简单的水热和煅烧工艺合成了形状和结晶度可控的二维掺钒MoSe₂纳米片（V-MoSe₂NSs）。采用p-XRD、FE-SEM、EDAX和FE-TEM等方法对VMo结构的Se去除率进行了评价。结果表明，物理参数的调整会改变晶体的相和织构特征。在两电极体系中，V-MoSe 2的比电容为369 F g−1，高于原始MoSe 2 （P-MoSe 2）电极。组装的锂离子超级电容器（LISC）也表现出令人印象深刻的电化学性能，其能量密度为479 Wh kg - 1，功率密度为8.7 kW kg - 1，具有良好的循环稳定性，循环5000次后电容保持率为88%。这项工作的新颖之处在于将钒合理地结合到MoSe₂晶格中，以设计其电子结构和表面性质，有效地提高了电荷存储能力和离子扩散动力学。V-MoSe₂电化学性能的提高是由于其独特的纳米片状形貌，具有高比表面积，低电荷转移电阻和降低离子扩散阻力。这项研究展示了一种实用的方案，即由金属元素钒和硒化物制成的电极组合。
{"title":"A straightforward approach for synthesizing vanadium-doped 2D MoSe2 as cathode in high-energy lithium-ion supercapacitors","authors":"Souvik Naskar, Ishita Naskar, Karan Kumar Gupta, Chung-Hsin Lu","doi":"10.1016/j.ica.2025.123038","DOIUrl":"10.1016/j.ica.2025.123038","url":null,"abstract":"<div><div>A simple hydrothermal and calcination procedure was used to synthesize 2D‑vanadium-doped MoSe₂ nanosheets (V-MoSe₂ NSs) with good control over shape and crystallinity in this study. Se removal from the V<img>Mo structure was assessed by p-XRD, FE-SEM, EDAX, and FE-TEM. The findings demonstrate that the crystal phase and textural characteristics alter as a result of physical parameter adjustment. The V-MoSe₂ in the two-electrode system was found to have a specific capacitance of 369 F g<sup>−1</sup>, which is higher than that of the pristine MoSe₂ (P-MoSe₂) electrode. The assembled lithium-ion supercapacitor (LISC) also exhibits impressive electrochemical performance, possessing an energy density of 479 Wh kg<sup>−1</sup> and a power density of 8.7 kW kg<sup>−1</sup>, with good cycling stability and 88 % capacitance retention after 5000 cycles. The novelty of this work lies in the rational incorporation of vanadium into the MoSe₂ lattice to engineer its electronic structure and surface properties, which effectively enhances charge storage capability and ion diffusion kinetics. The increase in the electrochemical performance of V-MoSe₂ was due to its distinctive nanosheet-like morphology, which features a high specific surface area, low charge transfer resistance, and reduced ion diffusion resistance. This study displays a practical scheme for a combination of electrodes made of the metallic element vanadium and selenide.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123038"},"PeriodicalIF":3.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837296","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}
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