Pub Date : 2025-12-06DOI: 10.1016/j.ica.2025.123015
Saili Vikram Lokhande , Ashis Kumar Satpati , Afsar Ali Siddiki , Rohit Singh Chauhan , Raymond J. Butcher
The study presents a comprehensive investigation into the synthesis, characterization, and evaluation of nickel thiolate complexes as potential molecular catalysts for the hydrogen evolution reaction (HER). The growing need for efficient, sustainable hydrogen production methods has led to the exploration of various catalysts, with nickel-based complexes being promising candidates due to their abundance, low cost, and favourable catalytic properties. With this impetus, two categories of nickel complexes viz mono and binuclear were synthesized. Reaction of [NiCl2(N∩N)] (N∩N = 1,10-phenanthroline, 2,2′-bipyridine) with sodium salt of 4,6-dimethylpyrimidine−2-thiolate in the presence of NaPF6 resulted in a mononuclear neutral complex of composition [Ni{L1}2(N∩N)] (L1 = SC4H(4,6-Me)2N2; N∩N = 1,10-phenanthroline 1a, 2,2′-bipyridine 1b). However, a similar reaction with dibenzyl disulfide ligand system in the presence of tBuOK base yielded a cationic binuclear moiety [Ni{L2}(N∩N)2]22+ (L2 = {O2(SC7H7)}; N∩N = 1,10-phenanthroline 2a, 2,2′-bipyridine 2b). An insertion of nascent oxygen between Ni−S bonds is quite interesting, probably a reason to stabilize an eight-membered ring having chair confirmation which is comprised of asymmetric fragments “[Ni(O2SCH2Ph)(N∩N)2]”. A mononuclear complex [Ni{L1}2(Phen)] (1a) and a dinuclear [Ni{L2}(Phen)2]2[PF6]2 (2a) have been structurally characterized by Single crystal X-ray diffraction. All the synthesized complexes have been employed as proton-reducing catalysts through electrocatalytic activity using cyclic voltammetry (CV) and chronoamperometry in an acidic medium where sulfuric acid act as proton source. In order to have better insights about the electrocatalytic behavior of the synthesized complexes, electrochemical impedance measurements (EIS) were also conducted.
{"title":"Engineering novel nickel(II) complexes: Unlocking electrocatalytic performance for efficient hydrogen evolution","authors":"Saili Vikram Lokhande , Ashis Kumar Satpati , Afsar Ali Siddiki , Rohit Singh Chauhan , Raymond J. Butcher","doi":"10.1016/j.ica.2025.123015","DOIUrl":"10.1016/j.ica.2025.123015","url":null,"abstract":"<div><div>The study presents a comprehensive investigation into the synthesis, characterization, and evaluation of nickel thiolate complexes as potential molecular catalysts for the hydrogen evolution reaction (HER). The growing need for efficient, sustainable hydrogen production methods has led to the exploration of various catalysts, with nickel-based complexes being promising candidates due to their abundance, low cost, and favourable catalytic properties. With this impetus, two categories of nickel complexes <em>viz</em> mono and binuclear were synthesized. Reaction of [NiCl<sub>2</sub>(N∩N)] (N∩<em>N</em> = 1,10-phenanthroline, 2,2′-bipyridine) with sodium salt of 4,6-dimethylpyrimidine−2-thiolate in the presence of NaPF<sub>6</sub> resulted in a mononuclear neutral complex of composition [Ni{L1}<sub>2</sub>(N∩N)] (L1 = SC<sub>4</sub>H(4,6-Me)<sub>2</sub>N<sub>2</sub>; N∩N = 1,10-phenanthroline <strong>1a</strong>, 2,2′-bipyridine <strong>1b</strong>). However, a similar reaction with dibenzyl disulfide ligand system in the presence of <sup>t</sup>BuOK base yielded a cationic binuclear moiety [Ni{L2}(N∩N)<sub>2</sub>]<sub>2</sub><sup>2+</sup> (L<sub>2</sub> = {O<sub>2</sub>(SC<sub>7</sub>H<sub>7</sub>)}; N∩N = 1,10-phenanthroline <strong>2a</strong>, 2,2′-bipyridine <strong>2b</strong>). An insertion of nascent oxygen between Ni−S bonds is quite interesting, probably a reason to stabilize an eight-membered ring having chair confirmation which is comprised of asymmetric fragments “[Ni(O<sub>2</sub>SCH<sub>2</sub>Ph)(N∩N)<sub>2</sub>]”. A mononuclear complex [Ni{L1}<sub>2</sub>(Phen)] (<strong>1a</strong>) and a dinuclear [Ni{L2}(Phen)<sub>2</sub>]<sub>2</sub>[PF<sub>6</sub>]<sub>2</sub> (<strong>2a</strong>) have been structurally characterized by Single crystal X-ray diffraction. All the synthesized complexes have been employed as proton-reducing catalysts through electrocatalytic activity using cyclic voltammetry (CV) and chronoamperometry in an acidic medium where sulfuric acid act as proton source. In order to have better insights about the electrocatalytic behavior of the synthesized complexes, electrochemical impedance measurements (EIS) were also conducted.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123015"},"PeriodicalIF":3.2,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734221","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 : 2025-12-04DOI: 10.1016/j.ica.2025.123023
Yingjie Zhang , Timothy A. Ablott , Tao Wei , Sophie Fletcher , Mohamed R. Rafiuddin
Uranium oxide hydrate frameworks (UOHFs) with lanthanide ions are fundamentally important to uranium crystal chemistry. Earlier works revealed a possible phase transition from high symmetry space groups (monoclinic or orthorhombic) for UOHF-Ln (Ln = Pr → Dy) to a low symmetry space group (triclinic) for UOHF-Ln (Ln = Er → Lu). However, given holmium lies close to this apparent transition boundary, whether these frameworks with holmium adopt a high or low symmetry structure is unknown. Herein, we report the synthesis of Ho2(H2O)4(OH)2[(UO2)10UO13(OH)4]·H2O (UOHF-Ho) and subsequent structural and spectroscopic investigations. Synchrotron single crystal X-ray diffraction confirmed that UOHF-Ho crystallises in the orthorhombic C2221 space group, further validated by electron diffraction with transmission electron microscopy. The framework structure is constructed with β-U3O8 type layers linked by double uranyl units in pentagonal bipyramids, with disordered Ho3+ ions lying inside the channels. While Raman spectroscopy revealed the U6+ dominant vibrational modes, diffuse reflectance spectroscopy unearthed characteristic absorption bands for both U6+ and Ho3+ ions. This work uncovers the exact phase transition for UOHF-Ln series and has implications to the uranium structural chemistry and possible spent nuclear fuel alterations.
{"title":"Towards uranium oxide hydrate framework with holmium(III) ions: High or low symmetry structure?","authors":"Yingjie Zhang , Timothy A. Ablott , Tao Wei , Sophie Fletcher , Mohamed R. Rafiuddin","doi":"10.1016/j.ica.2025.123023","DOIUrl":"10.1016/j.ica.2025.123023","url":null,"abstract":"<div><div>Uranium oxide hydrate frameworks (UOHFs) with lanthanide ions are fundamentally important to uranium crystal chemistry. Earlier works revealed a possible phase transition from high symmetry space groups (monoclinic or orthorhombic) for UOHF-Ln (Ln = Pr → Dy) to a low symmetry space group (triclinic) for UOHF-Ln (Ln = Er → Lu). However, given holmium lies close to this apparent transition boundary, whether these frameworks with holmium adopt a high or low symmetry structure is unknown. Herein, we report the synthesis of Ho<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>(OH)<sub>2</sub>[(UO<sub>2</sub>)<sub>10</sub>UO<sub>13</sub>(OH)<sub>4</sub>]·H<sub>2</sub>O (<strong>UOHF-Ho</strong>) and subsequent structural and spectroscopic investigations. Synchrotron single crystal X-ray diffraction confirmed that <strong>UOHF-Ho</strong> crystallises in the orthorhombic <em>C</em>222<sub>1</sub> space group, further validated by electron diffraction with transmission electron microscopy. The framework structure is constructed with β-U<sub>3</sub>O<sub>8</sub> type layers linked by double uranyl units in pentagonal bipyramids, with disordered Ho<sup>3+</sup> ions lying inside the channels. While Raman spectroscopy revealed the U<sup>6+</sup> dominant vibrational modes, diffuse reflectance spectroscopy unearthed characteristic absorption bands for both U<sup>6+</sup> and Ho<sup>3+</sup> ions. This work uncovers the exact phase transition for UOHF-Ln series and has implications to the uranium structural chemistry and possible spent nuclear fuel alterations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123023"},"PeriodicalIF":3.2,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683085","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}
The demand for metal ion sensors is growing at a rapid pace owing to the metal ions toxic effect on the environment, aquatic life and human health. Among these, Sn(II) detection holds particular importance due to its wide industrial use and potential bioaccumulation leading to neurological, hepatic and immunological disorders, making its sensitive and selective monitoring highly advantageous. This work presents the synthesis of a fluorometric turn-off sensor, a benzyloxy-derived triazole-based organosilane (5) for the selective detection of Sn(II). Probe 5 exhibited minimal interference from competing metal ions and achieved detection limits of 13.3 × 10−9 M (fluorometric spectroscopy) and 13.5 × 10−8 M (UV–Visible spectroscopy), both well below the WHO's permissible level for Sn(II) in drinking water. Its effectiveness was further validated in real water samples, showing recovery rates above 97%, thereby confirming its practical applicability. Moreover, molecular docking and molecular dynamics simulations revealed effective inhibition of the Matrix metalloproteinase-2 (MMP-2) enzyme with a binding energy of −9.41 kcal mol−1, and confirmed the interaction stability of probe 5 with the protein, supporting its potential as an anticancer drug candidate in the pharmaceutical domain.
{"title":"Benzyloxy triazole-functionalized organosilane: Dual application in Sn(II) detection and MMP-2 enzyme inhibition through in silico insights","authors":"Gurjaspreet Singh , Devina Sharma , Tsering Diskit , Anu Radha , Komal , Parul , Jandeep Singh , Nancy George","doi":"10.1016/j.ica.2025.123008","DOIUrl":"10.1016/j.ica.2025.123008","url":null,"abstract":"<div><div>The demand for metal ion sensors is growing at a rapid pace owing to the metal ions toxic effect on the environment, aquatic life and human health. Among these, Sn(II) detection holds particular importance due to its wide industrial use and potential bioaccumulation leading to neurological, hepatic and immunological disorders, making its sensitive and selective monitoring highly advantageous. This work presents the synthesis of a fluorometric turn-off sensor, a benzyloxy-derived triazole-based organosilane (<strong>5</strong>) for the selective detection of Sn(II). Probe <strong>5</strong> exhibited minimal interference from competing metal ions and achieved detection limits of 13.3 × 10<sup>−9</sup> M (fluorometric spectroscopy) and 13.5 × 10<sup>−8</sup> M (UV–Visible spectroscopy), both well below the WHO's permissible level for Sn(II) in drinking water. Its effectiveness was further validated in real water samples, showing recovery rates above 97%, thereby confirming its practical applicability. Moreover, molecular docking and molecular dynamics simulations revealed effective inhibition of the Matrix metalloproteinase-2 (MMP-2) enzyme with a binding energy of −9.41 kcal mol<sup>−1</sup>, and confirmed the interaction stability of probe <strong>5</strong> with the protein, supporting its potential as an anticancer drug candidate in the pharmaceutical domain.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123008"},"PeriodicalIF":3.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734151","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 : 2025-12-01DOI: 10.1016/j.ica.2025.123010
Yanling Zhu , Yufen Yang , Yi Han, Bin Li
Dinuclear germylenes 1 and 2 bearing bis(β-diketiminate) ligands with 1,3-phenylene and 1,2-cyclohexylene linkers, respectively, have been synthesized. The structure flexibility was verified by the variable-temperature NMR analysis. Further salt metathesis with AgOTf led to bis-germylene 3 with OTf substituent. The reaction of 1 with LiAl[OCH(CF3)2]4, aiming to get the dinuclear dication, resulted in the formation of alkoxyl substituted bis-germylene with the elimination of Al[OCH(CF3)2]3. All compounds have been characterized by nuclear magnetic resonance (NMR) and single-crystal X-ray diffraction (SC-XRD).
{"title":"Synthesis and characterization of bis-germylenes stabilized by bis(β-diketiminate) ligands","authors":"Yanling Zhu , Yufen Yang , Yi Han, Bin Li","doi":"10.1016/j.ica.2025.123010","DOIUrl":"10.1016/j.ica.2025.123010","url":null,"abstract":"<div><div>Dinuclear germylenes <strong>1</strong> and <strong>2</strong> bearing bis(β-diketiminate) ligands with 1,3-phenylene and 1,2-cyclohexylene linkers, respectively, have been synthesized. The structure flexibility was verified by the variable-temperature NMR analysis. Further salt metathesis with AgOTf led to bis-germylene <strong>3</strong> with OTf substituent. The reaction of <strong>1</strong> with LiAl[OCH(CF<sub>3</sub>)<sub>2</sub>]<sub>4</sub>, aiming to get the dinuclear dication, resulted in the formation of alkoxyl substituted bis-germylene with the elimination of Al[OCH(CF<sub>3</sub>)<sub>2</sub>]<sub>3</sub>. All compounds have been characterized by nuclear magnetic resonance (NMR) and single-crystal X-ray diffraction (SC-XRD).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123010"},"PeriodicalIF":3.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734222","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 : 2025-12-01DOI: 10.1016/j.ica.2025.123012
Iogann Tolbatov , Tiziano Marzo
{"title":"Editorial: Pharmacologically active metallodrugs: From design to mode of action studies","authors":"Iogann Tolbatov , Tiziano Marzo","doi":"10.1016/j.ica.2025.123012","DOIUrl":"10.1016/j.ica.2025.123012","url":null,"abstract":"","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123012"},"PeriodicalIF":3.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880280","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 : 2025-11-30DOI: 10.1016/j.ica.2025.123007
Daniel L. Singer , Jason G. Marmorstein , Joseph M. Tanski , Timothy J. Barnum , Laurie A. Tyler
The reactivity of ligated imines with alcohol-type nucleophiles has been investigated. Four Cu (II) complexes containing a N,N′-bis (2-pyridinylmethylene)-1,2-ethanediamine ((Py)2en) type ligand are reported, along with the hydrolysis or addition of solvent methanol across the imine CN bond. The products of this reactivity include the formation of ligated N,O-aminal or hemiacetal moieties as confirmed through single crystal X-ray crystallography. The observed product distribution is supported with ab initio and density functional theory calculations. A comprehensive 1H NMR study was performed with further derivatized ligand frames and diamagnetic Zn (II) species to explore the scope of the observed reactivity. These studies indicate that the ligand substituent strongly impacts the degree of imine activation toward reaction with solvent methanol and/or water (i.e. formation of mono N,O-aminal, bis N,O-aminal, hemiacetal or no reaction). The identity of the counterion in the hydrated zinc salt was also found to play a role, albeit to a lesser extent. The implications of the identity of the alcohol solvent on the CN reactivity was also investigated. Alcohols with decreased steric hindrance and increased nucleophilicity show the greatest propensity for addition.
研究了连接亚胺与醇型亲核试剂的反应性。报道了四种含有N，N ' -二（2-吡啶基亚甲基）-1,2-乙二胺（(Py)2en）型配体的Cu （II）配合物，并在亚胺CN键上水解或加成溶剂甲醇。这种反应的产物包括通过单晶x射线晶体学证实的连接的N， o -动物或半缩醛部分的形成。观察到的产品分布得到从头算和密度泛函理论计算的支持。对进一步衍生化配体框架和抗磁性Zn （II）进行了全面的1H NMR研究，以探索观察到的反应性范围。这些研究表明，配体取代基强烈影响亚胺与溶剂甲醇和/或水反应的活化程度（即形成单N， o -氨基，双N， o -氨基，半缩醛或不反应）。水合锌盐中反离子的特性也被发现起作用，尽管程度较小。研究了醇溶剂的性质对CN反应性的影响。空间位阻降低和亲核性增加的醇表现出最大的加成倾向。
{"title":"Factors influencing imine activation in M(II) complexes to afford ligated N,O-aminal and hemiacetal groups: XRD, 1H NMR, and computational studies","authors":"Daniel L. Singer , Jason G. Marmorstein , Joseph M. Tanski , Timothy J. Barnum , Laurie A. Tyler","doi":"10.1016/j.ica.2025.123007","DOIUrl":"10.1016/j.ica.2025.123007","url":null,"abstract":"<div><div>The reactivity of ligated imines with alcohol-type nucleophiles has been investigated. Four Cu (II) complexes containing a <em>N,N′</em>-bis (2-pyridinylmethylene)-1,2-ethanediamine ((Py)<sub>2</sub>en) type ligand are reported, along with the hydrolysis or addition of solvent methanol across the imine C<img>N bond. The products of this reactivity include the formation of ligated <em>N,O</em>-aminal or hemiacetal moieties as confirmed through single crystal X-ray crystallography. The observed product distribution is supported with ab initio and density functional theory calculations. A comprehensive <sup>1</sup>H NMR study was performed with further derivatized ligand frames and diamagnetic Zn (II) species to explore the scope of the observed reactivity. These studies indicate that the ligand substituent strongly impacts the degree of imine activation toward reaction with solvent methanol and/or water (i.e. formation of mono <em>N,O</em>-aminal, bis <em>N,O</em>-aminal, hemiacetal or no reaction). The identity of the counterion in the hydrated zinc salt was also found to play a role, albeit to a lesser extent. The implications of the identity of the alcohol solvent on the C<img>N reactivity was also investigated. Alcohols with decreased steric hindrance and increased nucleophilicity show the greatest propensity for addition.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123007"},"PeriodicalIF":3.2,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734154","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 : 2025-11-30DOI: 10.1016/j.ica.2025.123014
Hajer Bouznif , Licínia L.G. Justino , Telma Costa , Maria I.L. Soares , M. Luísa Ramos , Teresa M.V.D. Pinho e Melo , Nabil Zouari , Rui Fausto
Although the field of inorganic photophysics and photochemistry has traditionally been dominated by complexes of precious and rare metals, increasing concerns regarding their scarcity and cost have led to a growing interest in earth-abundant metal-based compounds as more sustainable and economically viable alternatives. In this study, we investigated the photophysical properties of two water-soluble compounds: the di-Schiff base N,N′-bis(3-methoxy-5-sulfonatosalicylidene)-1,2-ethylenediamine disodium salt (MSS) and its corresponding Al(III) complex. To better understand the enol-imine (O-H···N) vs. keto-enamine (O···H-N) tautomeric behavior of MSS, we also considered its non-methoxy analogue (SS) as a reference compound. Using UV–vis absorption and diffuse reflectance spectroscopy, we examined the tautomeric preferences of MSS and SS in both the solid state and various solvents. The spectral features of MSS exhibited a noticeable bathochromic shift relative to SS in all media. In protic solvents (H2O, MeOH) and in the solid state, MSS is found predominantly in the keto-enamine form, while in aprotic polar solvents (DMSO, DMF), a mixture of keto and enol forms coexist. In contrast, SS shows a dynamic coexistence of both tautomeric forms in protic solvents, while the SS enol form becomes dominant in DMSO and DMF; in the solid-state SS predominantly adopts the keto-enamine form. These differences were rationalized in terms of electronic effects. The direct band gap energies were determined to be 2.75 eV for SS, 2.61 eV for MSS and 3.03 eV for the Al(III)/MSS complex, revealing their wide-band-gap-semiconductor character. These values were supported by DFT calculations, which were found to be able to reproduce the experimental trends and were also used to provide insight into the electronic structure of the studied compounds. Photoluminescence analysis revealed that MSS emits in the green region, while the Al(III)/MSS complex exhibits a blue-white emission, making both compounds promising candidates for application in single-layer white OLEDs. Additionally, the Al(III)/MSS complex displayed photocatalytic activity toward the degradation of methylene blue (MB), with a rate constant of 0.032 min−1, indicating its potential as a multifunctional material for both optoelectronic and environmental applications.
{"title":"A water-soluble Schiff base ligand and its Al(III) complex: optical properties, computational studies and photocatalytic performance","authors":"Hajer Bouznif , Licínia L.G. Justino , Telma Costa , Maria I.L. Soares , M. Luísa Ramos , Teresa M.V.D. Pinho e Melo , Nabil Zouari , Rui Fausto","doi":"10.1016/j.ica.2025.123014","DOIUrl":"10.1016/j.ica.2025.123014","url":null,"abstract":"<div><div>Although the field of inorganic photophysics and photochemistry has traditionally been dominated by complexes of precious and rare metals, increasing concerns regarding their scarcity and cost have led to a growing interest in earth-abundant metal-based compounds as more sustainable and economically viable alternatives. In this study, we investigated the photophysical properties of two water-soluble compounds: the di-Schiff base <em>N</em>,<em>N′</em>-bis(3-methoxy-5-sulfonatosalicylidene)-1,2-ethylenediamine disodium salt (<strong>MSS</strong>) and its corresponding Al(III) complex. To better understand the enol-imine (O-H···N) <em>vs.</em> keto-enamine (O···H-N) tautomeric behavior of <strong>MSS</strong>, we also considered its non-methoxy analogue (<strong>SS</strong>) as a reference compound. Using UV–vis absorption and diffuse reflectance spectroscopy, we examined the tautomeric preferences of <strong>MSS</strong> and <strong>SS</strong> in both the solid state and various solvents. The spectral features of <strong>MSS</strong> exhibited a noticeable bathochromic shift relative to <strong>SS</strong> in all media. In protic solvents (H<sub>2</sub>O, MeOH) and in the solid state, <strong>MSS</strong> is found predominantly in the keto-enamine form, while in aprotic polar solvents (DMSO, DMF), a mixture of keto and enol forms coexist. In contrast, <strong>SS</strong> shows a dynamic coexistence of both tautomeric forms in protic solvents, while the <strong>SS</strong> enol form becomes dominant in DMSO and DMF; in the solid-state <strong>SS</strong> predominantly adopts the keto-enamine form. These differences were rationalized in terms of electronic effects. The direct band gap energies were determined to be 2.75 eV for <strong>SS</strong>, 2.61 eV for <strong>MSS</strong> and 3.03 eV for the <strong>Al(III)/MSS</strong> complex, revealing their wide-band-gap-semiconductor character. These values were supported by DFT calculations, which were found to be able to reproduce the experimental trends and were also used to provide insight into the electronic structure of the studied compounds. Photoluminescence analysis revealed that <strong>MSS</strong> emits in the green region, while the <strong>Al(III)/MSS</strong> complex exhibits a blue-white emission, making both compounds promising candidates for application in single-layer white OLEDs. Additionally, the <strong>Al(III)/MSS</strong> complex displayed photocatalytic activity toward the degradation of methylene blue (MB), with a rate constant of 0.032 min<sup>−1</sup>, indicating its potential as a multifunctional material for both optoelectronic and environmental applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123014"},"PeriodicalIF":3.2,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734220","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 : 2025-11-29DOI: 10.1016/j.ica.2025.123000
Dmitriy A. Lazovskiy , Ekaterina S. Gnedina , Ivan A. Nikitin , Hailong Wang , Pavel A. Stuzhin
Ethyl octaesters of phthalocyanine bearing eight carboxy-groups, [EstPcH2] (3), and its pyrazine fused analogue [EstTPyzPAH]2 (4) were synthesized by melting of corresponding dicarbonitriles in presence of sodium hydroxide or ethoxide. Reaction of these macrocycles with PBr3 in pyridine leads to contraction of the porphyrazine macrocycle and formation of the corresponding PV corrolazines, isolated as oxophosphorus(V) and dihydroxidophosphorus(V) complexes, [EstTBzCAP=O] (5) and [EstTPyzCAP(OH)2] (6). Fusion of electron-withdrawing pyrazine rings increases the NH acidity of the porphyrazine macrocycle leading to easy deprotonation of 4 and decreases the basicity of meso‑nitrogens – all of them can be protonated in 5 and only one in 6. Combination of electron-deficient pyrazine rings and electron-withdrawing COOEt groups leads to enhanced singlet oxygen generating ability not only by corrolazine 6, but also by dianionic form of porphyrazine 4 (ФΔ = 0.58 and 0.32, respectively). The obtained octaethyl esters can be considered as precursors for water-soluble octacarboxylated derivatives and building blocks for design of organic frameworks.
{"title":"Carboxylated benzo and pyrazine annulated PV corrolazines. I. Synthesis, spectral-luminescence and acid-base properties of octaethyl esters","authors":"Dmitriy A. Lazovskiy , Ekaterina S. Gnedina , Ivan A. Nikitin , Hailong Wang , Pavel A. Stuzhin","doi":"10.1016/j.ica.2025.123000","DOIUrl":"10.1016/j.ica.2025.123000","url":null,"abstract":"<div><div>Ethyl octaesters of phthalocyanine bearing eight carboxy-groups, [<sup>Est</sup><em>Pc</em>H<sub>2</sub>] (<strong>3</strong>), and its pyrazine fused analogue [<sup>Est</sup><em>TPyzPA</em>H]<sub>2</sub> (<strong>4</strong>) were synthesized by melting of corresponding dicarbonitriles in presence of sodium hydroxide or ethoxide. Reaction of these macrocycles with PBr<sub>3</sub> in pyridine leads to contraction of the porphyrazine macrocycle and formation of the corresponding P<sup>V</sup> corrolazines, isolated as oxophosphorus(V) and dihydroxidophosphorus(V) complexes, [<sup>Est</sup><em>TBzCA</em>P=O] (<strong>5</strong>) and [<sup>Est</sup><em>TPyzCA</em>P(OH)<sub>2</sub>] (<strong>6</strong>). Fusion of electron-withdrawing pyrazine rings increases the NH acidity of the porphyrazine macrocycle leading to easy deprotonation of <strong>4</strong> and decreases the basicity of <em>meso</em>‑nitrogens – all of them can be protonated in <strong>5</strong> and only one in <strong>6</strong>. Combination of electron-deficient pyrazine rings and electron-withdrawing COOEt groups leads to enhanced singlet oxygen generating ability not only by corrolazine <strong>6</strong>, but also by dianionic form of porphyrazine <strong>4</strong> (Ф<sub>Δ</sub> = 0.58 and 0.32, respectively). The obtained octaethyl esters can be considered as precursors for water-soluble octacarboxylated derivatives and building blocks for design of organic frameworks.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123000"},"PeriodicalIF":3.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683083","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 novel dinuclear Zn(II) complex, [Zn₂(3HBA)₄(HMTA)₂]·2H₂O (3HBA: 3-hydroxybenzoate and HMTA: hexamethylenetetramine), has been synthesized and fully characterized by single-crystal X-ray diffraction, FT-IR, NMR, UV–Vis, and DFT studies. The crystal structure reveals a centrosymmetric dimeric framework where each Zn(II) ion adopts a slightly distorted square-pyramidal geometry, coordinated by four bridging 3-hydroxybenzoate anions and one nitrogen atom from a monodentate hexamethylenetetramine (HMTA) ligand. The crystal packing is stabilized through an extensive network of O–H···O, O–H···N, C–H···O, and C–H···N hydrogen bonds, as confirmed by Hirshfeld surface analysis, in which H···H (47.5 %) and H···O/O···H (16.3 %) contacts dominate the intermolecular interactions. The void analysis revealed a low porosity (5.81 %), suggesting a densely packed and mechanically stable lattice. Spectroscopic data corroborate coordination through both carboxylate oxygen and HMTA nitrogen donors, while DFT calculations (B3LYP/LANL2DZ) indicate a large HOMO–LUMO gap (ΔE = 4.28 eV), consistent with high kinetic stability and moderate electrophilicity (ω = 2.99 eV). The molecular electrostatic potential (MEP) map highlights electron-rich carboxylate oxygen atoms as probable electrophilic sites. Molecular docking simulations against DNA gyrase B (PDB: 4URM) and New Delhi metallo-β-lactamase-1 (NDM-1, PDB: 4HL2) revealed strong binding affinities (−8.1 and − 10.2 kcal/mol, respectively), involving multiple hydrogen bonds and π-interactions with key active-site residues. Overall, the combined experimental and theoretical findings confirm the robust structural integrity, electronic stability, and notable antibacterial binding potential of the complex, particularly against β-lactamase-type bacterial enzymes.
{"title":"Unveiling the structural and electronic features of a hexamethylenetetramine complex of zinc 3-hydroxybenzoate: crystal structure, hirshfeld surface, DFT, and molecular docking studies","authors":"Giray Buğra Akbaba , Füreya Elif Öztürkkan , Elaheh Teymouri , Tuncer Hökelek , Hacali Necefoğlu","doi":"10.1016/j.ica.2025.123013","DOIUrl":"10.1016/j.ica.2025.123013","url":null,"abstract":"<div><div>A novel dinuclear Zn(II) complex, [Zn₂(3HBA)₄(HMTA)₂]·2H₂O (3HBA: 3-hydroxybenzoate and HMTA: hexamethylenetetramine), has been synthesized and fully characterized by single-crystal X-ray diffraction, FT-IR, NMR, UV–Vis, and DFT studies. The crystal structure reveals a centrosymmetric dimeric framework where each Zn(II) ion adopts a slightly distorted square-pyramidal geometry, coordinated by four bridging 3-hydroxybenzoate anions and one nitrogen atom from a monodentate hexamethylenetetramine (HMTA) ligand. The crystal packing is stabilized through an extensive network of O–H···O, O–H···N, C–H···O, and C–H···N hydrogen bonds, as confirmed by Hirshfeld surface analysis, in which H···H (47.5 %) and H···O/O···H (16.3 %) contacts dominate the intermolecular interactions. The void analysis revealed a low porosity (5.81 %), suggesting a densely packed and mechanically stable lattice. Spectroscopic data corroborate coordination through both carboxylate oxygen and HMTA nitrogen donors, while DFT calculations (B3LYP/LANL2DZ) indicate a large HOMO–LUMO gap (ΔE = 4.28 eV), consistent with high kinetic stability and moderate electrophilicity (ω = 2.99 eV). The molecular electrostatic potential (MEP) map highlights electron-rich carboxylate oxygen atoms as probable electrophilic sites. Molecular docking simulations against DNA gyrase B (PDB: <span><span>4URM</span><svg><path></path></svg></span>) and New Delhi metallo-β-lactamase-1 (NDM-1, PDB: <span><span>4HL2</span><svg><path></path></svg></span>) revealed strong binding affinities (−8.1 and − 10.2 kcal/mol, respectively), involving multiple hydrogen bonds and π-interactions with key active-site residues. Overall, the combined experimental and theoretical findings confirm the robust structural integrity, electronic stability, and notable antibacterial binding potential of the complex, particularly against β-lactamase-type bacterial enzymes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 123013"},"PeriodicalIF":3.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690758","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}
Alkyl derivatives of 2-nitrophenol are promising extractants for the selective recovery of lithium in the presence of large excesses of sodium and potassium ions. To probe the structural factors underpinning lithium selectivity, we synthesized coordination compounds of lithium, sodium and potassium with 2-nitrophenol and established their composition and structures by elemental analysis, single-crystal X-ray diffraction (SCXRD) and FT-IR spectroscopy. General regularities in the binding of 2-nitrophenol with Li+, Na+ and K+ were identified. The ability of 2-nitrophenol to form six-membered chelate metallacycles with alkali-metal cations has been confirmed. Notably, the geometry of lithium metallacycles, even within the same compound, varies from nearly planar to boat and envelope conformations.
{"title":"Coordination compounds of lithium, sodium, and potassium with 2-nitrophenol: Single-crystal X-ray diffraction and FT-IR spectroscopic study","authors":"A.A. Bezdomnikov , F.M. Dolgushin , L.I. Demina , V.E. Sharov , E.A. Kurenkova , V.E. Baulin , A.Yu. Tsivadze","doi":"10.1016/j.ica.2025.123006","DOIUrl":"10.1016/j.ica.2025.123006","url":null,"abstract":"<div><div>Alkyl derivatives of 2-nitrophenol are promising extractants for the selective recovery of lithium in the presence of large excesses of sodium and potassium ions. To probe the structural factors underpinning lithium selectivity, we synthesized coordination compounds of lithium, sodium and potassium with 2-nitrophenol and established their composition and structures by elemental analysis, single-crystal X-ray diffraction (SCXRD) and FT-IR spectroscopy. General regularities in the binding of 2-nitrophenol with Li<sup>+</sup>, Na<sup>+</sup> and K<sup>+</sup> were identified. The ability of 2-nitrophenol to form six-membered chelate metallacycles with alkali-metal cations has been confirmed. Notably, the geometry of lithium metallacycles, even within the same compound, varies from nearly planar to boat and envelope conformations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"591 ","pages":"Article 123006"},"PeriodicalIF":3.2,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621631","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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