This study presents the synthesis of ultralong silver nanowires (AgNWs) with high purity via a hydrothermal approach. AgCl hydrosol is first converted into polyhedral particles, which serve as heterogeneous nucleation sites and a source of Ag precursor for subsequent reduction by maltose to yield AgNWs. The presence of sufficient poly(vinylpyrrolidone) (PVP) helps to suppress the growth of Ag nanoparticles formed on the Ag(100)/AgCl(100) interface. The low concentration of Ag+ limited by the solubility product of AgCl hinders the secondary nucleation and growth of AgNPs in the bulk solution. A relatively high reduction rate, which is conducive to the self-catalyzed longitudinal growth of AgNWs along the ⟨110⟩ direction, can be achieved through the synergy among the low portion of AgNPs with pentagonal twinnings formed on the Ag(111)/AgCl(100) interface, stable concentration of maltose, and steady release of Ag+ from AgCl. Experimental parameters including temperature, the concentration of maltose, the concentration of metal chlorides, and so on exert their influence on the formation of AgNWs via altering the reduction rate of Ag+ in the reaction system. Optimal conditions result in AgNWs > 200 μm, 30 nm dia., with simplified NH4OH purification. This study provides a scalable method for high-purity AgNW production.
{"title":"Hydrothermal Synthesis of High-Purity, Ultralong Silver Nanowires by Heterogeneous Nucleation","authors":"Wenli Bi, Qi Zhang, Zhenzhen Mo, Wenlong Wang, Ruijing Li, Cheng Wang","doi":"10.1021/acs.inorgchem.5c01351","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01351","url":null,"abstract":"This study presents the synthesis of ultralong silver nanowires (AgNWs) with high purity via a hydrothermal approach. AgCl hydrosol is first converted into polyhedral particles, which serve as heterogeneous nucleation sites and a source of Ag precursor for subsequent reduction by maltose to yield AgNWs. The presence of sufficient poly(vinylpyrrolidone) (PVP) helps to suppress the growth of Ag nanoparticles formed on the Ag(100)/AgCl(100) interface. The low concentration of Ag<sup>+</sup> limited by the solubility product of AgCl hinders the secondary nucleation and growth of AgNPs in the bulk solution. A relatively high reduction rate, which is conducive to the self-catalyzed longitudinal growth of AgNWs along the ⟨110⟩ direction, can be achieved through the synergy among the low portion of AgNPs with pentagonal twinnings formed on the Ag(111)/AgCl(100) interface, stable concentration of maltose, and steady release of Ag<sup>+</sup> from AgCl. Experimental parameters including temperature, the concentration of maltose, the concentration of metal chlorides, and so on exert their influence on the formation of AgNWs via altering the reduction rate of Ag<sup>+</sup> in the reaction system. Optimal conditions result in AgNWs > 200 μm, 30 nm dia., with simplified NH<sub>4</sub>OH purification. This study provides a scalable method for high-purity AgNW production.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841214","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 : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00071
Brian J. Knight, Kevin J. Anderton, Juan F. Torres, Vincent J. Catalano, Ricardo Garcia-Serres, Leslie J. Murray
The reactivity of iron clusters with one of more μ-hydrides and in the weak field pertains to catalysis on surfaces and biological metal cluster cofactors. As a model, then, a reactivity survey of the weak-field ligated iron hydride clusters Fe3H3L (1) and (FeCO)2Fe(μ3–H)L (2) (where L3– is a tris(β-diketiminate)cyclophanate) with Brønsted acids, organochlorides, acetyl chloride, boron trihalides, and titanium electrophiles is reported. Complex 1 reacts with Brønsted acids H2O and [Et3NH][Cl] to afford Fe3(OH)3L (3) and Fe3H2ClL (4), respectively, consistent with hydridic reactivity. Clusters 1 and 2 react readily with organochlorides, such as CCl4, CHCl3, and CH2Cl2, with identified intermediates supporting a radical pathway. Complex 1 reacts with trityl chloride (2 equiv) to selectively afford Fe3HCl2L (5) with reductive elimination of dihydrogen observed. Mixed-valent complex 2 reacts with AcCl to afford (FeCO)Fe2HClL (9). The scope of reactivity displayed implicates possible pathways accessible to larger clusters in biology or on metal surfaces.
{"title":"Substrate-Dependent Hydridic and Radical Reactivity of Triiron Hydride Clusters","authors":"Brian J. Knight, Kevin J. Anderton, Juan F. Torres, Vincent J. Catalano, Ricardo Garcia-Serres, Leslie J. Murray","doi":"10.1021/acs.inorgchem.5c00071","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00071","url":null,"abstract":"The reactivity of iron clusters with one of more μ-hydrides and in the weak field pertains to catalysis on surfaces and biological metal cluster cofactors. As a model, then, a reactivity survey of the weak-field ligated iron hydride clusters Fe<sub>3</sub>H<sub>3</sub><b>L</b> (<b>1</b>) and (FeCO)<sub>2</sub>Fe(μ<sub>3</sub>–H)<b>L</b> (<b>2</b>) (where <b>L</b><sup><b>3–</b></sup> is a tris(β-diketiminate)cyclophanate) with Brønsted acids, organochlorides, acetyl chloride, boron trihalides, and titanium electrophiles is reported. Complex <b>1</b> reacts with Brønsted acids H<sub>2</sub>O and [Et<sub>3</sub>NH][Cl] to afford Fe<sub>3</sub>(OH)<sub>3</sub><b>L</b> (<b>3</b>) and Fe<sub>3</sub>H<sub>2</sub>Cl<b>L</b> (<b>4</b>), respectively, consistent with hydridic reactivity. Clusters <b>1</b> and <b>2</b> react readily with organochlorides, such as CCl<sub>4</sub>, CHCl<sub>3</sub>, and CH<sub>2</sub>Cl<sub>2</sub>, with identified intermediates supporting a radical pathway. Complex <b>1</b> reacts with trityl chloride (2 equiv) to selectively afford Fe<sub>3</sub>HCl<sub>2</sub><b>L</b> (<b>5</b>) with reductive elimination of dihydrogen observed. Mixed-valent complex <b>2</b> reacts with AcCl to afford (FeCO)Fe<sub>2</sub>HCl<b>L</b> (<b>9</b>). The scope of reactivity displayed implicates possible pathways accessible to larger clusters in biology or on metal surfaces.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841205","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 : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00317
Teresa Garcia-Mendoza, Björn Winkler, Wolfgang Morgenroth, Andrei Barkov, Alfredo Martinez-Garcia, Carlos G. Garay-Reyes, Fernando Chiñas-Castillo, Erick Adrian Juarez-Arellano
The recent discovery of new Pt-based minerals has opened up the opportunity to generate new synthetic materials. Here, geologically inspired approaches to designing and synthesizing novel platinum alloys, from ternary to high-entropy alloys (HEAs), are showcased. Empirical mathematical models of thermodynamic parameters were used to predict the formation of solid solutions with single-phase structures in the (Pt3–xPdx)(Cu2–yNiySn) system. Five new single-phase compounds, having ordered L10-type structures, have been obtained at comparatively low temperatures by solid-state reactions. Two of those phases are new noble metal HEAs, (Pt2Pd)(Cu1.7Ni0.3Sn) and (Pt2Pd)(Cu1.4Ni0.6Sn). Additionally, other three new multiprinciple element alloys (mixture of ordered L10-type and disordered FCC-type structures) were also obtained. SEM/EDX measurements gave no indication of chemical inhomogeneities on a micrometer length scale. A phase diagram is proposed. All products are thermally stable at up to 1100 K, and the two-phase samples show a tendency for nitrogen absorption. The results show that using geomimetic approaches in the design and synthesis of novel materials opened new opportunities for future materials design.
{"title":"Geomimetic Approaches in the Design and Synthesis of Ordered L10-Type Structure Platinum-Based Noble High-Entropy Alloys at Low Temperature","authors":"Teresa Garcia-Mendoza, Björn Winkler, Wolfgang Morgenroth, Andrei Barkov, Alfredo Martinez-Garcia, Carlos G. Garay-Reyes, Fernando Chiñas-Castillo, Erick Adrian Juarez-Arellano","doi":"10.1021/acs.inorgchem.5c00317","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00317","url":null,"abstract":"The recent discovery of new Pt-based minerals has opened up the opportunity to generate new synthetic materials. Here, geologically inspired approaches to designing and synthesizing novel platinum alloys, from ternary to high-entropy alloys (HEAs), are showcased. Empirical mathematical models of thermodynamic parameters were used to predict the formation of solid solutions with single-phase structures in the (Pt<sub>3–<i>x</i></sub>Pd<sub><i>x</i></sub>)(Cu<sub>2–<i>y</i></sub>Ni<sub><i>y</i></sub>Sn) system. Five new single-phase compounds, having ordered L1<sub>0</sub>-type structures, have been obtained at comparatively low temperatures by solid-state reactions. Two of those phases are new noble metal HEAs, (Pt<sub>2</sub>Pd)(Cu<sub>1.7</sub>Ni<sub>0.3</sub>Sn) and (Pt<sub>2</sub>Pd)(Cu<sub>1.4</sub>Ni<sub>0.6</sub>Sn). Additionally, other three new multiprinciple element alloys (mixture of ordered L1<sub>0</sub>-type and disordered FCC-type structures) were also obtained. SEM/EDX measurements gave no indication of chemical inhomogeneities on a micrometer length scale. A phase diagram is proposed. All products are thermally stable at up to 1100 K, and the two-phase samples show a tendency for nitrogen absorption. The results show that using geomimetic approaches in the design and synthesis of novel materials opened new opportunities for future materials design.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"108 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841208","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 mononuclear tetrahedral manganese complex containing all O-donor ligands has been prepared under mild conditions starting from a dialkylcarbamato manganese(II) precursor. Manganese(II) N,N-dibutylcarbamate [Mn(O2CNBu2)2]n, 1, can be conveniently prepared by extraction from a deoxygenated water solution of manganese(II) sulfate using a CO2-saturated toluene solution of dibutylamine. Access to the N,N-dibenzylcarbamato manganese complex [Mn(O2CNBz2)2]n, 2, occurs through metathesis by reaction with dibenzylamine and carbon dioxide. By reaction of 2 with pentafluorophenol, an almost quantitative reaction affords [Bz2NH2]2[Mn(OC6F5)4], 3, that has been crystallographically characterized through single-crystal X-ray diffraction. Compound 3 exhibits absorption and emission spectral features characteristic of Mn2+ ions in a tetrahedral coordination environment. Upon cooling, the emission intensity was observed to increase by approximately two orders of magnitude. The excited-state lifetimes exhibited significant temperature dependence, ranging from 12.7 ms at 80 K to 10 μs at 290 K. The temperature-dependent trends of both emission intensity and lifetimes showed nearly identical profiles. As a result, compound 3 functions as a dual-mode highly sensitive luminescent molecular thermometer, with a maximum relative thermal sensitivity (Sr) of 7.4% K–1 at 220 K and Sr >1 over the temperature range 170–270 K. A distinctive feature of compound 3 is its capacity to yield equivalent luminescent molecular thermometers (LMT) using either the emission intensity or lifetime, thus enhancing its versatility in thermal sensing applications.
{"title":"Luminescent Tetrahedral Manganese(II) Pentaphluorophenolate Complex as a Highly Sensitive Molecular Thermometer","authors":"Luca Labella, Gregorio Bottaro, Fabio Marchetti, Simona Samaritani, Lidia Armelao","doi":"10.1021/acs.inorgchem.4c05477","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05477","url":null,"abstract":"A mononuclear tetrahedral manganese complex containing all O-donor ligands has been prepared under mild conditions starting from a dialkylcarbamato manganese(II) precursor. Manganese(II) <i>N,N</i>-dibutylcarbamate [Mn(O<sub>2</sub>CNBu<sub>2</sub>)<sub>2</sub>]<sub><i>n</i></sub>, <b>1</b>, can be conveniently prepared by extraction from a deoxygenated water solution of manganese(II) sulfate using a CO<sub>2</sub>-saturated toluene solution of dibutylamine. Access to the <i>N</i>,<i>N</i>-dibenzylcarbamato manganese complex [Mn(O<sub>2</sub>CNBz<sub>2</sub>)<sub>2</sub>]<sub><i>n</i></sub>, <b>2</b>, occurs through metathesis by reaction with dibenzylamine and carbon dioxide. By reaction of <b>2</b> with pentafluorophenol, an almost quantitative reaction affords [Bz<sub>2</sub>NH<sub>2</sub>]<sub>2</sub>[Mn(OC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], <b>3</b>, that has been crystallographically characterized through single-crystal X-ray diffraction. Compound <b>3</b> exhibits absorption and emission spectral features characteristic of Mn<sup>2+</sup> ions in a tetrahedral coordination environment. Upon cooling, the emission intensity was observed to increase by approximately two orders of magnitude. The excited-state lifetimes exhibited significant temperature dependence, ranging from 12.7 ms at 80 K to 10 μs at 290 K. The temperature-dependent trends of both emission intensity and lifetimes showed nearly identical profiles. As a result, compound <b>3</b> functions as a dual-mode highly sensitive luminescent molecular thermometer, with a maximum relative thermal sensitivity (<i>S</i><sub>r</sub>) of 7.4% K<sup>–1</sup> at 220 K and <i>S</i><sub>r</sub> >1 over the temperature range 170–270 K. A distinctive feature of compound <b>3</b> is its capacity to yield equivalent luminescent molecular thermometers (LMT) using either the emission intensity or lifetime, thus enhancing its versatility in thermal sensing applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837332","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 : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00784
Guangxiang Lu, Zien Cheng, Maxim Avdeev, Pengfei Jiang, Rihong Cong, Tao Yang
Photocatalytic water splitting and CO2 reduction offer sustainable solutions to energy and environmental issues, but efficient semiconductor photocatalysts are still limited. Oxide photocatalysts with d0 and/or d10 metals often have wide bandgaps, and incorporating d10ns2 metals can raise the valence band maximum (VBM) and narrow the bandgap. Here, we synthesized BiTi4GaO11 (BTGO), a new photocatalyst containing d106s2, d0, and d10 metals. Structural analysis via powder X-ray and neutron diffraction confirmed BTGO crystallizes in the space group Cmcm, with Ga cooccupying all three Ti sites. Density functional theory calculations revealed that the conduction band minimum (CBM) of BTGO is primarily composed of Ti t2g - O 2p antibonding orbitals. Hybridization between Bi 6s and O 2p orbitals leads to the formation of antibonding orbitals, which further interact with Bi 6p orbitals to form the VBM. This interaction shifts the VBM upward, narrows the bandgap (Eg = 2.82 eV), and enables the visible-light absorption. Experimental results demonstrated that BTGO efficiently catalyzes photocatalytic H2 production and CO2 reduction. Furthermore, the incorporation of cocatalysts suppressed the recombination of photogenerated charge carriers, enhancing photocatalytic activity. This work highlights the importance of electronic structure and bonding analysis in understanding the fundamental mechanisms of photocatalysis.
{"title":"Exploring the Photocatalytic Mechanism of BiTi4GaO11: Insights from the Electronic Structure and Chemical Bonding","authors":"Guangxiang Lu, Zien Cheng, Maxim Avdeev, Pengfei Jiang, Rihong Cong, Tao Yang","doi":"10.1021/acs.inorgchem.5c00784","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00784","url":null,"abstract":"Photocatalytic water splitting and CO<sub>2</sub> reduction offer sustainable solutions to energy and environmental issues, but efficient semiconductor photocatalysts are still limited. Oxide photocatalysts with d<sup>0</sup> and/or d<sup>10</sup> metals often have wide bandgaps, and incorporating d<sup>10</sup>ns<sup>2</sup> metals can raise the valence band maximum (VBM) and narrow the bandgap. Here, we synthesized BiTi<sub>4</sub>GaO<sub>11</sub> (BTGO), a new photocatalyst containing d<sup>10</sup>6s<sup>2</sup>, d<sup>0</sup>, and d<sup>10</sup> metals. Structural analysis via powder X-ray and neutron diffraction confirmed BTGO crystallizes in the space group <i>Cmcm</i>, with Ga cooccupying all three Ti sites. Density functional theory calculations revealed that the conduction band minimum (CBM) of BTGO is primarily composed of Ti t<sub>2g</sub> - O 2p antibonding orbitals. Hybridization between Bi 6s and O 2p orbitals leads to the formation of antibonding orbitals, which further interact with Bi 6p orbitals to form the VBM. This interaction shifts the VBM upward, narrows the bandgap (<i>E</i><sub>g</sub> = 2.82 eV), and enables the visible-light absorption. Experimental results demonstrated that BTGO efficiently catalyzes photocatalytic H<sub>2</sub> production and CO<sub>2</sub> reduction. Furthermore, the incorporation of cocatalysts suppressed the recombination of photogenerated charge carriers, enhancing photocatalytic activity. This work highlights the importance of electronic structure and bonding analysis in understanding the fundamental mechanisms of photocatalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837378","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 : 2025-04-15DOI: 10.1021/acs.inorgchem.5c00841
Nazir Ud Din Mir, Subhrajyoti Ghosh, Kalimuthu Abirami Sundari, Amarajothi Dhakshinamoorthy, Shyam Biswas
The increasing impact of elevated atmospheric CO2 levels on climate and biological systems underscores the urgent need for effective materials to mitigate these concentrations. Simultaneously, the demand for quinoline derivatives has risen sharply due to their critical role in synthesizing life-saving drugs. Here, we present the synthesis, characterization, and catalytic activity of an aqua-stable Al(III) metal–organic framework (MOF 1′) and its postmodified variant doped with Ag(0) nanoparticles (1′-Ag NPs). The native MOF (1′) and its nanoparticle-anchored derivative exhibited remarkable efficacy in two key areas: the quantitative synthesis of quinoline heterocycles and irreversible chemical fixation of CO2 into various alkynes. Under ambient temperature and atmospheric CO2 pressure, 1′-Ag NPs demonstrated exceptional catalytic performance for the cyclization of propargylic alcohols. Moreover, the catalysts exhibited excellent recyclability across multiple reusability cycles. Detailed control experiments revealed that the outstanding performance of 1′ and 1′-Ag NPs stems from the anchored functional groups within 1′ and the highly exposed alkalophilic Ag(0) catalytic sites distributed along the surface of 1′-Ag NPs. This study highlights the dual utility of 1′ and 1′-Ag NPs, demonstrating their potential in both the selective synthesis of quinoline heterocycles and the environmentally sustainable capture and irreversible chemical conversion of CO2 under mild conditions.
{"title":"Strategic Design of a Functionalized Al(III) Metal–Organic Framework for Chemical Fixation of CO2 inside Alkynes under Ambient Conditions and Synthesis of Biologically Important Heterocycles","authors":"Nazir Ud Din Mir, Subhrajyoti Ghosh, Kalimuthu Abirami Sundari, Amarajothi Dhakshinamoorthy, Shyam Biswas","doi":"10.1021/acs.inorgchem.5c00841","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00841","url":null,"abstract":"The increasing impact of elevated atmospheric CO<sub>2</sub> levels on climate and biological systems underscores the urgent need for effective materials to mitigate these concentrations. Simultaneously, the demand for quinoline derivatives has risen sharply due to their critical role in synthesizing life-saving drugs. Here, we present the synthesis, characterization, and catalytic activity of an aqua-stable Al(III) metal–organic framework (MOF <b>1′</b>) and its postmodified variant doped with Ag(0) nanoparticles (<b>1′</b>-Ag NPs). The native MOF (<b>1′</b>) and its nanoparticle-anchored derivative exhibited remarkable efficacy in two key areas: the quantitative synthesis of quinoline heterocycles and irreversible chemical fixation of CO<sub>2</sub> into various alkynes. Under ambient temperature and atmospheric CO<sub>2</sub> pressure, <b>1′</b>-Ag NPs demonstrated exceptional catalytic performance for the cyclization of propargylic alcohols. Moreover, the catalysts exhibited excellent recyclability across multiple reusability cycles. Detailed control experiments revealed that the outstanding performance of <b>1′</b> and <b>1′</b>-Ag NPs stems from the anchored functional groups within <b>1′</b> and the highly exposed alkalophilic Ag(0) catalytic sites distributed along the surface of <b>1′</b>-Ag NPs. This study highlights the dual utility of <b>1′</b> and <b>1′</b>-Ag NPs, demonstrating their potential in both the selective synthesis of quinoline heterocycles and the environmentally sustainable capture and irreversible chemical conversion of CO<sub>2</sub> under mild conditions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837383","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 : 2025-04-15DOI: 10.1021/acs.inorgchem.5c00195
Pei-Pei Cui, Rakesh Kumar Gupta, Mohammad Azam, Ping Cui, Di Sun
The controlled assembly of silver nanoclusters (NCs) into tunable coordination polymers (CPs) presents opportunities for functional material design, although stability-related challenges persist. Herein, we report the synthesis of three silver CPs (1–3) by adjusting reaction conditions, such as method and solvent, facilitating the self-assembly of silver NCs with the 4,8-ethenobenzo[1,2-c:4,5-c′] dipyrrole-1,3,5,7(2H,6H)-tetrone (BDI) ligand. Single crystal X-ray diffraction analyses reveal three distinct architectures: a one-dimensional cyclic loop chain (1), a two-dimensional layered structure (2), and a 2-fold interpenetrated cyclic loop chain (3). We systematically explore the hydrogen bonding interactions, structural stability, and optical properties of these materials, demonstrating that the spatial arrangement of silver NCs and BDI ligands dictates both the dimensionality and the photophysical behavior. This study provides new insights into the design of silver-based CPs with enhanced optical properties and paves the way for advanced applications in optoelectronics and molecular sensing.
{"title":"Dimensional Control and Optical Properties of Tunable Silver Coordination Polymers via Nanocluster Assembly","authors":"Pei-Pei Cui, Rakesh Kumar Gupta, Mohammad Azam, Ping Cui, Di Sun","doi":"10.1021/acs.inorgchem.5c00195","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00195","url":null,"abstract":"The controlled assembly of silver nanoclusters (NCs) into tunable coordination polymers (CPs) presents opportunities for functional material design, although stability-related challenges persist. Herein, we report the synthesis of three silver CPs (<b>1</b>–<b>3</b>) by adjusting reaction conditions, such as method and solvent, facilitating the self-assembly of silver NCs with the 4,8-ethenobenzo[1,2-<i>c</i>:4,5-<i>c</i>′] dipyrrole-1,3,5,7(2<i>H</i>,6<i>H</i>)-tetrone (BDI) ligand. Single crystal X-ray diffraction analyses reveal three distinct architectures: a one-dimensional cyclic loop chain (<b>1</b>), a two-dimensional layered structure (<b>2</b>), and a 2-fold interpenetrated cyclic loop chain (<b>3</b>). We systematically explore the hydrogen bonding interactions, structural stability, and optical properties of these materials, demonstrating that the spatial arrangement of silver NCs and BDI ligands dictates both the dimensionality and the photophysical behavior. This study provides new insights into the design of silver-based CPs with enhanced optical properties and paves the way for advanced applications in optoelectronics and molecular sensing.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832175","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 : 2025-04-15DOI: 10.1021/acs.inorgchem.5c01211
Lei He, Peng Cao, Zi-Ning Zhou, Ya-Wen Yang, Le-Qi Chen, Qiong Ye
Organic–inorganic hybrid halide double perovskites have garnered significant attention because of their broad utility in data storage, transducers, and signal processing. However, halide double perovskites incorporating alkali metal components with ferroelectricity are still relatively scarce. Herein, we utilize the alkali metal substitution strategy to fabricate a new homochiral K/Bi-based halide double perovskite ferroelectric, (S-3-hydroxypyrrolidinium)2KBiBr6 (1). Compound 1 forms a three-dimensional (3D) inorganic framework and features a lon topology characterized by a Schläfli symbol of 66. The sp3 O atoms from the organic cations coordinate with the alkali metal K atoms, forming the twist dodecahedron and creating a large distortion in the inorganic framework. Structural analysis reveals 1 undergoes two phase transitions at 357 and 420 K. Symmetry-breaking with the 2F1 structural species leads to the emergence of ferroelasticity and ferroelectricity. 1 possesses clear ferroelectricity with a remnant polarization (Pr) value of 1.86 μC cm–2 and a low coercive field (Ec) value of 1.4 kV cm–1. Interestingly, the Pr value remains nearly unchanged, while the Ec value decreases by 17.6% after the alkali metal substitution. This work enlarges the family of hybrid bimetal halides containing alkali metals and provides new insights for exploring stable multifunctional ferroelectric materials.
{"title":"Alkali Metal Substitution for Modulating Three-Dimensional Halide Double Perovskite Ferroelectric","authors":"Lei He, Peng Cao, Zi-Ning Zhou, Ya-Wen Yang, Le-Qi Chen, Qiong Ye","doi":"10.1021/acs.inorgchem.5c01211","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01211","url":null,"abstract":"Organic–inorganic hybrid halide double perovskites have garnered significant attention because of their broad utility in data storage, transducers, and signal processing. However, halide double perovskites incorporating alkali metal components with ferroelectricity are still relatively scarce. Herein, we utilize the alkali metal substitution strategy to fabricate a new homochiral K/Bi-based halide double perovskite ferroelectric, (<i>S</i>-3-hydroxypyrrolidinium)<sub>2</sub>KBiBr<sub>6</sub> (<b>1</b>). Compound <b>1</b> forms a three-dimensional (3D) inorganic framework and features a lon topology characterized by a Schläfli symbol of 6<sup>6</sup>. The sp<sup>3</sup> O atoms from the organic cations coordinate with the alkali metal K atoms, forming the twist dodecahedron and creating a large distortion in the inorganic framework. Structural analysis reveals <b>1</b> undergoes two phase transitions at 357 and 420 K. Symmetry-breaking with the 2<i>F</i>1 structural species leads to the emergence of ferroelasticity and ferroelectricity. <b>1</b> possesses clear ferroelectricity with a remnant polarization (<i>P</i><sub>r</sub>) value of 1.86 μC cm<sup>–2</sup> and a low coercive field (<i>E</i><sub>c</sub>) value of 1.4 kV cm<sup>–1</sup>. Interestingly, the <i>P</i><sub>r</sub> value remains nearly unchanged, while the <i>E</i><sub>c</sub> value decreases by 17.6% after the alkali metal substitution. This work enlarges the family of hybrid bimetal halides containing alkali metals and provides new insights for exploring stable multifunctional ferroelectric materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837382","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 : 2025-04-15DOI: 10.1021/acs.inorgchem.5c00534
Joel Martínez-Visiedo, Susana Ibáñez, Dmitry G. Gusev, Macarena Poyatos, Eduardo Peris
We describe the synthesis of two rhodium and iridium complexes featuring a di-NHC macrocyclic ligand, which incorporates both a diphenylene moiety and a naphthalenediimide (NDI) unit. We observed that the addition of fluoride or chloride resulted in substantial alterations to the steric and electronic properties of both complexes. Specifically, fluoride addition led to the reduction of the NDI unit through the formation of an (OH–) NDI intermediate, while chloride produced a (Cl–)···NDI adduct. Both adducts were confirmed by mass spectrometry. The impact of fluoride and chloride addition on the steric and electronic properties of the rhodium and iridium NDI-containing complexes was examined using spectroscopic and computational methods. The presence of either halide significantly enhanced the catalytic activity of the complexes in the hydroboration of terminal alkenes. Finally, we demonstrated that this catalytic enhancement is reversible, with the catalytic process being activated and deactivated by the sequential introduction of excess halide and NOBF4. This observation reveals a rare example of a halide-induced redox-switchable catalytic (HIRSC) system.
{"title":"A Halide-Induced Redox-Switchable Catalyst for the Hydroboration of Terminal Alkenes","authors":"Joel Martínez-Visiedo, Susana Ibáñez, Dmitry G. Gusev, Macarena Poyatos, Eduardo Peris","doi":"10.1021/acs.inorgchem.5c00534","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00534","url":null,"abstract":"We describe the synthesis of two rhodium and iridium complexes featuring a di-NHC macrocyclic ligand, which incorporates both a diphenylene moiety and a naphthalenediimide (NDI) unit. We observed that the addition of fluoride or chloride resulted in substantial alterations to the steric and electronic properties of both complexes. Specifically, fluoride addition led to the reduction of the NDI unit through the formation of an (OH<sup>–</sup>) NDI intermediate, while chloride produced a (Cl<sup>–</sup>)···NDI adduct. Both adducts were confirmed by mass spectrometry. The impact of fluoride and chloride addition on the steric and electronic properties of the rhodium and iridium NDI-containing complexes was examined using spectroscopic and computational methods. The presence of either halide significantly enhanced the catalytic activity of the complexes in the hydroboration of terminal alkenes. Finally, we demonstrated that this catalytic enhancement is reversible, with the catalytic process being activated and deactivated by the sequential introduction of excess halide and NOBF<sub>4</sub>. This observation reveals a rare example of a halide-induced redox-switchable catalytic (HIRSC) system.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837385","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 crystals of a monophasic layered copper antimony oxy-sulfate, CuSb6O8(SO4)2, have been grown by the hydrothermal technique. SCXRD study reveals that it crystallizes in triclinic symmetry (SG: P1̅) and is comprised of [SO4] tetrahedra, [SbO4E] trigonal bipyramids, and [CuO4] square planar moieties. No structural phase transition was observed even upon lowering the temperature up to 100 K. The structure consists of [(CuO4)Sb2O5]n-[Sb2O7(SO4)]n layers along [001] and is connected to each other through weak nonbonding interactions via oxygens of the [SO4] tetrahedron and antimony atoms of the adjacent layer. It demonstrates high photocatalytic dye degradation efficiency, achieving 94.68 and 94.72% degradation of Methylene blue and Rhodamine B in the presence of 0.1 mL H2O2, respectively, with recyclability up to the sixth cycle with >90% efficiency. It also exhibits excellent HER activity with a low overpotential of 111 mV at 10 mA/cm2 and a Tafel slope of 157 mV/dec in 1 M KOH. The compound exhibits strong antibacterial activity against several Gram-positive and Gram-negative bacteria as investigated by agar well diffusion method. TG-DTA shows good thermal stability of the compound with a decomposition temperature above 273 °C. The phase purity of the compound and its structural consistency after HER and photocatalysis were confirmed by PXRD analysis.
{"title":"Hydrothermal Synthesis, Crystal Structure, and Thermal Studies of CuSb6O8(SO4)2 and Its Applications toward Dye Management, Hydrogen Evolution Reaction, and Antibacterial Studies","authors":"Sangita Das, Sayantani Paul, Debojyoti Kundu, Nilendu Basak, Nityananda Dutta, Tanmoy Dutta, Uttam Das, Priyabrata Banerjee, Ekramul Islam, Sk Imran Ali","doi":"10.1021/acs.inorgchem.5c00630","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00630","url":null,"abstract":"Single crystals of a monophasic layered copper antimony oxy-sulfate, CuSb<sub>6</sub>O<sub>8</sub>(SO<sub>4</sub>)<sub>2</sub>, have been grown by the hydrothermal technique. SCXRD study reveals that it crystallizes in triclinic symmetry (SG: <i>P</i>1̅) and is comprised of [SO<sub>4</sub>] tetrahedra, [SbO<sub>4</sub>E] trigonal bipyramids, and [CuO<sub>4</sub>] square planar moieties. No structural phase transition was observed even upon lowering the temperature up to 100 K. The structure consists of [(CuO<sub>4</sub>)Sb<sub>2</sub>O<sub>5</sub>]<i><sub>n</sub></i>-[Sb<sub>2</sub>O<sub>7</sub>(SO<sub>4</sub>)]<i><sub>n</sub></i> layers along [001] and is connected to each other through weak nonbonding interactions via oxygens of the [SO<sub>4</sub>] tetrahedron and antimony atoms of the adjacent layer. It demonstrates high photocatalytic dye degradation efficiency, achieving 94.68 and 94.72% degradation of Methylene blue and Rhodamine B in the presence of 0.1 mL H<sub>2</sub>O<sub>2</sub>, respectively, with recyclability up to the sixth cycle with >90% efficiency. It also exhibits excellent HER activity with a low overpotential of 111 mV at 10 mA/cm<sup>2</sup> and a Tafel slope of 157 mV/dec in 1 M KOH. The compound exhibits strong antibacterial activity against several Gram-positive and Gram-negative bacteria as investigated by agar well diffusion method. TG-DTA shows good thermal stability of the compound with a decomposition temperature above 273 °C. The phase purity of the compound and its structural consistency after HER and photocatalysis were confirmed by PXRD analysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837427","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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