Non-precious transition metal-based electrocatalysts with high activity are the promising candidates for substituting Pt- or Ru-based electrocatalyst in hydrogen evolution. In this study, we proposed a core-shell engineering to combine the amorphous NiCoP and crystalline Co2P (a-NiCoP/Co2P@NF), which requires an ultra-low overpotential of only 26 mV to achieve the benchmark current density of 10 mA cm-2. Furthermore, it achieves an industrial-level hydrogen evolution current density of 500 mA cm-2 with excellent stability. The superior catalytic performance and stability can be attributed to the hierarchical amorphous/crystalline interface and the electron-rich interfacial Co sites. Amorphous NiCoP shell can not only protect the internal Co2P from corrosion, but also provide a larger electrochemical active area. Together, the Co2P core provides fast electron transport and promotes H2 emission from the interfacial electron-rich Co sites. This work gives inspiration to the rational design of advanced core-shell structure between amorphous and crystalline.
{"title":"Achieving advanced hydrogen evolution under large current density by amorphous/crystalline core-shell electrocatalyst of a-NiCoP/Co2P","authors":"Xiaodong Chen, Zhi Cheng, Jiao Li, Hongyu Chen, Siyuan Liu, Shuxian Wei, Zhaojie Wang, Xiaoqing Lu","doi":"10.1039/d4dt03258f","DOIUrl":"https://doi.org/10.1039/d4dt03258f","url":null,"abstract":"Non-precious transition metal-based electrocatalysts with high activity are the promising candidates for substituting Pt- or Ru-based electrocatalyst in hydrogen evolution. In this study, we proposed a core-shell engineering to combine the amorphous NiCoP and crystalline Co2P (a-NiCoP/Co2P@NF), which requires an ultra-low overpotential of only 26 mV to achieve the benchmark current density of 10 mA cm-2. Furthermore, it achieves an industrial-level hydrogen evolution current density of 500 mA cm-2 with excellent stability. The superior catalytic performance and stability can be attributed to the hierarchical amorphous/crystalline interface and the electron-rich interfacial Co sites. Amorphous NiCoP shell can not only protect the internal Co2P from corrosion, but also provide a larger electrochemical active area. Together, the Co2P core provides fast electron transport and promotes H2 emission from the interfacial electron-rich Co sites. This work gives inspiration to the rational design of advanced core-shell structure between amorphous and crystalline.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940087","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}
We successfully synthesized perovskite-type RbTaO3 at 1173 K under 4 GPa. RbTaO3 crystalized as a cubic system(Pm-3m space group (SG), a = 4.04108(3) Å) at 300 K in contrast to the orthorhombic perovskite-type RbNbO3 prepared on the same condition. During the cooling process, it reversibly transformed into a tetragonal phase (SG: P4mm) at 270 K, and to an orthorhombic phase (SG: Amm2) at 80 K. Corresponding to the phase transition, the relative permittivity showed a peak at 270 K with a maximum value of approximately 2000 and a kink at 80 K. This transition scheme is analogous to well-known displacement-type ferroelectrics of BaTiO3 and KNbO3. This contrasts with KTaO3, which retains a cubic system and quantum paraelectric properties at the lowest temperature.
{"title":"Dielectric property depends on the crystal structure of perovskite-type RbTaO3 synthesized at high pressure","authors":"Kimitoshi Murase, Jun-ichi Yamaura, Yosuke Hamasaki, Takeharu Kato, Hajime Sagayama, Ayako Yamamoto","doi":"10.1039/d4dt03207a","DOIUrl":"https://doi.org/10.1039/d4dt03207a","url":null,"abstract":"We successfully synthesized perovskite-type RbTaO<small><sub>3</sub></small> at 1173 K under 4 GPa. RbTaO<small><sub>3</sub></small> crystalized as a cubic system(<em>Pm</em>-3<em>m</em> space group (SG), <em>a</em> = 4.04108(3) Å) at 300 K in contrast to the orthorhombic perovskite-type RbNbO<small><sub>3</sub></small> prepared on the same condition. During the cooling process, it reversibly transformed into a tetragonal phase (SG: <em>P</em>4<em>mm</em>) at 270 K, and to an orthorhombic phase (SG: <em>Amm</em>2) at 80 K. Corresponding to the phase transition, the relative permittivity showed a peak at 270 K with a maximum value of approximately 2000 and a kink at 80 K. This transition scheme is analogous to well-known displacement-type ferroelectrics of BaTiO<small><sub>3</sub></small> and KNbO<small><sub>3</sub></small>. This contrasts with KTaO<small><sub>3</sub></small>, which retains a cubic system and quantum paraelectric properties at the lowest temperature.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"83 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940137","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}
Herein, the cobalt ammine complexes are combined with alkali-resistant polyoxoniobates (PONbs) at the molecular level to obtain two new organic-inorganic hybrid Co-containing PONbs with same polyanions but different Co content. The Co-containing PONb with higher Co content exhibits superior hydrogen evolution reaction (HER) activity under high alkaline conditions, which is better than their similar Cu-containing PONb, highlighting the critical role of cobalt in improving HER performance. This study provides a new insight into the relationship between the structural properties of metal complexes during electrocatalysis
{"title":"Organic-Inorganic Hybrid Co-Containing Polyoxoniobates as Hydrogen Evolution Catalyst in Alkaline Media","authors":"Chun-Xia Chen, Shui-Lin Duan, Xiao-Yue Zhang, Rong-Zhi Sun, Pingwei Cai, Cai Sun, Shou-Tian Zheng","doi":"10.1039/d4dt03071k","DOIUrl":"https://doi.org/10.1039/d4dt03071k","url":null,"abstract":"Herein, the cobalt ammine complexes are combined with alkali-resistant polyoxoniobates (PONbs) at the molecular level to obtain two new organic-inorganic hybrid Co-containing PONbs with same polyanions but different Co content. The Co-containing PONb with higher Co content exhibits superior hydrogen evolution reaction (HER) activity under high alkaline conditions, which is better than their similar Cu-containing PONb, highlighting the critical role of cobalt in improving HER performance. This study provides a new insight into the relationship between the structural properties of metal complexes during electrocatalysis","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"67 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940088","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}
William Medroa del Pino, Andres Alejandro Forero Pico, Abhishek V Muralidharan, Manisha Gupta, Eric Rivard
This article provides an alternative pathway towards cyclosilapentenes (e.g., SiH2-iPr and SpiroSi) involving the use of Rieke magnesium to activate the requisite dienes for synthesis. Subsequent metal-mediated dehydrocoupling of this cyclosilapentene and mixtures with another cyclogermapentene gives oligomers with backbone Si-Si (number average molecular weight, Mn = 1.0 kDa) and Si-Ge (Mn = 1.4 kDa) linkages, respectively. UV-irradiation (248 nm) of the abovementioned oligotetrelenes and the molecular spirosilane SpiroSi were examined in solution; while evidence for SixGey-type materials was noted through Raman and EDX spectroscopy, the presence of substantial amorphous carbon as a contaminant was also observed. (TD)-DFT computations studies on the spirosilane SpiroSi provide some insight into the lack of efficient SixGey photodeposition noted in this study.
{"title":"Towards the photodeposition of SixGey-type materials via oligomers of cyclogermapentenes and cyclosilapentenes","authors":"William Medroa del Pino, Andres Alejandro Forero Pico, Abhishek V Muralidharan, Manisha Gupta, Eric Rivard","doi":"10.1039/d4dt03446e","DOIUrl":"https://doi.org/10.1039/d4dt03446e","url":null,"abstract":"This article provides an alternative pathway towards cyclosilapentenes (<em>e.g.</em>, <strong>SiH<small><sub>2</sub></small></strong>-<strong><small><sup>i</sup></small>Pr</strong> and <strong>SpiroSi</strong>) involving the use of Rieke magnesium to activate the requisite dienes for synthesis. Subsequent metal-mediated dehydrocoupling of this cyclosilapentene and mixtures with another cyclogermapentene gives oligomers with backbone Si-Si (number average molecular weight, M<small><sub>n</sub></small> = 1.0 kDa) and Si-Ge (M<small><sub>n</sub></small> = 1.4 kDa) linkages, respectively. UV-irradiation (248 nm) of the abovementioned oligotetrelenes and the molecular spirosilane <strong>SpiroSi</strong> were examined in solution; while evidence for Si<small><sub>x</sub></small>Ge<small><sub>y</sub></small>-type materials was noted through Raman and EDX spectroscopy, the presence of substantial amorphous carbon as a contaminant was also observed. (TD)-DFT computations studies on the spirosilane <strong>SpiroSi</strong> provide some insight into the lack of efficient Si<small><sub>x</sub></small>Ge<small><sub>y</sub></small> photodeposition noted in this study.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937663","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}
Róża Dziewiątkowska, Joanna Krzeszczakowska, Marta Glodek, Michał Łomzik, Damian Plazuk, Anna Maria Makal
Stimuli-responsive molecular materials are highly desirable because of the wide range of their potential applications. In particular, physical properties switching opens application pathways for molecular materials as sensors or actuators. Property switching in solids can be achieved by inducing single-crystal-to-single-crystal (SCSC) phase transitions. Elucidating the mechanisms of such transformations and identifying the factors and (supra)molecular motifs which increase their probability is thus paramount to understanding property switching and materials design. Here we present a new compound, (p-methoxy-phenylacetylide)(triethylphosphine)gold(I) (ArPEt), combining the photoluminescent core of gold(I) acetylide with triethylphosphine that should provide rich conformational landscape and should thus favor SCSC phase transitions. We demonstrate its potential to undergo multiple pressure-induced SCSC transformations at ≈0.5 GPa and ≈2 GPa, the obtainable phases being dependent on the type of applied pressure-transmitting media. We describe structures of high-pressure polymorphs of ArPEt and propose mechanism ('molecular gears') of pressure-induced structural reorganizations based on very high-quality single crystal X-ray diffraction data.
{"title":"Pressure-induced phase transitions in new luminescent gold(I)-arylacetylide","authors":"Róża Dziewiątkowska, Joanna Krzeszczakowska, Marta Glodek, Michał Łomzik, Damian Plazuk, Anna Maria Makal","doi":"10.1039/d4dt03036b","DOIUrl":"https://doi.org/10.1039/d4dt03036b","url":null,"abstract":"Stimuli-responsive molecular materials are highly desirable because of the wide range of their potential applications. In particular, physical properties switching opens application pathways for molecular materials as sensors or actuators. Property switching in solids can be achieved by inducing single-crystal-to-single-crystal (SCSC) phase transitions. Elucidating the mechanisms of such transformations and identifying the factors and (supra)molecular motifs which increase their probability is thus paramount to understanding property switching and materials design. Here we present a new compound, (p-methoxy-phenylacetylide)(triethylphosphine)gold(I) (ArPEt), combining the photoluminescent core of gold(I) acetylide with triethylphosphine that should provide rich conformational landscape and should thus favor SCSC phase transitions. We demonstrate its potential to undergo multiple pressure-induced SCSC transformations at ≈0.5 GPa and ≈2 GPa, the obtainable phases being dependent on the type of applied pressure-transmitting media. We describe structures of high-pressure polymorphs of ArPEt and propose mechanism ('molecular gears') of pressure-induced structural reorganizations based on very high-quality single crystal X-ray diffraction data.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"45 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937171","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}
Although the green light emission of Tb3+ ions is able to be effectively improved by utilizing the energy transfer from Eu2+ to Tb3+ ions, obtaining phosphors with high quantum efficiency still remains as a big problem. Here, we achieved a novel type of apatite structure Ca4La(PO4)3O (CLPO) containing Eu2+ and Tb3+ ions. The CLPO:Eu2+ is capable of effectively excited by the near-ultraviolet light and emits blue light at about 460 nm. The energy transfer from the Eu2+ to Tb3+ ions in CLPO:Eu2+,Tb3+ can be readily constructed by utilizing the energy transfer from the Eu2+ to Tb3+ ions. The optimized phosphor CLPO:0.02Eu2+,0.7Tb3+ has a great internal quantum efficiency of 96.6% and an external quantum efficiency of 64.7%. CLPO:0.02Eu2+,0.7Tb3+, commercially available blue and red phosphors were coupled with a 365 nm chip package to form the WLEDs, presenting a nice Ra value (89.9) and a correlated color temperature (3808 K). Our work points out the avenue to realize novel and efficient green phosphors by selecting suitable hosts and constructing efficient energy transfer.
{"title":"Highly Efficient Green PhosphorCa4La(PO4)3O:Eu2+,Tb3+for white LEDs","authors":"Congcong Fan, Dashuai Sun, Zeyu Lyu, Luhui Zhou, Pengcheng Luo, Zheng Lu, Xiaowei Zhang, Shuai Wei, Hongpeng You","doi":"10.1039/d4dt03241a","DOIUrl":"https://doi.org/10.1039/d4dt03241a","url":null,"abstract":"Although the green light emission of Tb3+ ions is able to be effectively improved by utilizing the energy transfer from Eu2+ to Tb3+ ions, obtaining phosphors with high quantum efficiency still remains as a big problem. Here, we achieved a novel type of apatite structure Ca4La(PO4)3O (CLPO) containing Eu2+ and Tb3+ ions. The CLPO:Eu2+ is capable of effectively excited by the near-ultraviolet light and emits blue light at about 460 nm. The energy transfer from the Eu2+ to Tb3+ ions in CLPO:Eu2+,Tb3+ can be readily constructed by utilizing the energy transfer from the Eu2+ to Tb3+ ions. The optimized phosphor CLPO:0.02Eu2+,0.7Tb3+ has a great internal quantum efficiency of 96.6% and an external quantum efficiency of 64.7%. CLPO:0.02Eu2+,0.7Tb3+, commercially available blue and red phosphors were coupled with a 365 nm chip package to form the WLEDs, presenting a nice Ra value (89.9) and a correlated color temperature (3808 K). Our work points out the avenue to realize novel and efficient green phosphors by selecting suitable hosts and constructing efficient energy transfer.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937126","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}
Pablo Crujeiras, Irene Vázquez-Carballo, ANTONIO SOUSA-PEDRARES
The aza-Wittig reaction was successfully applied to the synthesis of carboranyl-imines, which are difficult to obtain by classical methods. A variety of functionalized carboranyl Schiff bases was obtained proving the great scope of the methodology. All compounds were fully characterized, including the solid-state structures of six of them. The aza-Wittig reaction was modified to permit the synthesis in one step of carboranyl-benzothiazole and carboranyl-benzoselenazoline derivatives. The stability studies show that the carboranyl-imines and benzothiazole promote deboronation to the nido-derivatives, which is achieved by simple reaction with methanol or protic solvents. The structures of the nido-derivatives were also studied by X-ray diffraction. In contrast, the saturated derivatives, amine and benzoselenazoline, do not promote deboronation and are stable in protic solvents.
{"title":"Application of the aza-Wittig reaction for the synthesis of carboranyl Schiff bases, benzothiazoles and benzoselenazolines","authors":"Pablo Crujeiras, Irene Vázquez-Carballo, ANTONIO SOUSA-PEDRARES","doi":"10.1039/d4dt03378g","DOIUrl":"https://doi.org/10.1039/d4dt03378g","url":null,"abstract":"The aza-Wittig reaction was successfully applied to the synthesis of carboranyl-imines, which are difficult to obtain by classical methods. A variety of functionalized carboranyl Schiff bases was obtained proving the great scope of the methodology. All compounds were fully characterized, including the solid-state structures of six of them. The aza-Wittig reaction was modified to permit the synthesis in one step of carboranyl-benzothiazole and carboranyl-benzoselenazoline derivatives. The stability studies show that the carboranyl-imines and benzothiazole promote deboronation to the nido-derivatives, which is achieved by simple reaction with methanol or protic solvents. The structures of the nido-derivatives were also studied by X-ray diffraction. In contrast, the saturated derivatives, amine and benzoselenazoline, do not promote deboronation and are stable in protic solvents.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"76 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937122","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}
In my proposed mechanism of Mo-nitrogenase there are two roles for separate N2 molecules. One N2 diffuses into the reaction zone between Fe2 and Fe6 where a strategic gallery of H atoms can capture N2 to form the Fe-bound HNNH intermediate which is then progressively hydrogenated through intermediates containing HNNH2, NH and NH2 entities and then two NH3 in sequence. The second N2 can be parked in an N2-pocket about 3.2Å from Fe2 or bind end-on at the exo coordination site of Fe2. This second N2 is outside the reaction zone, not exposed to H atom donors, and so is 'non-reducible'. Here density functional calculations using a 485+ atom model describe the thermodynamics for non-reducible N2 moving between the N2-pocket and the exo-Fe2 position, for the resting state and 19 intermediates in the mechanism. The entropy component is estimated and included. The result is that for all intermediates with ligation by H or NHx at the endo-Fe2 position the free energy for association of non-reducible N2 at exo-Fe2 is negative. There remains some uncertainty about the status of exo-Fe2-N2 during the step in which H2 exchanges with the incoming reducible N2, where at least two unbound molecules are present. At Fe2 it is evident that attainment of octahedral coordination stereochemistry dominates the binding thermodynamics for non-reducible N2. Possibilities for experimental support of these computational conclusions are discussed.
{"title":"Understanding non-reducible N2 in the mechanism of Mo-nitrogenase","authors":"Ian Dance","doi":"10.1039/d4dt03146f","DOIUrl":"https://doi.org/10.1039/d4dt03146f","url":null,"abstract":"In my proposed mechanism of Mo-nitrogenase there are two roles for separate N<small><sub>2</sub></small> molecules. One N<small><sub>2</sub></small> diffuses into the reaction zone between Fe2 and Fe6 where a strategic gallery of H atoms can capture N<small><sub>2</sub></small> to form the Fe-bound HNNH intermediate which is then progressively hydrogenated through intermediates containing HNNH<small><sub>2</sub></small>, NH and NH<small><sub>2</sub></small> entities and then two NH<small><sub>3</sub></small> in sequence. The second N<small><sub>2</sub></small> can be parked in an N<small><sub>2</sub></small>-pocket about 3.2Å from Fe2 or bind end-on at the <em>exo</em> coordination site of Fe2. This second N<small><sub>2</sub></small> is outside the reaction zone, not exposed to H atom donors, and so is 'non-reducible'. Here density functional calculations using a 485+ atom model describe the thermodynamics for non-reducible N<small><sub>2</sub></small> moving between the N<small><sub>2</sub></small>-pocket and the <em>exo</em>-Fe2 position, for the resting state and 19 intermediates in the mechanism. The entropy component is estimated and included. The result is that for all intermediates with ligation by H or NH<small><sub>x</sub></small> at the <em>endo</em>-Fe2 position the free energy for association of non-reducible N<small><sub>2</sub></small> at <em>exo</em>-Fe2 is negative. There remains some uncertainty about the status of <em>exo</em>-Fe2-N<small><sub>2</sub></small> during the step in which H<small><sub>2</sub></small> exchanges with the incoming reducible N<small><sub>2</sub></small>, where at least two unbound molecules are present. At Fe2 it is evident that attainment of octahedral coordination stereochemistry dominates the binding thermodynamics for non-reducible N<small><sub>2</sub></small>. Possibilities for experimental support of these computational conclusions are discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"75 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937221","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}
Giammarco Maria Romano, Yschtar Tecla Simonini Steiner, Francesco Bartoli, Luca Conti, Eleonora Macedi, Carla Bazzicalupi, Patrizia Rossi, Paola Paoli, Massimo Innocenti, Andrea Bencini, Matteo Savastano
Correction for ‘Selective binding and fluorescence sensing of Zn(II)/Cd(II) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals’ by Giammarco Maria Romano et al., Dalton Trans., 2025, https://doi.org/10.1039/d4dt02415j.
{"title":"Correction: Selective binding and fluorescence sensing of Zn(II)/Cd(II) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals","authors":"Giammarco Maria Romano, Yschtar Tecla Simonini Steiner, Francesco Bartoli, Luca Conti, Eleonora Macedi, Carla Bazzicalupi, Patrizia Rossi, Paola Paoli, Massimo Innocenti, Andrea Bencini, Matteo Savastano","doi":"10.1039/d5dt90009c","DOIUrl":"https://doi.org/10.1039/d5dt90009c","url":null,"abstract":"Correction for ‘Selective binding and fluorescence sensing of Zn(<small>II</small>)/Cd(<small>II</small>) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals’ by Giammarco Maria Romano <em>et al.</em>, <em>Dalton Trans.</em>, 2025, https://doi.org/10.1039/d4dt02415j.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"3 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937123","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}
JOSE DE JESUS VELAZQUEZ GARCIA, Luis de los Santos Valladares, Crispin Barnes, Sandra König, Michael Fröba, Volodymyr Baran, Bassima Knjo, Faegheh Khademhir, Aliyenur Ekineken, Fabienne Hain, Evke Carstens, Tom Spillner, Lina Maria Asprilla Herrera, Weronika Łukaszczyk, Simone Techert
Two Co(II) mixed-ligand metal-organic frameworks (MOFs) based on 2-methylimidazole and trimesate were synthesised at room temperature. The structure and properties of the two MOFs, named mDESY-1 and mDESY-2, were verified by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), SQUID magnetic susceptibility and N2 adsorption. The structural analysis indicates that mDESY-1 is a 3-D ionic framework with 2-methyl-1H-imidazol-3-ium counterions residing in its pores, while mDESY- 2 is a 2D neutral framework isostructural to ITH-1, with water as co-crystallising solvent. PXRD data demonstrated that mDESY-1 exhibit better crystallinity than mDESY-2. Magnetic measurements indicate that both MOFs are paramagnetic with a weak ferromagnetic transition above room temperature. Although both structures suggest the presence of voids, N2 adsorption data confirmed that these voids are not accessible in either MOF. Nevertheless, mDESY-1 was capable of encapsulating azobenzene during synthesis, which can be observed via SCXRD. The encapsulated molecules were then slowly released in ethanol, with a release of up-to 30mg of azobenzene per g of MOF in a period of 60 days.
{"title":"Neutral and ionic Co(II) Metal-Organic Frameworks with 2-Methylimidazole and Trimesate: Design and Evaluation for Molecule Encapsulation and Slow Release","authors":"JOSE DE JESUS VELAZQUEZ GARCIA, Luis de los Santos Valladares, Crispin Barnes, Sandra König, Michael Fröba, Volodymyr Baran, Bassima Knjo, Faegheh Khademhir, Aliyenur Ekineken, Fabienne Hain, Evke Carstens, Tom Spillner, Lina Maria Asprilla Herrera, Weronika Łukaszczyk, Simone Techert","doi":"10.1039/d4dt02679a","DOIUrl":"https://doi.org/10.1039/d4dt02679a","url":null,"abstract":"Two Co(II) mixed-ligand metal-organic frameworks (MOFs) based on 2-methylimidazole and trimesate were synthesised at room temperature. The structure and properties of the two MOFs, named mDESY-1 and mDESY-2, were verified by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), SQUID magnetic susceptibility and N2 adsorption. The structural analysis indicates that mDESY-1 is a 3-D ionic framework with 2-methyl-1H-imidazol-3-ium counterions residing in its pores, while mDESY- 2 is a 2D neutral framework isostructural to ITH-1, with water as co-crystallising solvent. PXRD data demonstrated that mDESY-1 exhibit better crystallinity than mDESY-2. Magnetic measurements indicate that both MOFs are paramagnetic with a weak ferromagnetic transition above room temperature. Although both structures suggest the presence of voids, N2 adsorption data confirmed that these voids are not accessible in either MOF. Nevertheless, mDESY-1 was capable of encapsulating azobenzene during synthesis, which can be observed via SCXRD. The encapsulated molecules were then slowly released in ethanol, with a release of up-to 30mg of azobenzene per g of MOF in a period of 60 days.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"44 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940089","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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