Pub Date : 2025-03-06DOI: 10.1021/acs.inorgchem.4c05296
Lifeng Shi, Mixiang Qi, Lehua Han, Wenya Liang, Alexander M. Kirillov, Wei Dou, Weisheng Liu, Lizi Yang
There is an increasing demand for the development of lanthanide metal–organic frameworks and derived multifunctional materials. The functional properties of such compounds are influenced by the arrangement of various Lewis basic sites or structural configurations of the ligands. In this study, a series of isostructural Ln-MOFs containing a phosphine-dicarboxylate ligand, [Ln(HL)(L)(DMF)]·DMF (where H2L = 5-(diphenylphosphanyl)isophthalic acid, Ln = Tb3+ (1), Eu3+ (2), Gd3+ (3), Ce3+ (4), and Nd3+ (5)), was synthesized under solvothermal conditions and characterized in detail. Among the obtained compounds, Tb-MOF 1 demonstrated excellent luminescent properties with a high quantum yield (90.45%) and considerable lifetime (1266 μs). Furthermore, 1 acts as a unique luminescent Ln sensor for 4-formylphenylboronic acid and 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole, exhibiting low detection limits of 1.38 and 3.62 mM, respectively. Additionally, Nd-MOF 5 acts as an efficient catalyst for coupling carbon dioxide to epoxy compounds, resulting in high conversion rates (up to 96%). This study further extends the growing family of Ln-MOFs and provides insights for preparing multifunctional materials through the modification of organic ligands with specific functional groups.
{"title":"Bifunctional Lanthanide MOFs with Phosphorus Ligands: Selective Luminescent Detection of Borides and CO2 Conversion","authors":"Lifeng Shi, Mixiang Qi, Lehua Han, Wenya Liang, Alexander M. Kirillov, Wei Dou, Weisheng Liu, Lizi Yang","doi":"10.1021/acs.inorgchem.4c05296","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05296","url":null,"abstract":"There is an increasing demand for the development of lanthanide metal–organic frameworks and derived multifunctional materials. The functional properties of such compounds are influenced by the arrangement of various Lewis basic sites or structural configurations of the ligands. In this study, a series of isostructural Ln-MOFs containing a phosphine-dicarboxylate ligand, [Ln(HL)(L)(DMF)]·DMF (where H<sub>2</sub>L = 5-(diphenylphosphanyl)isophthalic acid, Ln = Tb<sup>3+</sup> (<b>1</b>), Eu<sup>3+</sup> (<b>2</b>), Gd<sup>3+</sup> (<b>3</b>), Ce<sup>3+</sup> (<b>4</b>), and Nd<sup>3+</sup> (<b>5</b>)), was synthesized under solvothermal conditions and characterized in detail. Among the obtained compounds, Tb-MOF <b>1</b> demonstrated excellent luminescent properties with a high quantum yield (90.45%) and considerable lifetime (1266 μs). Furthermore, <b>1</b> acts as a unique luminescent Ln sensor for 4-formylphenylboronic acid and 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole, exhibiting low detection limits of 1.38 and 3.62 mM, respectively. Additionally, Nd-MOF <b>5</b> acts as an efficient catalyst for coupling carbon dioxide to epoxy compounds, resulting in high conversion rates (up to 96%). This study further extends the growing family of Ln-MOFs and provides insights for preparing multifunctional materials through the modification of organic ligands with specific functional groups.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570166","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}
Inorganic pigments offer excellent potential because of their resilience in a variety of environments, and high-reflectance near-infrared (NIR) pigments are a useful tactic to reduce the heat island effect. Nonetheless, the design of inorganic pigments is still dominated by serendipity, and it has never been easy to come up with logical designs for NIR reflective inorganic pigments. By modifying the coordination environment of Ni2+ using the generic formulas LiMg1–xNixPO4 and LiZn1–xNixPO4 (x = 0.02–0.12), yellow and violet pigments were successfully developed in this research. According to structural investigations, Ni2+ effectively replaced Mg2+ and Zn2+ to create [NiO4] tetrahedra and [NiO6] octahedra, causing an orderly alteration of the cell parameters. The diverse transition modes of Ni2+ in various crystal fields are the cause of the noticeable color changes caused by the solid solutions, according to the UV–vis-NIR spectra. Furthermore, both pigments have outstanding NIR solar reflectivity and coloring capabilities. Both the sample-colored coatings and the coating’s surface under infrared light demonstrated lower temperatures than the commercial pigmented coatings for thermal insulation applications.
{"title":"Rational Design of Near-Infrared Reflective Pigments by Adjusting the Ni2+ Coordination Environment","authors":"Jiawan Wei, Yi Wu, Kangzhen Sun, Pengzhai Li, Qiuli Fang, Yin Zhang","doi":"10.1021/acs.inorgchem.5c00230","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00230","url":null,"abstract":"Inorganic pigments offer excellent potential because of their resilience in a variety of environments, and high-reflectance near-infrared (NIR) pigments are a useful tactic to reduce the heat island effect. Nonetheless, the design of inorganic pigments is still dominated by serendipity, and it has never been easy to come up with logical designs for NIR reflective inorganic pigments. By modifying the coordination environment of Ni<sup>2+</sup> using the generic formulas LiMg<sub>1–<i>x</i></sub>Ni<sub><i>x</i></sub>PO<sub>4</sub> and LiZn<sub>1–<i>x</i></sub>Ni<sub><i>x</i></sub>PO<sub>4</sub> (<i>x</i> = 0.02–0.12), yellow and violet pigments were successfully developed in this research. According to structural investigations, Ni<sup>2+</sup> effectively replaced Mg<sup>2+</sup> and Zn<sup>2+</sup> to create [NiO<sub>4</sub>] tetrahedra and [NiO<sub>6</sub>] octahedra, causing an orderly alteration of the cell parameters. The diverse transition modes of Ni<sup>2+</sup> in various crystal fields are the cause of the noticeable color changes caused by the solid solutions, according to the UV–vis-NIR spectra. Furthermore, both pigments have outstanding NIR solar reflectivity and coloring capabilities. Both the sample-colored coatings and the coating’s surface under infrared light demonstrated lower temperatures than the commercial pigmented coatings for thermal insulation applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570165","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.4c04731
Barbara Chiavarino, Lucretia Rotari, Maria Elisa Crestoni, Davide Corinti, Debora Scuderi, Jean-Yves Salpin
Ionic complexes containing the nucleobase adenine and either carboplatin (CarboPt) or oxaliplatin (OxaliPt) were generated in solution and subsequently studied in the gas phase by combining tandem mass spectrometry, infrared multiple photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The protonated complexes of the general formula [Pt drug+H+adenine]+ were first analyzed by collision-induced dissociation (CID). Their CID mass spectra show only one fragment, corresponding to the loss of neutral adenine. The structure of these complexes was elucidated by comparing their IRMPD spectra recorded in the fingerprint and H-X stretching ranges with DFT-calculated IR spectra. Unexpectedly, the IRMPD spectra of both complexes were not consistent with the calculated vibrational spectra of structures characterized by direct platinum–adenine coordination. All spectroscopic evidence suggest that each sampled [Pt drug+H+adenine]+ ion population comprises multiple proton-bound complexes stabilized by hydrogen bonds between the drug carboxylate groups and protonated adenine. Interestingly, while calculations support an external binding scheme in protonated adenine-oxaliplatin complexes, in the case of carboplatin, a direct monodentate interaction of Pt with N1, N3, or N7 positions of adenine turns out to be energetically favored. This study adds further evidence of the intrinsic lower affinity of platinum for adenine relative to guanine.
{"title":"Encounter Complex of Adenine with Carboplatin and Oxaliplatin Anticancer Drugs Elucidated by IRMPD Spectroscopy and Theoretical Study","authors":"Barbara Chiavarino, Lucretia Rotari, Maria Elisa Crestoni, Davide Corinti, Debora Scuderi, Jean-Yves Salpin","doi":"10.1021/acs.inorgchem.4c04731","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04731","url":null,"abstract":"Ionic complexes containing the nucleobase adenine and either carboplatin (CarboPt) or oxaliplatin (OxaliPt) were generated in solution and subsequently studied in the gas phase by combining tandem mass spectrometry, infrared multiple photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The protonated complexes of the general formula [Pt drug+H+adenine]<sup>+</sup> were first analyzed by collision-induced dissociation (CID). Their CID mass spectra show only one fragment, corresponding to the loss of neutral adenine. The structure of these complexes was elucidated by comparing their IRMPD spectra recorded in the fingerprint and H-X stretching ranges with DFT-calculated IR spectra. Unexpectedly, the IRMPD spectra of both complexes were not consistent with the calculated vibrational spectra of structures characterized by direct platinum–adenine coordination. All spectroscopic evidence suggest that each sampled [Pt drug+H+adenine]<sup>+</sup> ion population comprises multiple proton-bound complexes stabilized by hydrogen bonds between the drug carboxylate groups and protonated adenine. Interestingly, while calculations support an external binding scheme in protonated adenine-oxaliplatin complexes, in the case of carboplatin, a direct monodentate interaction of Pt with N1, N3, or N7 positions of adenine turns out to be energetically favored. This study adds further evidence of the intrinsic lower affinity of platinum for adenine relative to guanine.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"131 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561140","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.4c04469
Suo-Shu Zhang, Guang-Liang Wu, Zhao-Ting Yang, Shu-Yu Wang, Xun Ma, Yan-Ting Chen, Yuan-Yuan Guo, Lin Du, Qi-Hua Zhao
This study demonstrates an effective strategy to enhance proton conductivity by synthesizing 2 three-dimensional metal–organic frameworks (MOFs), [Zn(DTD22)]n (MOF 1) and [Cd2(DTD22)2]n (MOF 2), (DTD22 = 4,4″-diamino-[1,1′:4′,1″-terphenyl]-2,2″-dicarboxylic acid). The DTD22 ligand used formed a continuous hydrogen-bonding network in the structure, constructing excellent hydrophilic channels. MOF 1 and MOF 2 were further postsynthesized and modified (PSM) by Schiff base reaction, and 4-chloro-3-formylbenzenesulfonic acid ligands containing −SO3H and −Cl were successfully introduced into the framework to form PSM-MOF 1 and PSM-MOF 2. Experiments showed that this modification significantly enhanced the proton conductivity of the materials, especially at 90 °C and 98% RH: PSM-MOF 1 (2.38 × 10–1 S·cm–1) and PSM-MOF 2 (3.50 × 10–1 S·cm–1). In comparison, the conductivities of unmodified MOF 1 and MOF 2 were 8.55 × 10–2 S·cm–1 and 9.50 × 10–5 S·cm–1, respectively. The present study demonstrates that the proton conductivity of MOFs can be effectively enhanced by the covalent postmodification method, which provides a new idea for the application of MOFs.
{"title":"High Proton Conductivity Enhancement Obtained by a Covalent Postsynthesis Modification Approach for Two Metal–Organic Frameworks","authors":"Suo-Shu Zhang, Guang-Liang Wu, Zhao-Ting Yang, Shu-Yu Wang, Xun Ma, Yan-Ting Chen, Yuan-Yuan Guo, Lin Du, Qi-Hua Zhao","doi":"10.1021/acs.inorgchem.4c04469","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04469","url":null,"abstract":"This study demonstrates an effective strategy to enhance proton conductivity by synthesizing 2 three-dimensional metal–organic frameworks (MOFs), [Zn(DTD22)]<sub><i>n</i></sub> (MOF 1) and [Cd<sub>2</sub>(DTD22)<sub>2</sub>]<sub><i>n</i></sub> (MOF 2), (DTD22 = 4,4″-diamino-[1,1′:4′,1″-terphenyl]-2,2″-dicarboxylic acid). The DTD22 ligand used formed a continuous hydrogen-bonding network in the structure, constructing excellent hydrophilic channels. MOF 1 and MOF 2 were further postsynthesized and modified (PSM) by Schiff base reaction, and 4-chloro-3-formylbenzenesulfonic acid ligands containing −SO<sub>3</sub>H and −Cl were successfully introduced into the framework to form PSM-MOF 1 and PSM-MOF 2. Experiments showed that this modification significantly enhanced the proton conductivity of the materials, especially at 90 °C and 98% RH: PSM-MOF 1 (2.38 × 10<sup>–1</sup> S·cm<sup>–1</sup>) and PSM-MOF 2 (3.50 × 10<sup>–1</sup> S·cm<sup>–1</sup>). In comparison, the conductivities of unmodified MOF 1 and MOF 2 were 8.55 × 10<sup>–2</sup> S·cm<sup>–1</sup> and 9.50 × 10<sup>–5</sup> S·cm<sup>–1</sup>, respectively. The present study demonstrates that the proton conductivity of MOFs can be effectively enhanced by the covalent postmodification method, which provides a new idea for the application of MOFs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561139","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.5c00476
Xue Cao, Xuemei Shi, Piao Tang, Xin Wen, Jindong Chen, Guang Peng, Ning Ye
Herein, a series of unprecedented alkaline earth metal methylsulfonate halides, M(SO3CH3)X·nH2O (M = Sr, Ba; X = Cl, Br, I; n = 2, 4), and Ba2(SO3CH3)3I·4H2O were synthesized. They all feature two-dimensional (2D) layered structures with halogen elements inserted between the 2D layers constructed by metal ions and [SO3CH3] groups, which are suitable for exploring the influence of halogens on their refractive index. The refractive indexes both parallel and (almost) perpendicular to the 2D layers were calculated through theoretical calculations. We found that the nonpolar halogens exhibited different enhancement in the two directions. The result may guide regulating the birefringence properties of such 2D crystal materials. Besides, the ultraviolet (UV) cutoff edge of Sr(SO3CH3)Cl·4H2O and Ba(SO3CH3)Cl·4H2O can reach 183 and 184 nm, respectively, indicating their potential application in the deep-UV region.
{"title":"Regulation of Refractive Index by Halogens in Two-Dimensional Layered Methylsulfonate Halides","authors":"Xue Cao, Xuemei Shi, Piao Tang, Xin Wen, Jindong Chen, Guang Peng, Ning Ye","doi":"10.1021/acs.inorgchem.5c00476","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00476","url":null,"abstract":"Herein, a series of unprecedented alkaline earth metal methylsulfonate halides, M(SO<sub>3</sub>CH<sub>3</sub>)X·<i>n</i>H<sub>2</sub>O (M = Sr, Ba; X = Cl, Br, I; <i>n</i> = 2, 4), and Ba<sub>2</sub>(SO<sub>3</sub>CH<sub>3</sub>)<sub>3</sub>I·4H<sub>2</sub>O were synthesized. They all feature two-dimensional (2D) layered structures with halogen elements inserted between the 2D layers constructed by metal ions and [SO<sub>3</sub>CH<sub>3</sub>] groups, which are suitable for exploring the influence of halogens on their refractive index. The refractive indexes both parallel and (almost) perpendicular to the 2D layers were calculated through theoretical calculations. We found that the nonpolar halogens exhibited different enhancement in the two directions. The result may guide regulating the birefringence properties of such 2D crystal materials. Besides, the ultraviolet (UV) cutoff edge of Sr(SO<sub>3</sub>CH<sub>3</sub>)Cl·4H<sub>2</sub>O and Ba(SO<sub>3</sub>CH<sub>3</sub>)Cl·4H<sub>2</sub>O can reach 183 and 184 nm, respectively, indicating their potential application in the deep-UV region.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561143","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}
Using chiral amino acids as terminal ligands, colorless crystals of Cd3(SCN)6(l-C5H9NO3)2(H2O)2·0.5CH3OH (1) and Cd(SCN)2(l-C6H14N4O2)2 (2) were obtained by a solvent evaporation method. Compound 1 has a layered structure with a moderate second harmonic generation (SHG) efficiency (0.2 × KH2PO4) and a large birefringence (0.301 at 546 nm). Compound 2 features a molecular structure with a strong SHG efficiency (2.67 × KH2PO4) and a wide band gap (4.84 eV). Theoretical calculations were performed to elucidate the origin of the large SHG response of compound 2.
{"title":"Second-Harmonic Generation in Organic–Inorganic Hybrid Cadmium Thiocyanates Containing Terminal Amino Acids","authors":"Yue Zhou, Gangji Yi, Qinglan Zhong, Guohong Zou, Hongmei Zeng, Zhien Lin","doi":"10.1021/acs.inorgchem.5c00633","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00633","url":null,"abstract":"Using chiral amino acids as terminal ligands, colorless crystals of Cd<sub>3</sub>(SCN)<sub>6</sub>(<span>l</span>-C<sub>5</sub>H<sub>9</sub>NO<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>·0.5CH<sub>3</sub>OH (<b>1</b>) and Cd(SCN)<sub>2</sub>(<span>l</span>-C<sub>6</sub>H<sub>14</sub>N<sub>4</sub>O<sub>2</sub>)<sub>2</sub> (<b>2</b>) were obtained by a solvent evaporation method. Compound <b>1</b> has a layered structure with a moderate second harmonic generation (SHG) efficiency (0.2 × KH<sub>2</sub>PO<sub>4</sub>) and a large birefringence (0.301 at 546 nm). Compound <b>2</b> features a molecular structure with a strong SHG efficiency (2.67 × KH<sub>2</sub>PO<sub>4</sub>) and a wide band gap (4.84 eV). Theoretical calculations were performed to elucidate the origin of the large SHG response of compound <b>2</b>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561142","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.4c05111
Bartosz Orzel, Malgorzata Ostrowska, Slawomir Potocki, Maria Antonietta Zoroddu, Henryk Kozlowski, Massimiliano Peana, Elzbieta Gumienna-Kontecka
Often necessary for efficient Fe(II) trafficking into bacterial cell, the Feo system is a vital transporter for many pathogenic bacteria and indispensable for proper development and survival in the host organism during infection. In this work, we present the metal-binding characteristics of the peptidic models of two putative Fe(II)-binding sites of E. coliFeoB: L1 (Ac-477IMRGEATPFVMELPVYHVPH496–CONH2) being a fragment of the Core CFeoB region located between the transmembrane helices and L2 (Ac-38VERKEG43-CONH2), which represents the ExxE motif found within the NFeoB domain. With a variety of physicochemical methods, such as potentiometry, mass spectrometry, NMR, and EPR spectroscopy, we have determined the stability constants and metal-binding residues for the complexes of Fe(II), Mn(II), and Zn(II) with two ligands, L1 and L2, acting as models for the Core CFeoB and ExxE motif. We compare their affinities toward the studied metal ions with the previously studied C-terminal part of the protein and discuss a possible role in metal trafficking by the whole protein.
{"title":"The Coordination Chemistry of Two Peptidic Models of NFeoB and Core CFeoB Regions of FeoB Protein: Complexes of Fe(II), Mn(II), and Zn(II)","authors":"Bartosz Orzel, Malgorzata Ostrowska, Slawomir Potocki, Maria Antonietta Zoroddu, Henryk Kozlowski, Massimiliano Peana, Elzbieta Gumienna-Kontecka","doi":"10.1021/acs.inorgchem.4c05111","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05111","url":null,"abstract":"Often necessary for efficient Fe(II) trafficking into bacterial cell, the Feo system is a vital transporter for many pathogenic bacteria and indispensable for proper development and survival in the host organism during infection. In this work, we present the metal-binding characteristics of the peptidic models of two putative Fe(II)-binding sites of <i>E. coli</i>FeoB: <b>L1</b> (Ac-<sub>477</sub>IMRGEATPFVMELPVYHVPH<sub>496</sub>–CONH<sub>2</sub>) being a fragment of the Core CFeoB region located between the transmembrane helices and <b>L2 (</b>Ac-<sub>38</sub>VERKEG<sub>43</sub>-CONH<sub>2</sub>), which represents the ExxE motif found within the NFeoB domain. With a variety of physicochemical methods, such as potentiometry, mass spectrometry, NMR, and EPR spectroscopy, we have determined the stability constants and metal-binding residues for the complexes of Fe(II), Mn(II), and Zn(II) with two ligands, <b>L1</b> and <b>L2</b>, acting as models for the Core CFeoB and ExxE motif. We compare their affinities toward the studied metal ions with the previously studied C-terminal part of the protein and discuss a possible role in metal trafficking by the whole protein.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570164","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.5c00444
Qingyu Zhou, Xinming Wang, Shuang Rong, Gang Li, Qiushuang Jiang, Haijun Pang, Huiyuan Ma
The electrochemical conversion of nitrate to ammonia has garnered growing attention, as it aims to reduce carbon emissions and promote environmental sustainability. Nevertheless, developing an electrocatalyst that exhibits outstanding activity, selectivity, and stability is still a significant challenge. Here, we report three Anderson-type polyoxometalates (POMs)-modified cobalt metal–organic framework (Co-MOF), namely, Co-MOF/MMo6 (M = Fe, Co, Ni) composite electrocatalyst, fabricated using an easy standing method. Among them, POMs not only facilitated the formation of lamellar structures with a high specific surface area of Co-MOF as a morphology regulator but also contributed to electron transfer between Co-MOF as an electron-rich cluster, achieving an enhancement in the catalytic performance of NO3RR to NH3. In particular, Co-MOF/NiMo6 exhibits NO3RR performance with maximal Faradaic efficiency of 98.2% at −0.8 V vs the reverse hydrogen electrode (vs reversible hydrogen electrode (RHE)) and NH3 yield rate of up to 10.88 mg h–1 mgcat.–1, better than most previously reported MOF-based catalysts. By in situ spectrometric measurement, we demonstrate that the NH3 formation via a kinetically favored pathway of NO3– → *NO3 → *NO2 → *NO → *NH2OH → *NH3. This work indicates the considerable potential of POM-based MOF materials for the electrochemical NO3RR to NH3.
{"title":"Efficient Electrocatalytic Conversion of Nitrate in Water with Anderson-Type Polyoxometalate-Modified Co-MOF","authors":"Qingyu Zhou, Xinming Wang, Shuang Rong, Gang Li, Qiushuang Jiang, Haijun Pang, Huiyuan Ma","doi":"10.1021/acs.inorgchem.5c00444","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00444","url":null,"abstract":"The electrochemical conversion of nitrate to ammonia has garnered growing attention, as it aims to reduce carbon emissions and promote environmental sustainability. Nevertheless, developing an electrocatalyst that exhibits outstanding activity, selectivity, and stability is still a significant challenge. Here, we report three Anderson-type polyoxometalates (POMs)-modified cobalt metal–organic framework (Co-MOF), namely, Co-MOF/MMo<sub>6</sub> (M = Fe, Co, Ni) composite electrocatalyst, fabricated using an easy standing method. Among them, POMs not only facilitated the formation of lamellar structures with a high specific surface area of Co-MOF as a morphology regulator but also contributed to electron transfer between Co-MOF as an electron-rich cluster, achieving an enhancement in the catalytic performance of NO<sub>3</sub>RR to NH<sub>3</sub>. In particular, Co-MOF/NiMo<sub>6</sub> exhibits NO<sub>3</sub>RR performance with maximal Faradaic efficiency of 98.2% at −0.8 V vs the reverse hydrogen electrode (vs reversible hydrogen electrode (RHE)) and NH<sub>3</sub> yield rate of up to 10.88 mg h<sup>–1</sup> mg<sub>cat.</sub><sup>–1</sup>, better than most previously reported MOF-based catalysts. By in situ spectrometric measurement, we demonstrate that the NH<sub>3</sub> formation via a kinetically favored pathway of NO<sub>3</sub><sup>–</sup> → *NO<sub>3</sub> → *NO<sub>2</sub> → *NO → *NH<sub>2</sub>OH → *NH<sub>3</sub>. This work indicates the considerable potential of POM-based MOF materials for the electrochemical NO<sub>3</sub>RR to NH<sub>3</sub>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570169","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 : 2025-03-06DOI: 10.1021/acs.inorgchem.5c00066
Zilong Chen, Bingliang Cheng, Abudukadi Tudi, Xiaojing Li, Zhihua Yang, Fangfang Zhang, Shilie Pan
Three new metal borates containing d10 cations, namely, Li4PbZn3B12O24, Na2Cd2B8O15, and K2Sr4ZnB10O19(CO3)2, were synthesized using the flux method. K2Sr4ZnB10O19(CO3)2 is the first Zn-containing borate carbonate and has an unprecedented fundamental building block, [B10O22]. Furthermore, experimental and first-principles theoretical studies were performed.
{"title":"Three Cases of Borates with Different Dimensional Frameworks Induced by Metal Cations","authors":"Zilong Chen, Bingliang Cheng, Abudukadi Tudi, Xiaojing Li, Zhihua Yang, Fangfang Zhang, Shilie Pan","doi":"10.1021/acs.inorgchem.5c00066","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00066","url":null,"abstract":"Three new metal borates containing d<sup>10</sup> cations, namely, Li<sub>4</sub>PbZn<sub>3</sub>B<sub>12</sub>O<sub>24</sub>, Na<sub>2</sub>Cd<sub>2</sub>B<sub>8</sub>O<sub>15,</sub> and K<sub>2</sub>Sr<sub>4</sub>ZnB<sub>10</sub>O<sub>19</sub>(CO<sub>3</sub>)<sub>2</sub>, were synthesized using the flux method. K<sub>2</sub>Sr<sub>4</sub>ZnB<sub>10</sub>O<sub>19</sub>(CO<sub>3</sub>)<sub>2</sub> is the first Zn-containing borate carbonate and has an unprecedented fundamental building block, [B<sub>10</sub>O<sub>22</sub>]. Furthermore, experimental and first-principles theoretical studies were performed.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561141","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 : 2025-03-05DOI: 10.1021/acs.inorgchem.4c05225
Sibo Chetry, Prantik Sarkar, Volodymyr Bon, Muhammad Fernadi Lukman, Andreas Pöppl, Michael Hirscher, Stefan Kaskel, Harald Krautscheid
A Cu2 paddle wheel-based metal–organic framework, [Cu2(trz-ia)2] (trz-ia2– = 5-(4H-1,2,4-triazol-4-yl) isophthalate), is investigated for hydrogen adsorption and hydrogen isotopologue separation. Its ultramicroporous structure with pore diameters ranging from 0.35 to 0.53 nm allows for strong interactions with dihydrogen molecules, resulting in steep H2 uptake and heat of adsorption Qads = 9.7 kJ mol–1. Notably, the hydrogen density inside the pores is 43.9 g L–1 at 77 K and 100 kPa. Thermal desorption spectroscopy (TDS) after exposure to a H2/D2 mixture indicates dihydrogen isotopologue separation with a selectivity of S = 6 at 30 K and a high uptake of D2. These findings are compared with numerous other metal–organic frameworks (MOFs) and related to their pore size.
{"title":"[Cu2(trz-ia)2]─An Ultramicroporous Cu2 Paddle Wheel Triazolyl Isophthalate MOF: A Comparative Study of Its Properties in Dihydrogen Adsorption and Isotopologue Separation","authors":"Sibo Chetry, Prantik Sarkar, Volodymyr Bon, Muhammad Fernadi Lukman, Andreas Pöppl, Michael Hirscher, Stefan Kaskel, Harald Krautscheid","doi":"10.1021/acs.inorgchem.4c05225","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05225","url":null,"abstract":"A Cu<sub>2</sub> paddle wheel-based metal–organic framework, [Cu<sub>2</sub>(trz-ia)<sub>2</sub>] (trz-ia<sup>2–</sup> = 5-(4<i>H</i>-1,2,4-triazol-4-yl) isophthalate), is investigated for hydrogen adsorption and hydrogen isotopologue separation. Its ultramicroporous structure with pore diameters ranging from 0.35 to 0.53 nm allows for strong interactions with dihydrogen molecules, resulting in steep H<sub>2</sub> uptake and heat of adsorption <i>Q</i><sub>ads</sub> = 9.7 kJ mol<sup>–1</sup>. Notably, the hydrogen density inside the pores is 43.9 g L<sup>–1</sup> at 77 K and 100 kPa. Thermal desorption spectroscopy (TDS) after exposure to a H<sub>2</sub>/D<sub>2</sub> mixture indicates dihydrogen isotopologue separation with a selectivity of <i>S</i> = 6 at 30 K and a high uptake of D<sub>2</sub>. These findings are compared with numerous other metal–organic frameworks (MOFs) and related to their pore size.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"86 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143545888","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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