Pub Date : 2024-10-22DOI: 10.1021/acs.inorgchem.4c03868
Xu-Dong Xue, Shi-Cheng Wang, Meng-Yang Li, Zheng Wang
In recent years, metal–organic framework (MOF) materials with long persistent luminescence (LPL) have inspired extensive attention and presented various applications in security systems, information anticounterfeiting, and biological imaging fields. However, obtaining LPL materials with ultralong lifetime remains challenging. Halogen atoms, as nonmetallic elements existing in the frameworks, can not only induce the heavy-atom effect, effectively enhancing spin–orbit coupling and promoting intersystem crossing (ISC) processes, but also suppress non-radiative transition of the triplet states through the intra- and intermolecular interactions. Specifically, fluorine atoms with the strongest electronegativity may form intermolecular aggregate interlockings through halogen-bonding interactions that restrict molecular motions and vibrations, thereby improving phosphorescent lifetime. With the aforementioned considerations, two distinct types of MOFs with/without fluorine atoms (namely, Ca-MOF and 5FCa-MOF) were synthesized. Notably, by introducing fluorine atoms into MOFs, fluorine-induced intermolecular aggregate interlockings effectively enhanced the phosphorescent lifetime of 5FCa-MOF exceeding 264 ms compared to that of Ca-MOF (103.94 ms). Remarkably, both MOFs displayed bright LPL to the naked eye after removal of the irradiation source, especially 5FCa-MOF which can last for about 2 s. By introducing fluorine atoms, 5FCa-MOF exhibits greatly enhanced ISC with a rate constant up to 4.1 × 106 s–1 and suppressed non-radiative decay down to 3.73 s–1, thereby extending the LPL time. The thus obtained LPL provides potential in information encryption, security systems, optical anticounterfeiting, and so on.
{"title":"Ultralong Room-Temperature Phosphorescence in Ca(II) Metal–Organic Frameworks Based on Nicotinic Acid Ligands","authors":"Xu-Dong Xue, Shi-Cheng Wang, Meng-Yang Li, Zheng Wang","doi":"10.1021/acs.inorgchem.4c03868","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03868","url":null,"abstract":"In recent years, metal–organic framework (MOF) materials with long persistent luminescence (LPL) have inspired extensive attention and presented various applications in security systems, information anticounterfeiting, and biological imaging fields. However, obtaining LPL materials with ultralong lifetime remains challenging. Halogen atoms, as nonmetallic elements existing in the frameworks, can not only induce the heavy-atom effect, effectively enhancing spin–orbit coupling and promoting intersystem crossing (ISC) processes, but also suppress non-radiative transition of the triplet states through the intra- and intermolecular interactions. Specifically, fluorine atoms with the strongest electronegativity may form intermolecular aggregate interlockings through halogen-bonding interactions that restrict molecular motions and vibrations, thereby improving phosphorescent lifetime. With the aforementioned considerations, two distinct types of MOFs with/without fluorine atoms (namely, Ca-MOF and 5FCa-MOF) were synthesized. Notably, by introducing fluorine atoms into MOFs, fluorine-induced intermolecular aggregate interlockings effectively enhanced the phosphorescent lifetime of 5FCa-MOF exceeding 264 ms compared to that of Ca-MOF (103.94 ms). Remarkably, both MOFs displayed bright LPL to the naked eye after removal of the irradiation source, especially 5FCa-MOF which can last for about 2 s. By introducing fluorine atoms, 5FCa-MOF exhibits greatly enhanced ISC with a rate constant up to 4.1 × 10<sup>6</sup> s<sup>–1</sup> and suppressed non-radiative decay down to 3.73 s<sup>–1</sup>, thereby extending the LPL time. The thus obtained LPL provides potential in information encryption, security systems, optical anticounterfeiting, and so on.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486577","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c03260
Savannah E. Benjamin, Daniel C. Martin, Jay A. LaVerne, Kyson R. Smith, David B. Go, Peter C. Burns
Extraction of uranium from water is an essential step in in situ leach (ISL) mining and environmental decontamination. This is often done by precipitating uranium in solution as the uranyl peroxide studtite, [(UO2)(O2)(H2O)2](H2O)2, by adding hydrogen peroxide, which is energy-intensive to produce and hazardous to transport. Here, we present a method for synthesizing studtite, by generating reactive oxygen species in solution using a nonthermal plasma. Precipitation of studtite is observed within 5 min of the onset of plasma treatment as confirmed by X-ray diffraction and Raman spectral analysis. The faradaic efficiency of studtite formation is analyzed to estimate the values of hydrogen peroxide yield, 1.23 molecules per incident ion, and the rate constant of the studtite-forming reaction, 4.44 × 107 M–1 s–1. This work is a proof of concept and identifies significant parameters for the future development of a larger scale, higher throughput system.
{"title":"In Situ Uranium Extraction through the Synthesis of the Uranyl Peroxide Studtite Using a Nonthermal Plasma","authors":"Savannah E. Benjamin, Daniel C. Martin, Jay A. LaVerne, Kyson R. Smith, David B. Go, Peter C. Burns","doi":"10.1021/acs.inorgchem.4c03260","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03260","url":null,"abstract":"Extraction of uranium from water is an essential step in <i>in situ</i> leach (ISL) mining and environmental decontamination. This is often done by precipitating uranium in solution as the uranyl peroxide studtite, [(UO<sub>2</sub>)(O<sub>2</sub>)(H<sub>2</sub>O)<sub>2</sub>](H<sub>2</sub>O)<sub>2</sub>, by adding hydrogen peroxide, which is energy-intensive to produce and hazardous to transport. Here, we present a method for synthesizing studtite, by generating reactive oxygen species in solution using a nonthermal plasma. Precipitation of studtite is observed within 5 min of the onset of plasma treatment as confirmed by X-ray diffraction and Raman spectral analysis. The faradaic efficiency of studtite formation is analyzed to estimate the values of hydrogen peroxide yield, 1.23 molecules per incident ion, and the rate constant of the studtite-forming reaction, 4.44 × 10<sup>7</sup> M<sup>–1</sup> s<sup>–1</sup>. This work is a proof of concept and identifies significant parameters for the future development of a larger scale, higher throughput system.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487120","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c02894
Rukai Liu, Jie Li, Kun Liu, Artem Okulov
Special structures and prominent performance make 2D iodinene more appealing and valuable at the molecular level. Here, new-type electronic devices have been constructed with iodinene-based nanoflakes in different sizes and are theoretically studied for electronic transport properties. Our findings reveal that iodinene-based nanoflakes possess great electron transport suppression, achieving the same function as SiO2 on single molecule scale. Such transport suppression shows surprisingly nonlinear “V”-shaped trend with the width of the iodinene-based nanoflake. The medium-width iodinene-based nanoflake exhibits the strongest electron transport suppression, while the narrowest and widest ones display the largest electron transmission coefficients due to delocalized transmission eigenstates. Essentially, the weakest electron transport originates from an extremely small DOS and wide HOMO–LUMO gap. Specifically, increasing the width would diminish the extension of electronic states for the dominant transport orbitals, resulting in more butterfly-like electronic states. In non-equilibrium, negative differential resistance effect can be observed in iodinene-based devices, caused by the weakening and staying away from the Fermi level of transmission peaks influenced by the bias. Our findings provide insights into the relationship between the width of iodinene-based nanoflake and electronic transport properties, and lay a foundation in the device design and applications in molecular insulators and controllable-functional devices.
{"title":"“V”-Shaped Changing Electronic Performance of Iodinene-Based Nanoflakes as a Function of Width","authors":"Rukai Liu, Jie Li, Kun Liu, Artem Okulov","doi":"10.1021/acs.inorgchem.4c02894","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02894","url":null,"abstract":"Special structures and prominent performance make 2D iodinene more appealing and valuable at the molecular level. Here, new-type electronic devices have been constructed with iodinene-based nanoflakes in different sizes and are theoretically studied for electronic transport properties. Our findings reveal that iodinene-based nanoflakes possess great electron transport suppression, achieving the same function as SiO<sub>2</sub> on single molecule scale. Such transport suppression shows surprisingly nonlinear “V”-shaped trend with the width of the iodinene-based nanoflake. The medium-width iodinene-based nanoflake exhibits the strongest electron transport suppression, while the narrowest and widest ones display the largest electron transmission coefficients due to delocalized transmission eigenstates. Essentially, the weakest electron transport originates from an extremely small DOS and wide HOMO–LUMO gap. Specifically, increasing the width would diminish the extension of electronic states for the dominant transport orbitals, resulting in more butterfly-like electronic states. In non-equilibrium, negative differential resistance effect can be observed in iodinene-based devices, caused by the weakening and staying away from the Fermi level of transmission peaks influenced by the bias. Our findings provide insights into the relationship between the width of iodinene-based nanoflake and electronic transport properties, and lay a foundation in the device design and applications in molecular insulators and controllable-functional devices.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487162","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c03498
Parmissa Randhawa, Karthika J Kadassery, Brooke L McNeil, Samantha N MacMillan, Luke Wharton, Hua Yang, Justin J Wilson, Caterina F Ramogida
The effects of replacing nitrogen with sulfur atoms in the 18-membered macrocycle of the H2macropa chelator on the binding affinity and stability of "intermediate" (radio)metal [203Pb]Pb2+ and [213Bi]Bi3+ complexes are investigated. The 1,4,10,13-tetraoxo-7,16-diazacyclooctadecane backbone was replaced with derivatives containing sulfur in the 1,4- or the 1,4,10,13-positions to yield the novel chelators H2S2macropa (N4O4S2) and H2S4macropa (N4O2S4), respectively. Trends on the nat/203Pb- and nat/213Bi-complex stability constants, coordination chemistry, radiolabeling, and kinetic inertness were assessed via potentiometric titrations, UV-vis spectroscopy, NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. 1H-207Pb NMR spectroscopy confirmed the involvement of backbone S and/or O donors in the metal coordination sphere. Overall, the trend demonstrated that increasing the softness of the donor atoms within the ligand backbone decreased the thermodynamic stability and kinetic inertness of both the Pb2+ and Bi3+ complexes. Conversely, DFT calculations with mock compounds dimethyl ether (DME) and dimethyl sulfide (DMS) demonstrated enhanced affinity of the S atom to both Pb2+ and Bi3+ with DMS compared to DME evinced by large ΔG° values for both Pb2+ and Bi3+ complexes. The decreased stability of Pb/Bi-Sxmacropa (x = 0, 2, 4) upon increased sulfur atom incorporation may be a result of the increased steric strain within the macrocyclic backbone upon sulfur atom introduction. Nonetheless, [203Pb]Pb2+ and [213Bi]Bi3+ labeling (pH = 7, 30 min reaction time; 10-4-10-8 M chelator) resulted in both S2macropa2- and macropa2- attaining similarly high radiolabeling efficiency. Meanwhile, S4macropa2- only possessed the ability to complex [213Bi]Bi3+. Both [203Pb][Pb(macropa)] and [203Pb][Pb(S2macropa)] remained greater than 97% intact when challenged against human serum over 72 h. The results of this study reveal the effects of incorporating sulfur donor atoms into macrocyclic chelators for [203Pb]Pb2+ and [213Bi]Bi3+ radiopharmaceuticals.
{"title":"The H<sub>2</sub>S<i><sub>x</sub></i>macropa Series: Increasing the Chemical Softness of H<sub>2</sub>macropa with Sulfur Atoms to Chelate Radiometals [<sup>213</sup>Bi]Bi<sup>3+</sup> and [<sup>203</sup>Pb]Pb<sup>2+</sup> for Radiopharmaceutical Applications.","authors":"Parmissa Randhawa, Karthika J Kadassery, Brooke L McNeil, Samantha N MacMillan, Luke Wharton, Hua Yang, Justin J Wilson, Caterina F Ramogida","doi":"10.1021/acs.inorgchem.4c03498","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03498","url":null,"abstract":"<p><p>The effects of replacing nitrogen with sulfur atoms in the 18-membered macrocycle of the H<sub>2</sub>macropa chelator on the binding affinity and stability of \"intermediate\" (radio)metal [<sup>203</sup>Pb]Pb<sup>2+</sup> and [<sup>213</sup>Bi]Bi<sup>3+</sup> complexes are investigated. The 1,4,10,13-tetraoxo-7,16-diazacyclooctadecane backbone was replaced with derivatives containing sulfur in the 1,4- or the 1,4,10,13-positions to yield the novel chelators H<sub>2</sub>S<sub>2</sub>macropa (N<sub>4</sub>O<sub>4</sub>S<sub>2</sub>) and H<sub>2</sub>S<sub>4</sub>macropa (N<sub>4</sub>O<sub>2</sub>S<sub>4</sub>), respectively. Trends on the <sup>nat/203</sup>Pb- and <sup>nat/213</sup>Bi-complex stability constants, coordination chemistry, radiolabeling, and kinetic inertness were assessed via potentiometric titrations, UV-vis spectroscopy, NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. <sup>1</sup>H-<sup>207</sup>Pb NMR spectroscopy confirmed the involvement of backbone S and/or O donors in the metal coordination sphere. Overall, the trend demonstrated that increasing the softness of the donor atoms within the ligand backbone decreased the thermodynamic stability and kinetic inertness of both the Pb<sup>2+</sup> and Bi<sup>3+</sup> complexes. Conversely, DFT calculations with mock compounds dimethyl ether (DME) and dimethyl sulfide (DMS) demonstrated enhanced affinity of the S atom to both Pb<sup>2+</sup> and Bi<sup>3+</sup> with DMS compared to DME evinced by large Δ<i>G</i>° values for both Pb<sup>2+</sup> and Bi<sup>3+</sup> complexes. The decreased stability of Pb/Bi-S<sub><i>x</i></sub>macropa (<i>x</i> = 0, 2, 4) upon increased sulfur atom incorporation may be a result of the increased steric strain within the macrocyclic backbone upon sulfur atom introduction. Nonetheless, [<sup>203</sup>Pb]Pb<sup>2+</sup> and [<sup>213</sup>Bi]Bi<sup>3+</sup> labeling (pH = 7, 30 min reaction time; 10<sup>-4</sup>-10<sup>-8</sup> M chelator) resulted in both S<sub>2</sub>macropa<sup>2-</sup> and macropa<sup>2-</sup> attaining similarly high radiolabeling efficiency. Meanwhile, S<sub>4</sub>macropa<sup>2-</sup> only possessed the ability to complex [<sup>213</sup>Bi]Bi<sup>3+</sup>. Both [<sup>203</sup>Pb][Pb(macropa)] and [<sup>203</sup>Pb][Pb(S<sub>2</sub>macropa)] remained greater than 97% intact when challenged against human serum over 72 h. The results of this study reveal the effects of incorporating sulfur donor atoms into macrocyclic chelators for [<sup>203</sup>Pb]Pb<sup>2+</sup> and [<sup>213</sup>Bi]Bi<sup>3+</sup> radiopharmaceuticals.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453346","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c03449
Christopher Z. Ye, Iker Del Rosal, Sheridon N. Kelly, Erik T. Ouellette, Laurent Maron, Clément Camp, John Arnold
The synthesis of actinide tetrarhenate complexes completes a series of iridate, osmate, and rhenate polyhydrides, allowing for structural and bonding comparisons to be made. Computational studies examine the bonding interactions, particularly between metals, in these complexes. Several factors─including metal oxidation state, coordination number, and dispersion effects─affect metal–metal distances and covalency in these actinide tetrametallates. Related osmium and rhenium octametallic U2M6 clusters are synthesized and described, and subjected to similar structural and electronic analyses.
{"title":"Synthesis, Structure, and Bonding of Actinide–Rhenium Polyhydrides","authors":"Christopher Z. Ye, Iker Del Rosal, Sheridon N. Kelly, Erik T. Ouellette, Laurent Maron, Clément Camp, John Arnold","doi":"10.1021/acs.inorgchem.4c03449","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03449","url":null,"abstract":"The synthesis of actinide tetrarhenate complexes completes a series of iridate, osmate, and rhenate polyhydrides, allowing for structural and bonding comparisons to be made. Computational studies examine the bonding interactions, particularly between metals, in these complexes. Several factors─including metal oxidation state, coordination number, and dispersion effects─affect metal–metal distances and covalency in these actinide tetrametallates. Related osmium and rhenium octametallic U<sub>2</sub>M<sub>6</sub> clusters are synthesized and described, and subjected to similar structural and electronic analyses.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486584","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}
Negative thermal quenching (NTQ) of the phosphors is critically important for both scientific research and practical applications, but the design of efficient NTQ phosphors is still a challenging task. Herein, we report a new strategy for developing NTQ materials by cation-vacancy engineering. Specifically, a new color-tunable Ba9La1–x(VO4):xEu3+ (BLVO:xEu3+) phosphor with abundant intrinsic cation vacancy was developed, exhibiting superior NTQ behavior under 365 nm excitation. The NTQ performance can be modulated via adjusting Eu3+ doping levels, and the emission intensity of Eu3+ ions in the BLVO:0.20Eu3+ phosphor increased by 275% at 473 K compared to room temperature. Furthermore, the reported material emitting bright white light under 365 nm excitation was well-suited for use in white light-emitting diode (WLED) phosphor and fluorescent temperature sensors, exhibiting outstanding color-rendering index (90.1) in lighting and high sensitivity (Sa = 11.83% K–1, Sr = 2.33% K–1) in temperature detecting. Lastly, the operating temperature of WLED at different currents can be monitored and displayed in real time through emission spectroscopy. All of the results demonstrated that the designed NTQ BLVO:xEu3+ can be used as a single-phase white phosphor and optical thermometry. This work provides a fresh perspective for designing high-efficient NTQ phosphors and expands the application of phosphors in WLED in situ temperature detection.
{"title":"Defect-Enabled Superior Negative Thermal Quenching in Palmierite Ba9La(VO4)7:Eu3+ for WLED In Situ Temperature Measuring","authors":"Juanjuan Kong, Naijia Liu, Yun Xu, Yunjian Wang, Zibo Wang, Lei Geng","doi":"10.1021/acs.inorgchem.4c03199","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03199","url":null,"abstract":"Negative thermal quenching (NTQ) of the phosphors is critically important for both scientific research and practical applications, but the design of efficient NTQ phosphors is still a challenging task. Herein, we report a new strategy for developing NTQ materials by cation-vacancy engineering. Specifically, a new color-tunable Ba<sub>9</sub>La<sub>1–<i>x</i></sub>(VO<sub>4</sub>):<i>x</i>Eu<sup>3+</sup> (BLVO:<i>x</i>Eu<sup>3+</sup>) phosphor with abundant intrinsic cation vacancy was developed, exhibiting superior NTQ behavior under 365 nm excitation. The NTQ performance can be modulated via adjusting Eu<sup>3+</sup> doping levels, and the emission intensity of Eu<sup>3+</sup> ions in the BLVO:0.20Eu<sup>3+</sup> phosphor increased by 275% at 473 K compared to room temperature. Furthermore, the reported material emitting bright white light under 365 nm excitation was well-suited for use in white light-emitting diode (WLED) phosphor and fluorescent temperature sensors, exhibiting outstanding color-rendering index (90.1) in lighting and high sensitivity (<i>S</i><sub>a</sub> = 11.83% K<sup>–1</sup>, <i>S</i><sub>r</sub> = 2.33% K<sup>–1</sup>) in temperature detecting. Lastly, the operating temperature of WLED at different currents can be monitored and displayed in real time through emission spectroscopy. All of the results demonstrated that the designed NTQ BLVO:<i>x</i>Eu<sup>3+</sup> can be used as a single-phase white phosphor and optical thermometry. This work provides a fresh perspective for designing high-efficient NTQ phosphors and expands the application of phosphors in WLED in situ temperature detection.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487119","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}
The possible emergence of superconductivity in layered metal boride carbide compounds MB2C2 (M = Sc, Y, Be, Ca) was investigated using density functional theory calculations upon the topology of a boron–carbon network and the nature of the metal. ScB2C2 and YB2C2 show metallic and superconductive properties with low critical temperatures (Tcs). The semiconducting BeB2C2 compound may show superconductivity upon carrier doping with a high Tc of 47.8 K by hole doping─comparable to the structurally related MgB2 superconductor─but with a low Tc by electron doping. In contrast, the semiconducting CaB2C2 compound is predicted to be a superconductor by hole and electron doping but with low Tcs. These differences arise from the spatial distribution of electrons at the Fermi level. For compounds with low Tcs, electrons at the Fermi level are localized primarily on B and C π states perpendicular to the BC layers, experiencing minimal influence from atomic oscillations and resulting in weak electron–phonon interactions. Conversely, for a high Tc, electrons are found in σ-bonding states, leading to strong electron–phonon interactions. Electrons at the Fermi level in boron–carbon σ-bonding states seem to be a prerequisite to expect high Tc superconductivity in this kind of compound.
利用密度泛函理论计算硼碳网络的拓扑结构和金属的性质，研究了层状金属硼碳化物 MB2C2（M = Sc、Y、Be、Ca）中可能出现的超导现象。ScB2C2 和 YB2C2 具有金属和超导特性，临界温度（Tcs）较低。半导体 BeB2C2 化合物在掺入载流子后可显示出超导性，掺入空穴后的临界温度高达 47.8 K，与结构相关的 MgB2 超导体不相上下，但掺入电子后的临界温度较低。相反，掺入空穴和电子后，半导体 CaB2C2 化合物被预测为超导体，但 Tcs 较低。这些差异源于费米级电子的空间分布。对于低 Tcs 的化合物，费米级电子主要集中在垂直于 BC 层的 B 和 C π 态上，受原子振荡的影响极小，因此电子与声子的相互作用很弱。相反，在高 Tc 时，电子处于σ键态，从而产生较强的电子-声子相互作用。硼碳σ键态费米级电子似乎是这类化合物具有高 Tc 超导性的先决条件。
{"title":"Possible Superconductivity for Layered Metal Boride Carbide Compounds MB2C2 (M = Alkali, Alkaline-Earth, or Rare-Earth Metals)","authors":"Wataru Hayami, Xavier Rocquefelte, Jean-François Halet","doi":"10.1021/acs.inorgchem.4c02221","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02221","url":null,"abstract":"The possible emergence of superconductivity in layered metal boride carbide compounds MB<sub>2</sub>C<sub>2</sub> (M = Sc, Y, Be, Ca) was investigated using density functional theory calculations upon the topology of a boron–carbon network and the nature of the metal. ScB<sub>2</sub>C<sub>2</sub> and YB<sub>2</sub>C<sub>2</sub> show metallic and superconductive properties with low critical temperatures (<i>T</i><sub>c</sub>s). The semiconducting BeB<sub>2</sub>C<sub>2</sub> compound may show superconductivity upon carrier doping with a high <i>T</i><sub><i>c</i></sub> of 47.8 K by hole doping─comparable to the structurally related MgB<sub>2</sub> superconductor─but with a low <i>T</i><sub>c</sub> by electron doping. In contrast, the semiconducting CaB<sub>2</sub>C<sub>2</sub> compound is predicted to be a superconductor by hole and electron doping but with low <i>T</i><sub>c</sub>s. These differences arise from the spatial distribution of electrons at the Fermi level. For compounds with low <i>T</i><sub>c</sub>s, electrons at the Fermi level are localized primarily on B and C π states perpendicular to the BC layers, experiencing minimal influence from atomic oscillations and resulting in weak electron–phonon interactions. Conversely, for a high <i>T</i><sub>c</sub>, electrons are found in σ-bonding states, leading to strong electron–phonon interactions. Electrons at the Fermi level in boron–carbon σ-bonding states seem to be a prerequisite to expect high <i>T</i><sub>c</sub> superconductivity in this kind of compound.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486583","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c02544
Hicham Nimoh, Olivier Mentré, Eva-Maria Hammer, Maximilian Jähnig, Volker Dittrich, Claire Minaud, Claire V. Colin, Angel Arevalo-Lopéz, Robert Glaum
Blue/turquoise crystals of Sr2CrII(PO4)2 with prismatic shape and edge-length of up to 1 mm were obtained by a vapor-phase moderated solid-state reaction at 1273 K in sealed silica tubes. Its crystal structure was solved and refined from a triply twinned (“trilling”) crystal [Pbca (no. 61), Z = 12, a = 10.7064(6) Å, b = 9.2730(5) Å, c = 21.2720(7) Å, R1 = 0.038]. Sr2Cr(PO4)2 belongs to the small family of inorganic solids containing divalent chromium, where the rare Cr2+ ions are stabilized by the inductive effect of the phosphate groups. As expected from its d4 (S = 2) electronic configuration, the Jahn–Teller effect (JT) is prominent, leading for the two independent Cr2+ ions to square-pyramidal Cr(1)O4+1 and square-planar Cr(2)O4 coordination within a 3D chromium phosphate network [CrII2(PO4)4]8. Topologically, the Cr(1) and Cr(2) cations are arranged in separate alternating layers stacked along the c axis. In their respective layers, Cr(1) shows a gapped 2D topology and only weak interaction with the adjacent Cr(2) layers. However, below TN1 ∼11.3 K, Cr(1) orders antiferromagnetically into a noncollinear structure, leaving nearly paramagnetic Cr(2) idle spins, strongly frustrated by the Cr(1) moments of the next layers. On further cooling, below TN2 ∼3.6 K, the ordering of Cr(2) occurs via an additional magnetic irreducible representation, which splits the Cr(1) into Cr(1)a and Cr(1)b orbits, thus lifting the frustration on Cr(2). The corresponding P21ca.29.99 magnetic space group forces a crystal symmetry lowering, plausibly signed by a change of the magnetostrictive coefficient from positive to negative below TN2. The optical transitions observed for the JT d4 ions are in good agreement with our crystal picture from the DFT calculations. A detailed analysis within the angular overlap model explains the surprisingly different d orbital splitting by the ligand field for the chromophores Cr(1)O4+1 and Cr(2)O4.
{"title":"Layer-By-Layer Magnetic Ordering via Idle Spins and the Optical Signature of Jahn–Teller Cr2+ Ions in Sr2Cr(PO4)2","authors":"Hicham Nimoh, Olivier Mentré, Eva-Maria Hammer, Maximilian Jähnig, Volker Dittrich, Claire Minaud, Claire V. Colin, Angel Arevalo-Lopéz, Robert Glaum","doi":"10.1021/acs.inorgchem.4c02544","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02544","url":null,"abstract":"Blue/turquoise crystals of Sr<sub>2</sub>Cr<sup>II</sup>(PO<sub>4</sub>)<sub>2</sub> with prismatic shape and edge-length of up to 1 mm were obtained by a vapor-phase moderated solid-state reaction at 1273 K in sealed silica tubes. Its crystal structure was solved and refined from a triply twinned (“trilling”) crystal [<i>Pbca</i> (no. 61), <i>Z</i> = 12, <i>a</i> = 10.7064(6) Å, <i>b</i> = 9.2730(5) Å, <i>c</i> = 21.2720(7) Å, <i>R</i><sub>1</sub> = 0.038]. Sr<sub>2</sub>Cr(PO<sub>4</sub>)<sub>2</sub> belongs to the small family of inorganic solids containing divalent chromium, where the rare Cr<sup>2+</sup> ions are stabilized by the inductive effect of the phosphate groups. As expected from its <i>d</i><sup>4</sup> (<i>S</i> = 2) electronic configuration, the Jahn–Teller effect (JT) is prominent, leading for the two independent Cr<sup>2+</sup> ions to square-pyramidal Cr(1)O<sub>4+1</sub> and square-planar Cr(2)O<sub>4</sub> coordination within a 3D chromium phosphate network [Cr<sup>II</sup><sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>]<sup>8</sup>. Topologically, the Cr(1) and Cr(2) cations are arranged in separate alternating layers stacked along the <i>c</i> axis. In their respective layers, Cr(1) shows a gapped 2D topology and only weak interaction with the adjacent Cr(2) layers. However, below <i>T</i><sub>N1</sub> ∼11.3 K, Cr(1) orders antiferromagnetically into a noncollinear structure, leaving nearly paramagnetic Cr(2) idle spins, strongly frustrated by the Cr(1) moments of the next layers. On further cooling, below <i>T</i><sub>N2</sub> ∼3.6 K, the ordering of Cr(2) occurs via an additional magnetic irreducible representation, which splits the Cr(1) into Cr(1)a and Cr(1)b orbits, thus lifting the frustration on Cr(2). The corresponding <i>P2</i><sub>1</sub><i>ca.29.99</i> magnetic space group forces a crystal symmetry lowering, plausibly signed by a change of the magnetostrictive coefficient from positive to negative below <i>T</i><sub>N2</sub>. The optical transitions observed for the JT <i>d</i><sup>4</sup> ions are in good agreement with our crystal picture from the DFT calculations. A detailed analysis within the angular overlap model explains the surprisingly different <i>d</i> orbital splitting by the ligand field for the chromophores Cr(1)O<sub>4+1</sub> and Cr(2)O<sub>4</sub>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486576","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}
Four structurally bent porphyrin(2.1.2.1) Pt(II) complexes have been obtained and verified well. Main absorbance of Pt(II) porphyrin(2.1.2.1) displayed a significant red-shift compared to that of porphyrin(1.1.1.1) Pt(II) molecules. 1O2 study indicated that electron-withdrawing group and intramolecular charge transfer effect synergistically endowed Pt(II) porphyrin(2.1.2.1) with good singlet oxygen-sensitizing capacity under blue LED light irradiation. This work presents a simple synthesis way to develop a new series of efficient porphyrinoid singlet oxygen photosensitizers for PDT through molecular engineering.
{"title":"Effect of Peripheral Functionalization of Pt(II) Porphyrin(2.1.2.1) on Singlet Oxygen Generation","authors":"Feng Chen, Xiaojuan Lv, Daiki Kuzuhara, Tao Zhang, Jianming Pan, Fengxian Qiu, Toshiharu Teranishi, Songlin Xue","doi":"10.1021/acs.inorgchem.4c02924","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02924","url":null,"abstract":"Four structurally bent porphyrin(2.1.2.1) Pt(II) complexes have been obtained and verified well. Main absorbance of Pt(II) porphyrin(2.1.2.1) displayed a significant red-shift compared to that of porphyrin(1.1.1.1) Pt(II) molecules. <sup>1</sup>O<sub>2</sub> study indicated that electron-withdrawing group and intramolecular charge transfer effect synergistically endowed Pt(II) porphyrin(2.1.2.1) with good singlet oxygen-sensitizing capacity under blue LED light irradiation. This work presents a simple synthesis way to develop a new series of efficient porphyrinoid singlet oxygen photosensitizers for PDT through molecular engineering.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487118","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 : 2024-10-22DOI: 10.1021/acs.inorgchem.4c02981
Manzhu Zhao, Haiyan Yuan, Jingping Zhang
Transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil the mechanism and enantioselectivity of Pd-catalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligand-to-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C–H···O interactions and the electrostatic interactions. For the enantioselective C–O bond formation process, the orientation of the substrate in the chiral pocket plays a significant role in controlling the enantioselectivity by contributing different noncovalent interactions. On the basis of the distortion/interaction model and energy decomposition analysis, the distortion energy is identified as the dominant factor controlling the product chemoselectivity. BnOH acts as the substrate, proton shuttle, and stabilizer to facilitate the H-transfer process in both LLHT and the C–O bond formation process. This study provides molecular-level insights into the collaborative effect of the base and P,N-ligand to perform the catalytic activity in the asymmetric hydrofunctionalization of conjugated dienes, which might open a new avenue for designing more efficient base-assisted enantioselective hydrofunctionalization by Pd catalysis.
{"title":"Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes","authors":"Manzhu Zhao, Haiyan Yuan, Jingping Zhang","doi":"10.1021/acs.inorgchem.4c02981","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02981","url":null,"abstract":"Transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil the mechanism and enantioselectivity of Pd-catalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligand-to-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C–H···O interactions and the electrostatic interactions. For the enantioselective C–O bond formation process, the orientation of the substrate in the chiral pocket plays a significant role in controlling the enantioselectivity by contributing different noncovalent interactions. On the basis of the distortion/interaction model and energy decomposition analysis, the distortion energy is identified as the dominant factor controlling the product chemoselectivity. BnOH acts as the substrate, proton shuttle, and stabilizer to facilitate the H-transfer process in both LLHT and the C–O bond formation process. This study provides molecular-level insights into the collaborative effect of the base and <i>P</i>,<i>N</i>-ligand to perform the catalytic activity in the asymmetric hydrofunctionalization of conjugated dienes, which might open a new avenue for designing more efficient base-assisted enantioselective hydrofunctionalization by Pd catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486579","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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