Pub Date : 2026-03-25DOI: 10.1021/acs.inorgchem.6c01017
Lichen Bai,Zhi-Peng Tao,Kechao Wang,Qi Zhang,Jialu Li,Lin Liu,Zheng-bo Han
Photocatalytic oxygen reduction offers a green route to hydrogen peroxide (H2O2) production, yet practical efficiency is often limited by insufficient visible-light harvesting, fast charge recombination, and the kinetic mismatch between proton supply and interfacial electron transfer. Inspired by the industrial anthraquinone (AQ) redox cycle, we report the in situ embedding of an anthraquinone unit into a zirconium-based metal–organic framework (Zr-AQ-MOF) to create a highly efficient and stable photocatalyst for H2O2 synthesis. Comprehensive characterization reveals that the AQ centers extend light absorption, provide abundant active sites, promote charge separation and transport, and facilitate a two-electron oxygen reduction pathway via superoxide radicals (•O2–), significantly enhancing the H2O2 production efficiency. Notably, 2-propanol functions as both a hole scavenger and a proton source, promoting rapid proton delivery to AQ centers and enabling a proton-coupled electron transfer that suppresses charge recombination and accelerates H2O2 formation. Furthermore, Zr-AQ-MOF exhibits excellent broad-spectrum antibacterial activity of both E. coli and S. aureus under light irradiation, highlighting its potential for integrated H2O2 generation and water purification.
{"title":"Anthraquinone-Based Metal–Organic Framework with Proton Transfer for Enhanced H2O2 Photosynthesis","authors":"Lichen Bai,Zhi-Peng Tao,Kechao Wang,Qi Zhang,Jialu Li,Lin Liu,Zheng-bo Han","doi":"10.1021/acs.inorgchem.6c01017","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01017","url":null,"abstract":"Photocatalytic oxygen reduction offers a green route to hydrogen peroxide (H2O2) production, yet practical efficiency is often limited by insufficient visible-light harvesting, fast charge recombination, and the kinetic mismatch between proton supply and interfacial electron transfer. Inspired by the industrial anthraquinone (AQ) redox cycle, we report the in situ embedding of an anthraquinone unit into a zirconium-based metal–organic framework (Zr-AQ-MOF) to create a highly efficient and stable photocatalyst for H2O2 synthesis. Comprehensive characterization reveals that the AQ centers extend light absorption, provide abundant active sites, promote charge separation and transport, and facilitate a two-electron oxygen reduction pathway via superoxide radicals (•O2–), significantly enhancing the H2O2 production efficiency. Notably, 2-propanol functions as both a hole scavenger and a proton source, promoting rapid proton delivery to AQ centers and enabling a proton-coupled electron transfer that suppresses charge recombination and accelerates H2O2 formation. Furthermore, Zr-AQ-MOF exhibits excellent broad-spectrum antibacterial activity of both E. coli and S. aureus under light irradiation, highlighting its potential for integrated H2O2 generation and water purification.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506400","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 : 2026-03-25DOI: 10.1021/acs.inorgchem.6c01209
Yujian Wang,Peng Wang,Xuebing Leng,Dongyang Wang,Liang Deng
Iron(–I) remains among the least understood oxidation states of iron due to the scarcity of structurally well-defined iron(–I) complexes. Herein, we demonstrate that a combined ligand set of N-heterocyclic carbene (NHC) with divinyltetramethyldisiloxane (dvtms) can effectively stabilize iron(–I) complexes [K(18-C-6)(THF)n][(NHC)Fe(N2)(η:2η2-dvtms)] behaving like masked low-coordinate iron(–I) species in reactions. The series of iron(-I) complexes [K(18-C-6)(THF)n][(NHC)Fe(N2)(η:2η2-dvtms)] bearing different NHC ligands (NHC = IiPr, 1a; ICy, 1b; IMesCy, 1c; IMes, 1d; IDep, 1e; IPr, 1f; Me2-cAAC, 1g) were prepared from the reactions of the iron(0) complexes [(NHC)Fe(η:2η2-dvtms)] with KC8 and 18-C-6 in THF under a dinitrogen atmosphere. These iron(–I) complexes have been characterized by 1H NMR, solution magnetic susceptibility measurement, electron paramagnetic resonance spectroscopy, elemental analysis, and single-crystal X-ray diffraction study. Reactivity studies established their conversions to the iron(I) complexes [(NHC)Fe(NNSiiPr3)(η:2η2-dvtms)] (2), [(18-C-6)K(μ-σ:σ-dIDep)Fe(σ:η2-MeCHSiMe2OSiMe2CH = CH2)] (3), and [K(18-C-6)(THF)2][Fe(σ:σ:η:2η2-CH2=CHSiMe2OSiMe2CHCH2CH2CHMe2SiOMe2SiCH = CH2)] (4) under corresponding reaction conditions, showing the capability of low-coordinate iron(–I) species in mediating two-electron reductive transformations of dinitrogen and alkenes. Furthermore, these iron(–I) complexes facilitate the hydrodehalogenation of nonactivated organic halides upon one-electron redox reactions, yielding iron(0) complexes and hydrodehalogenated organic products. The straightforward synthesis and rich reactivity of these iron(–I) complexes highlight their potential utility as reagents and catalysts for challenging chemical transformations.
{"title":"Masked Low-Coordinate Fe(–I) Species: NHC- and Alkene-Supported Fe(–I)-Dinitrogen Complexes","authors":"Yujian Wang,Peng Wang,Xuebing Leng,Dongyang Wang,Liang Deng","doi":"10.1021/acs.inorgchem.6c01209","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01209","url":null,"abstract":"Iron(–I) remains among the least understood oxidation states of iron due to the scarcity of structurally well-defined iron(–I) complexes. Herein, we demonstrate that a combined ligand set of N-heterocyclic carbene (NHC) with divinyltetramethyldisiloxane (dvtms) can effectively stabilize iron(–I) complexes [K(18-C-6)(THF)n][(NHC)Fe(N2)(η:2η2-dvtms)] behaving like masked low-coordinate iron(–I) species in reactions. The series of iron(-I) complexes [K(18-C-6)(THF)n][(NHC)Fe(N2)(η:2η2-dvtms)] bearing different NHC ligands (NHC = IiPr, 1a; ICy, 1b; IMesCy, 1c; IMes, 1d; IDep, 1e; IPr, 1f; Me2-cAAC, 1g) were prepared from the reactions of the iron(0) complexes [(NHC)Fe(η:2η2-dvtms)] with KC8 and 18-C-6 in THF under a dinitrogen atmosphere. These iron(–I) complexes have been characterized by 1H NMR, solution magnetic susceptibility measurement, electron paramagnetic resonance spectroscopy, elemental analysis, and single-crystal X-ray diffraction study. Reactivity studies established their conversions to the iron(I) complexes [(NHC)Fe(NNSiiPr3)(η:2η2-dvtms)] (2), [(18-C-6)K(μ-σ:σ-dIDep)Fe(σ:η2-MeCHSiMe2OSiMe2CH = CH2)] (3), and [K(18-C-6)(THF)2][Fe(σ:σ:η:2η2-CH2=CHSiMe2OSiMe2CHCH2CH2CHMe2SiOMe2SiCH = CH2)] (4) under corresponding reaction conditions, showing the capability of low-coordinate iron(–I) species in mediating two-electron reductive transformations of dinitrogen and alkenes. Furthermore, these iron(–I) complexes facilitate the hydrodehalogenation of nonactivated organic halides upon one-electron redox reactions, yielding iron(0) complexes and hydrodehalogenated organic products. The straightforward synthesis and rich reactivity of these iron(–I) complexes highlight their potential utility as reagents and catalysts for challenging chemical transformations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506402","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 : 2026-03-25DOI: 10.1021/acs.inorgchem.6c00208
Alexander Allgaier,Felix R. Fischer,Somnath Bhattacharya,Kevin Balliet,Michael R. Buchmeiser,Matthias Bauer,Joris van Slageren
Chromium-catalyzed ethylene oligomerization is an industrially important reaction, but improving the product specificity remains essential. In-depth spectroscopic and theoretical investigations of this catalytic reaction have allowed a great deal of insight into it. However, fundamental issues, such as the oxidation states relevant to the catalysis, are still unclear. This study makes the case for high-frequency electron paramagnetic resonance spectroscopy as a powerful method for studying this catalytic reaction, profiting from high g-value resolution and access to large energy splittings. The results confirm the occurrence of chromium(I) species but also show that such species are not necessarily dead ends in the catalytic cycle. Second, no unambiguous evidence for the relevance of chromium(II) was found, in spite of the unequivocal ability of HFEPR to detect such species. X-ray Absorption Spectroscopy (XAS) and TD-DFT calculations enabled the structural and electronic ground-state characterization of the dimeric, chloride-bridged Cr(III) precatalyst Cr-NHC-N as a precondition for its following HFEPR investigation.
{"title":"Relevant Metal Oxidation States of MAO-Activated Chromium Catalysts for Ethylene Oligomerization","authors":"Alexander Allgaier,Felix R. Fischer,Somnath Bhattacharya,Kevin Balliet,Michael R. Buchmeiser,Matthias Bauer,Joris van Slageren","doi":"10.1021/acs.inorgchem.6c00208","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00208","url":null,"abstract":"Chromium-catalyzed ethylene oligomerization is an industrially important reaction, but improving the product specificity remains essential. In-depth spectroscopic and theoretical investigations of this catalytic reaction have allowed a great deal of insight into it. However, fundamental issues, such as the oxidation states relevant to the catalysis, are still unclear. This study makes the case for high-frequency electron paramagnetic resonance spectroscopy as a powerful method for studying this catalytic reaction, profiting from high g-value resolution and access to large energy splittings. The results confirm the occurrence of chromium(I) species but also show that such species are not necessarily dead ends in the catalytic cycle. Second, no unambiguous evidence for the relevance of chromium(II) was found, in spite of the unequivocal ability of HFEPR to detect such species. X-ray Absorption Spectroscopy (XAS) and TD-DFT calculations enabled the structural and electronic ground-state characterization of the dimeric, chloride-bridged Cr(III) precatalyst Cr-NHC-N as a precondition for its following HFEPR investigation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"48 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel oxonitridosilicate, Li2La8Si6N12O7 was successfully synthesized at 1200 °C using Li3N as a flux. The crystal structure was determined through single-crystal and synchrotron powder X-ray diffraction. Li2La8Si6N12O7 crystallizes in orthorhombic space group Pcca (no. 54) with unit-cell parameters a = 15.5319(1) Å, b = 7.7382(1) Å, c = 15.5019(1) Å, and Z = 4. The structure features a layered framework built from vertex-sharing Si[N/O]4 tetrahedra, with Li[N/O]6 octahedra connecting and stabilizing both the interlayer and intralayer linkages. The octahedral coordination of Li+ was confirmed by solid-state 7Li NMR spectroscopy. Notably, the incorporation of Pr3+ and Tb3+ into the Li2La8Si6N12O7 host yields narrow-band red emission at 630 nm and green emission at 545 nm. This combination facilitates the fabrication of 365 nm near-ultraviolet light-emitting diode (UV LED) chip-based WLEDs with superior color rendering performance.
以Li3N为助熔剂，在1200℃下成功合成了新型氧化氮硅酸盐Li2La8Si6N12O7。通过单晶和同步加速器粉末x射线衍射测定了晶体结构。Li2La8Si6N12O7在正交空间群Pcca中结晶。54)，单元参数a = 15.5319(1) Å， b = 7.7382(1) Å， c = 15.5019(1) Å， Z = 4。该结构的特点是由顶点共享的Si[N/O]4四面体构建的分层框架，由Li[N/O]6八面体连接并稳定层间和层内的连接。用固态7Li核磁共振谱证实了Li+的八面体配位。值得注意的是，Pr3+和Tb3+掺入Li2La8Si6N12O7主体后，在630 nm处产生窄带红色发射，在545 nm处产生绿色发射。这种组合有助于制造365 nm近紫外发光二极管（UV LED）芯片的wled，具有优越的显色性能。
{"title":"Li2La8Si6N12O7: A Promising Oxonitridosilicate Host for Pr3+ and Tb3+ Activated Phosphors Grown in Li3N Flux","authors":"Jialing Li,Xiaoming Wang,Yongkang Zheng,Jiayao Zhang,Congling Yin,Xiaohui Li,Tianhui Liu,Zupei Yang,Huan Jiao","doi":"10.1021/acs.inorgchem.6c00528","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00528","url":null,"abstract":"A novel oxonitridosilicate, Li2La8Si6N12O7 was successfully synthesized at 1200 °C using Li3N as a flux. The crystal structure was determined through single-crystal and synchrotron powder X-ray diffraction. Li2La8Si6N12O7 crystallizes in orthorhombic space group Pcca (no. 54) with unit-cell parameters a = 15.5319(1) Å, b = 7.7382(1) Å, c = 15.5019(1) Å, and Z = 4. The structure features a layered framework built from vertex-sharing Si[N/O]4 tetrahedra, with Li[N/O]6 octahedra connecting and stabilizing both the interlayer and intralayer linkages. The octahedral coordination of Li+ was confirmed by solid-state 7Li NMR spectroscopy. Notably, the incorporation of Pr3+ and Tb3+ into the Li2La8Si6N12O7 host yields narrow-band red emission at 630 nm and green emission at 545 nm. This combination facilitates the fabrication of 365 nm near-ultraviolet light-emitting diode (UV LED) chip-based WLEDs with superior color rendering performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506383","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 : 2026-03-25DOI: 10.1021/acs.inorgchem.5c04646
Mubashar Ilyas,Nagesh Manurkar,Muhammad Abbas,Mudassar Ilyas,Muhammad Haider Zaman,Tahreem Saleem,Maroof Ahmad Khan,Hui Li
The most significant factor in the design of high-performance nonlinear optical (NLO) materials is electronic symmetry, which directly influences hyperpolarizability and second harmonic generation (SHG) response. This work presents two isostructural one-dimensional coordination complexes, {[Co2(CMP)2(BIPY)2(H2O)6]·11H2O}n (I) and {[Ni2(CMP)2(BIPY)2(H2O)6]·11H2O}n (II), (CMP = Cytidine Monophosphate, BIPY = 4,4′-bipyridine), crystallized in the noncentrosymmetric (NCS) P21 space group. The cobalt-based complex (I) establishes an NCS environment due to its pronounced octahedral distortion and lower electronic symmetry, coupled with intrachain hydrogen bonding and π–π stacking, resulting in enhanced hyperpolarizability and a robust second-harmonic generation response. Conversely, the nickel-based complex (II) demonstrates comparatively weaker NLO characteristics attributable to its higher symmetry. Experimental and theoretical findings have established that the superior NLO performance of complex (I) is intrinsically linked to its low symmetry, narrow band gap, and significant intermolecular interactions. This research demonstrates that disrupting electronic symmetry can significantly amplify the nonlinear optical response through supramolecular architecture in coordination polymers.
{"title":"Exploring the Effect of Electronic Symmetry on the Hyperpolarizabilities of Co(II) and Ni(II) Coordination Complexes with Cytidine Nucleotide","authors":"Mubashar Ilyas,Nagesh Manurkar,Muhammad Abbas,Mudassar Ilyas,Muhammad Haider Zaman,Tahreem Saleem,Maroof Ahmad Khan,Hui Li","doi":"10.1021/acs.inorgchem.5c04646","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04646","url":null,"abstract":"The most significant factor in the design of high-performance nonlinear optical (NLO) materials is electronic symmetry, which directly influences hyperpolarizability and second harmonic generation (SHG) response. This work presents two isostructural one-dimensional coordination complexes, {[Co2(CMP)2(BIPY)2(H2O)6]·11H2O}n (I) and {[Ni2(CMP)2(BIPY)2(H2O)6]·11H2O}n (II), (CMP = Cytidine Monophosphate, BIPY = 4,4′-bipyridine), crystallized in the noncentrosymmetric (NCS) P21 space group. The cobalt-based complex (I) establishes an NCS environment due to its pronounced octahedral distortion and lower electronic symmetry, coupled with intrachain hydrogen bonding and π–π stacking, resulting in enhanced hyperpolarizability and a robust second-harmonic generation response. Conversely, the nickel-based complex (II) demonstrates comparatively weaker NLO characteristics attributable to its higher symmetry. Experimental and theoretical findings have established that the superior NLO performance of complex (I) is intrinsically linked to its low symmetry, narrow band gap, and significant intermolecular interactions. This research demonstrates that disrupting electronic symmetry can significantly amplify the nonlinear optical response through supramolecular architecture in coordination polymers.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506381","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 : 2026-03-25DOI: 10.1021/acs.inorgchem.5c05836
Jing-Feng Hou,Jian-Fei Gao,Yan-Dong Ma,Zheng-Hua He,Zhe Li,Ling-Bin Kong
Due to the increasing demand for high-performance, sustainable, and reliable energy, the pursuit of advanced electrode materials for lithium-ion capacitors (LICs) has attracted great attention within the field of energy storage. Among various candidates, molybdenum borides (MoBX, where X = 1 or 2) have emerged as promising anode materials owing to their remarkable electrical conductivity, chemical stability, and high theoretical capacity. However, the synthesis of phase-pure crystalline MoBX nanoparticles remains a challenge. This study investigates the ionothermal route as an efficient synthesis method to overcome this obstacle while also exploring the lithium-ion energy storage mechanism of MoBX nanoparticles and their potential as LIC anodes. The MoB and MoB2 electrodes exhibit excellent cycling stability, with capacities reaching 159 and 207 mAh g–1, respectively, after 800 cycles at 0.1 A g–1. Additionally, LICs using MoB and MoB2 as anodes, paired with commercial activated carbon as cathodes, demonstrate exceptional capacity retention rates of 51.5% and 72.1%, respectively, after 10,000 cycles. These results not only confirm the potential of MoBX nanoparticles as superior anode materials for LICs, but also provide a foundation for future research aimed at developing high-performance and long-lasting energy storage systems.
随着人们对高性能、可持续、可靠能源的需求日益增长，对锂离子电容器电极材料的研究成为储能领域的热点。在各种候选材料中，钼硼化物（MoBX，其中X = 1或2）由于其卓越的导电性，化学稳定性和高理论容量而成为有前途的阳极材料。然而，相纯结晶型MoBX纳米颗粒的合成仍然是一个挑战。本研究探讨了离子热途径作为一种有效的合成方法来克服这一障碍，同时也探索了MoBX纳米颗粒的锂离子储能机制及其作为LIC阳极的潜力。MoB和MoB2电极表现出优异的循环稳定性，在0.1 A g-1下循环800次后，容量分别达到159和207 mAh g-1。此外，使用MoB和MoB2作为阳极，搭配商业活性炭作为阴极的锂离子电池，在10,000次循环后，容量保持率分别为51.5%和72.1%。这些结果不仅证实了MoBX纳米颗粒作为锂离子电池优良阳极材料的潜力，而且为未来开发高性能、长效储能系统的研究奠定了基础。
{"title":"Phase and Structural Evolution in Molten Inorganic Salts of Molybdenum Borides for Electrochemical Applications","authors":"Jing-Feng Hou,Jian-Fei Gao,Yan-Dong Ma,Zheng-Hua He,Zhe Li,Ling-Bin Kong","doi":"10.1021/acs.inorgchem.5c05836","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05836","url":null,"abstract":"Due to the increasing demand for high-performance, sustainable, and reliable energy, the pursuit of advanced electrode materials for lithium-ion capacitors (LICs) has attracted great attention within the field of energy storage. Among various candidates, molybdenum borides (MoBX, where X = 1 or 2) have emerged as promising anode materials owing to their remarkable electrical conductivity, chemical stability, and high theoretical capacity. However, the synthesis of phase-pure crystalline MoBX nanoparticles remains a challenge. This study investigates the ionothermal route as an efficient synthesis method to overcome this obstacle while also exploring the lithium-ion energy storage mechanism of MoBX nanoparticles and their potential as LIC anodes. The MoB and MoB2 electrodes exhibit excellent cycling stability, with capacities reaching 159 and 207 mAh g–1, respectively, after 800 cycles at 0.1 A g–1. Additionally, LICs using MoB and MoB2 as anodes, paired with commercial activated carbon as cathodes, demonstrate exceptional capacity retention rates of 51.5% and 72.1%, respectively, after 10,000 cycles. These results not only confirm the potential of MoBX nanoparticles as superior anode materials for LICs, but also provide a foundation for future research aimed at developing high-performance and long-lasting energy storage systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506380","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 development of novel nonplanar, twisted macrocyclic ligands remains an important challenge. Schiff-base condensation of bissalicylaldehyde derivatives and diamines typically affords cyclic salen oligomers, but many of the reported examples have planar structures. We now report figure-eight-shaped twisted macrocyclic salen dimers and its boron complex. An o-phenylene-bridged bissalicylaldehyde designed for this purpose adopts a nonplanar structure due to the steric hindrance between its hydroxy groups and the o-phenylene linker. Furthermore, its intramolecular dipole moments stabilize a conformation in which the two hydroxy groups are positioned on opposite sides. Due to these structural characteristics, the reaction with diamines led to the successful formation of the figure-eight-shaped frameworks. Furthermore, by leveraging the twisted nature of the ligand, which orients the NO salicylaldimine moieties outward, a chiral macrocyclic tetranuclear boron-difluoride complex has been successfully synthesized.
{"title":"Figure-Eight Macrocyclic Salen Dimers Synthesized from ortho-Phenylene-Bridged Bissalicylaldehyde","authors":"Takashi Nakamura,Xuehan Wang,Ayato Shiina,Masaru Kondo","doi":"10.1021/acs.inorgchem.6c01066","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01066","url":null,"abstract":"The development of novel nonplanar, twisted macrocyclic ligands remains an important challenge. Schiff-base condensation of bissalicylaldehyde derivatives and diamines typically affords cyclic salen oligomers, but many of the reported examples have planar structures. We now report figure-eight-shaped twisted macrocyclic salen dimers and its boron complex. An o-phenylene-bridged bissalicylaldehyde designed for this purpose adopts a nonplanar structure due to the steric hindrance between its hydroxy groups and the o-phenylene linker. Furthermore, its intramolecular dipole moments stabilize a conformation in which the two hydroxy groups are positioned on opposite sides. Due to these structural characteristics, the reaction with diamines led to the successful formation of the figure-eight-shaped frameworks. Furthermore, by leveraging the twisted nature of the ligand, which orients the NO salicylaldimine moieties outward, a chiral macrocyclic tetranuclear boron-difluoride complex has been successfully synthesized.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"270 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506401","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 : 2026-03-25DOI: 10.1021/acs.inorgchem.6c00539
Maocai Pi,Ilya Semenov,Evgenia Komleva,Xi Shen,Huifen Ren,Zhehong Liu,Jie Zhang,Shuai Tang,Xubin Ye,Zhiwei Hu,Chang-Yang Kuo,Chien-Te Chen,Zhao Pan,Yao Shen,Richeng Yu,Sergey V. Streltsov,Youwen Long
An A-site-ordered AA′3B4O12-type quadruple perovskite oxide LaHg3Mn4O12 was prepared by using high-pressure and high-temperature methods. The compound crystallizes in cubic Im3̅ symmetry with a lattice parameter a = 7.5949(2) Å. The introduction of Hg2+ at the A′ site leads to a significant increase in the Mn–O–Mn bond angle, up to 159.5°. A ferromagnetic phase transition is found to occur at the Curie temperature: TC ≈ 280 K, accompanied by a large saturation magnetic moment of 13.0 μB/f.u. A corresponding anomaly in the electrical resistivity is observed near TC. First-principles calculations reveal a half-metallic electronic band structure with a wide minority-spin energy gap of ∼2.0 eV, while the majority-spin states contribute to metallic electrical transport. The current sample, LaHg3Mn4O12 thus provides the first example of A’-site nonmagnetic quadruple perovskite oxide with half-metallic behavior. Moreover, compared with other isostructural RCu3Mn4O12 (R = rare earth and Bi) half-metals with magnetic Cu2+ at the A’ site, LaHg3Mn4O12 exhibits significant enhancement in both the minority-spin energy gap and saturation magnetization, making it promising for potential spintronic applications.
{"title":"LaHg3Mn4O12: An A-Site Nonmagnetic Quadruple Perovskite Oxide with Enhanced Half-Metallic Performances","authors":"Maocai Pi,Ilya Semenov,Evgenia Komleva,Xi Shen,Huifen Ren,Zhehong Liu,Jie Zhang,Shuai Tang,Xubin Ye,Zhiwei Hu,Chang-Yang Kuo,Chien-Te Chen,Zhao Pan,Yao Shen,Richeng Yu,Sergey V. Streltsov,Youwen Long","doi":"10.1021/acs.inorgchem.6c00539","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00539","url":null,"abstract":"An A-site-ordered AA′3B4O12-type quadruple perovskite oxide LaHg3Mn4O12 was prepared by using high-pressure and high-temperature methods. The compound crystallizes in cubic Im3̅ symmetry with a lattice parameter a = 7.5949(2) Å. The introduction of Hg2+ at the A′ site leads to a significant increase in the Mn–O–Mn bond angle, up to 159.5°. A ferromagnetic phase transition is found to occur at the Curie temperature: TC ≈ 280 K, accompanied by a large saturation magnetic moment of 13.0 μB/f.u. A corresponding anomaly in the electrical resistivity is observed near TC. First-principles calculations reveal a half-metallic electronic band structure with a wide minority-spin energy gap of ∼2.0 eV, while the majority-spin states contribute to metallic electrical transport. The current sample, LaHg3Mn4O12 thus provides the first example of A’-site nonmagnetic quadruple perovskite oxide with half-metallic behavior. Moreover, compared with other isostructural RCu3Mn4O12 (R = rare earth and Bi) half-metals with magnetic Cu2+ at the A’ site, LaHg3Mn4O12 exhibits significant enhancement in both the minority-spin energy gap and saturation magnetization, making it promising for potential spintronic applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506384","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 : 2026-03-24DOI: 10.1021/acs.inorgchem.5c05959
Prashanth K. Poddutoori,Peyton Ellis,Jatan K. Sharma,Niloofar Zarrabi,Art van der Est,Francis D’Souza
A covalently linked cofacial homodimer has been synthesized using hypervalent antimony(V) porphyrins. The two porphyrins are connected by an −OCH2O– bridge, maintaining a distance of 5.85 Å between the Sb centers. Despite the positive charge on the porphyrin entities, the resulting homodimer is structurally stable, with minimal or no repulsive forces between them. Density functional theory (DFT)-optimized structures show that the two porphyrins are nearly coplanar with an angle of ∼15° between the two planes. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the ground state of the dimer are delocalized over both porphyrins, indicating the existence of exciton coupling between them. Optical studies support this observation, suggesting H-type exciton coupling based on the spectral shift of the Soret band. Similar behavior is observed in electrochemical studies as well. Results from the femtosecond transient absorption studies support the existence of exciton coupling, while the triplet-state lifetimes measured by nanosecond transient absorption studies show only minor differences. Time-resolved electron paramagnetic resonance and DFT studies of the lowest triplet state show that it is localized on a single porphyrin. While the localization of the triplet state is consistent with the expected weak coupling between the triplet states due to their small transition dipoles, the optical data, DFT calculations, and structure of the dimer all indicate that the dipole–dipole model of the excitonic coupling is not capable of adequately describing the excited-state properties. Notably, the role of p-block Sb in cofacial porphyrin dimer promoting exciton coupling, irrespective of its higher oxidation state of +5, is borne out from this study.
{"title":"Electronically Coupled, Cofacially Linked, Hypervalent Antimony(V) Porphyrin Homodimer: Synthesis, Spectroscopy, and Photochemistry","authors":"Prashanth K. Poddutoori,Peyton Ellis,Jatan K. Sharma,Niloofar Zarrabi,Art van der Est,Francis D’Souza","doi":"10.1021/acs.inorgchem.5c05959","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05959","url":null,"abstract":"A covalently linked cofacial homodimer has been synthesized using hypervalent antimony(V) porphyrins. The two porphyrins are connected by an −OCH2O– bridge, maintaining a distance of 5.85 Å between the Sb centers. Despite the positive charge on the porphyrin entities, the resulting homodimer is structurally stable, with minimal or no repulsive forces between them. Density functional theory (DFT)-optimized structures show that the two porphyrins are nearly coplanar with an angle of ∼15° between the two planes. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the ground state of the dimer are delocalized over both porphyrins, indicating the existence of exciton coupling between them. Optical studies support this observation, suggesting H-type exciton coupling based on the spectral shift of the Soret band. Similar behavior is observed in electrochemical studies as well. Results from the femtosecond transient absorption studies support the existence of exciton coupling, while the triplet-state lifetimes measured by nanosecond transient absorption studies show only minor differences. Time-resolved electron paramagnetic resonance and DFT studies of the lowest triplet state show that it is localized on a single porphyrin. While the localization of the triplet state is consistent with the expected weak coupling between the triplet states due to their small transition dipoles, the optical data, DFT calculations, and structure of the dimer all indicate that the dipole–dipole model of the excitonic coupling is not capable of adequately describing the excited-state properties. Notably, the role of p-block Sb in cofacial porphyrin dimer promoting exciton coupling, irrespective of its higher oxidation state of +5, is borne out from this study.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506406","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 scope and limitations of a germole-to-borole rearrangement are reported. Double salt metathesis reactions of dipotassium germolediides with amino-, aryl-, and ferrocenyl-substituted boron dihalides allow for the preparation of borole complexes of Ge(II) in synthetically useful yields and quantities. The analogous silole-to-borole transformation is viable but is less selective and of limited synthetic use. The analysis of the molecular and electronic structure of the obtained Ge(II) borole complexes classifies them as boragerma[5]pyramidanes, molecular nido-type clusters. The molecular structure can be fine-tuned as strongly electron-donating substituents at the boron atom induce an opening of the cluster. The boragerma[5]pyramidanes bind via the germanium atom to transition metal complexes and behave as σ-donors with only insignificant π-acceptor abilities. Their reduction with elemental lithium and their reaction with strong nucleophiles such as N-heterocylic carbenes (NHCs) lead to the elimination of germanium and isolation of borole derivatives.
{"title":"Boragerma[5]pyramidanes via a Germole-to-Borole Rearrangement","authors":"Lukas Bührmann,Amrit Chandi,Nadeschda Geibel,Lena Albers,Marc Schmidtmann,Thomas Müller","doi":"10.1021/acs.inorgchem.6c00260","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00260","url":null,"abstract":"The scope and limitations of a germole-to-borole rearrangement are reported. Double salt metathesis reactions of dipotassium germolediides with amino-, aryl-, and ferrocenyl-substituted boron dihalides allow for the preparation of borole complexes of Ge(II) in synthetically useful yields and quantities. The analogous silole-to-borole transformation is viable but is less selective and of limited synthetic use. The analysis of the molecular and electronic structure of the obtained Ge(II) borole complexes classifies them as boragerma[5]pyramidanes, molecular nido-type clusters. The molecular structure can be fine-tuned as strongly electron-donating substituents at the boron atom induce an opening of the cluster. The boragerma[5]pyramidanes bind via the germanium atom to transition metal complexes and behave as σ-donors with only insignificant π-acceptor abilities. Their reduction with elemental lithium and their reaction with strong nucleophiles such as N-heterocylic carbenes (NHCs) lead to the elimination of germanium and isolation of borole derivatives.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506404","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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