Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100764
Ya-Xuan Xue , Han Xu , Jia-Nan Chen , Hai-Quan Tian , Tao Jia , Wei-Dong Liu , Chong-Yang Li , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong
Heterometallic 3d-4f clusters represent a promising class of multifunctional molecular materials, driven by the synergistic interactions between d- and f-electrons. Incorporating chirality into these systems further expands their potential applications, particularly in chiroptical and magneto-optical technologies. Herein, we report the successful synthesis of chiral [Ln3Co5] (Ln = Er and Y) clusters using binaphthol-based ligands. Single-crystal X-ray diffraction reveals the coexistence of two distinct Co2+ coordination geometries: six-coordinate octahedron and five-coordinate trigonal bipyramid. Spectroscopic analyses demonstrate geometry-dependent chiroptical behavior: pentacoordinate Co2+ ions predominantly contribute to the circular dichroism (CD) features, while both geometries exhibit distinguishable signals in the magnetic circular dichroism (MCD) spectra. Notably, a pronounced magnetic dipole transition (4I15/2 → 4I13/2) from Er3+ centers is observed in the near-infrared MCD region, displaying a high g-factor of 0.0078 T−1. This work highlights the configuration- and ligand field-dependent chiroptical responses in 3d-4f systems, providing new insights for the rational design of advanced magneto-optical devices.
{"title":"Chiral Ln3Co5 clusters with geometry-dependent chiroptical and magneto-optical properties","authors":"Ya-Xuan Xue , Han Xu , Jia-Nan Chen , Hai-Quan Tian , Tao Jia , Wei-Dong Liu , Chong-Yang Li , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong","doi":"10.1016/j.cjsc.2025.100764","DOIUrl":"10.1016/j.cjsc.2025.100764","url":null,"abstract":"<div><div>Heterometallic 3d-4f clusters represent a promising class of multifunctional molecular materials, driven by the synergistic interactions between d- and f-electrons. Incorporating chirality into these systems further expands their potential applications, particularly in chiroptical and magneto-optical technologies. Herein, we report the successful synthesis of chiral [Ln<sub>3</sub>Co<sub>5</sub>] (Ln = Er and Y) clusters using binaphthol-based ligands. Single-crystal X-ray diffraction reveals the coexistence of two distinct Co<sup>2+</sup> coordination geometries: six-coordinate octahedron and five-coordinate trigonal bipyramid. Spectroscopic analyses demonstrate geometry-dependent chiroptical behavior: pentacoordinate Co<sup>2+</sup> ions predominantly contribute to the circular dichroism (CD) features, while both geometries exhibit distinguishable signals in the magnetic circular dichroism (MCD) spectra. Notably, a pronounced magnetic dipole transition (<sup>4</sup>I<sub>15/2</sub> → <sup>4</sup>I<sub>13/2</sub>) from Er<sup>3+</sup> centers is observed in the near-infrared MCD region, displaying a high g-factor of 0.0078 T<sup>−</sup><sup>1</sup>. This work highlights the configuration- and ligand field-dependent chiroptical responses in 3d-4f systems, providing new insights for the rational design of advanced magneto-optical devices.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100764"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100768
Lao-Bang Wang , Yaoyao Peng , Yu Fang , Jian-Ping Lang
Metal sulfide-bridged clusters exhibit unique topologies and functional properties, offering potential for advanced materials and biomimetic systems. However, challenges persist in their controlled synthesis, particularly in precise sulfide incorporation and structural modulation to form high-nuclearity clusters. Herein, we report an insitu molecular tailoring strategy using protonation of the [Tp∗WS3]− synthon by NH4+ to gradually release S2− ions, which react with in situ formed fragments such as [Tp∗WS3Cu3]2+ and [Tp∗WS3Cu2]+. Under the cooperative influence of Cl−, CN−, or Cu+, three low-nuclearity clusters with complex polyhedral structures are assembled. Solvent-induced post-scissoring and reassembly of these precursors afford two unprecedented high-nuclearity clusters with novel topological frameworks. Thin films derived from single crystals of all five clusters display significantly enhanced third-order nonlinear optical (NLO) responses compared to their solution-state counterparts. Importantly, the high-nuclearity clusters display NLO responses, surpassing not only those of their precursors but also the additive contributions of the individual units. Density functional theory (DFT) calculations attribute this enhancement to improved intracluster charge separation and synergistic interactions via linkers. This work establishes a versatile platform for constructing high-nuclearity metal sulfide clusters and provides new insights into designing functional analogues of nitrogenase-active sites.
{"title":"Molecular tailoring strategies for the controlled assembly of high-nuclearity sulfide-bridged metal clusters","authors":"Lao-Bang Wang , Yaoyao Peng , Yu Fang , Jian-Ping Lang","doi":"10.1016/j.cjsc.2025.100768","DOIUrl":"10.1016/j.cjsc.2025.100768","url":null,"abstract":"<div><div>Metal sulfide-bridged clusters exhibit unique topologies and functional properties, offering potential for advanced materials and biomimetic systems. However, challenges persist in their controlled synthesis, particularly in precise sulfide incorporation and structural modulation to form high-nuclearity clusters. Herein, we report an <em>in</em> <em>situ</em> molecular tailoring strategy using protonation of the [Tp<sup>∗</sup>WS<sub>3</sub>]<sup>−</sup> synthon by NH<sub>4</sub><sup>+</sup> to gradually release S<sup>2−</sup> ions, which react with <em>in situ</em> formed fragments such as [Tp<sup>∗</sup>WS<sub>3</sub>Cu<sub>3</sub>]<sup>2+</sup> and [Tp<sup>∗</sup>WS<sub>3</sub>Cu<sub>2</sub>]<sup>+</sup>. Under the cooperative influence of Cl<sup>−</sup>, CN<sup>−</sup>, or Cu<sup>+</sup>, three low-nuclearity clusters with complex polyhedral structures are assembled. Solvent-induced post-scissoring and reassembly of these precursors afford two unprecedented high-nuclearity clusters with novel topological frameworks. Thin films derived from single crystals of all five clusters display significantly enhanced third-order nonlinear optical (NLO) responses compared to their solution-state counterparts. Importantly, the high-nuclearity clusters display NLO responses, surpassing not only those of their precursors but also the additive contributions of the individual units. Density functional theory (DFT) calculations attribute this enhancement to improved intracluster charge separation and synergistic interactions via linkers. This work establishes a versatile platform for constructing high-nuclearity metal sulfide clusters and provides new insights into designing functional analogues of nitrogenase-active sites.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100768"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100762
Dongdong Liu , Ziqi Tang , Haoyu Wang , Xinjie Li , Jingyang Li , Chao Zhu , Shan Ding , Yuan-Sheng Cheng , Hui Zhang , Peipei Li , Ju Wu , Guozan Yuan
Using solar energy to convert CO2 into chemicals presents an economical, environmentally friendly, and sustainable approach. However, single-component photocatalysts exhibit limitations, including a narrow light absorption range, rapid carrier recombination, and weak reduction capabilities. To mitigate charge carrier recombination and enhance reduction efficiency, this study prepared heterojunction photocatalysts by in situ growing zinc indium sulfide (ZnIn2S4) on a covalent organic framework (COF) substrate. Under visible light irradiation, the 30% ZIS-COF heterojunction demonstrated the highest CO2 reduction performance (1187.2 μmol g−1) and selectivity exceeding 99%, outperforming the single-component system. The electron transfer mechanism and catalytic process were further explored through photoluminescence (PL), time-resolved fluorescence decay spectra, attenuated total reflection Fourier transform infrared spectroscopy, and spin polarized density functional theory (DFT) calculations. The results reveal that, upon photoexcitation, electrons in COF migrate to ZnIn2S4 (ZIS), and the efficient flow of photoexcited electrons is facilitated by the intimate interface contact between COF and ZIS. Moreover, the porous structure of COF promotes CO2 adsorption and enhances mass transfer. This study establishes a versatile platform for developing various hybrid combinations of CO2-reducing metal semiconductors and photosensitizing COF materials, paving the way for enhanced photocatalytic performance.
{"title":"Rational design of ZnIn2S4–COF heterojunction to inhibit photogenerated carrier dynamics for enhanced photocatalytic CO2 reduction","authors":"Dongdong Liu , Ziqi Tang , Haoyu Wang , Xinjie Li , Jingyang Li , Chao Zhu , Shan Ding , Yuan-Sheng Cheng , Hui Zhang , Peipei Li , Ju Wu , Guozan Yuan","doi":"10.1016/j.cjsc.2025.100762","DOIUrl":"10.1016/j.cjsc.2025.100762","url":null,"abstract":"<div><div>Using solar energy to convert CO<sub>2</sub> into chemicals presents an economical, environmentally friendly, and sustainable approach. However, single-component photocatalysts exhibit limitations, including a narrow light absorption range, rapid carrier recombination, and weak reduction capabilities. To mitigate charge carrier recombination and enhance reduction efficiency, this study prepared heterojunction photocatalysts by <em>in situ</em> growing zinc indium sulfide (ZnIn<sub>2</sub>S<sub>4</sub>) on a covalent organic framework (COF) substrate. Under visible light irradiation, the 30% ZIS-COF heterojunction demonstrated the highest CO<sub>2</sub> reduction performance (1187.2 μmol g<sup>−1</sup>) and selectivity exceeding 99%, outperforming the single-component system. The electron transfer mechanism and catalytic process were further explored through photoluminescence (PL), time-resolved fluorescence decay spectra, attenuated total reflection Fourier transform infrared spectroscopy, and spin polarized density functional theory (DFT) calculations. The results reveal that, upon photoexcitation, electrons in COF migrate to ZnIn<sub>2</sub>S<sub>4</sub> (ZIS), and the efficient flow of photoexcited electrons is facilitated by the intimate interface contact between COF and ZIS. Moreover, the porous structure of COF promotes CO<sub>2</sub> adsorption and enhances mass transfer. This study establishes a versatile platform for developing various hybrid combinations of CO<sub>2</sub>-reducing metal semiconductors and photosensitizing COF materials, paving the way for enhanced photocatalytic performance.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100762"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100760
Yiming Jin , Mingming Pan , Wei Luo
Addressing the CO-sensitive and catalytic efficiency issues of noble metal-based electrocatalysts towards alkaline hydrogen oxidation reaction (HOR) is indispensable for the practical commercialization of advanced anion exchange membrane fuel cells (AEMFCs). Here, Ni–N–C supported Ir catalysts denoted as Ir/Ni–N–C have been constructed and demonstrated greatly improved resistance towards CO impurities compared to conventional N–C or pure C anchored Ir nanoparticles after long-term CO poisoning. Besides, Ir/Ni–N–C possesses superior specific and mass activity of 0.557 mA cm−2 and 1.15 mA μgPGM−1, which is approximately 2-times higher than that of Ir/C and even outperforms the state-of-the-art commercial Pt/C catalysts. Combining in-situ surface-enhanced infrared absorption spectroscopy and density functional calculation, the band structure modulation and coordination effect of Ni–N–C supports lead to strengthened hydroxyl binding energy, promoted CO oxidative desorption under working potential, and lowered activation barrier of the rate-determining process of alkaline HOR. This work sheds light on the importance of metal–N–C substrates for solving the CO-tolerance and intrinsic activity challenges, and provides new insights for noble-metal based catalysts designing.
解决贵金属基电催化剂对碱性氢氧化反应（HOR）的co敏感性和催化效率问题是先进阴离子交换膜燃料电池（aemfc）实际商业化的必要条件。本文构建了Ni-N-C负载的Ir催化剂，表示为Ir/ Ni-N-C，与传统的N-C或纯C锚定的Ir纳米颗粒相比，在长期CO中毒后，它们对CO杂质的抵抗力大大提高。Ir/ Ni-N-C催化剂的比活性和质量活性分别为0.557 mA cm−2和1.15 mA μgPGM−1，比Ir/C催化剂高约2倍，甚至优于目前最先进的商业Pt/C催化剂。结合原位表面增强红外吸收光谱和密度泛函计算，发现Ni-N-C载体的能带结构调制和配位效应增强了羟基结合能，促进了CO在工作电位下的氧化解吸，降低了碱性HOR定速过程的激活势垒。这项工作揭示了金属- n - c底物对解决co耐受性和内在活性挑战的重要性，并为贵金属基催化剂的设计提供了新的见解。
{"title":"Ir/Ni–N–C electrocatalyst with promoted CO-tolerance towards alkaline hydrogen oxidation reaction","authors":"Yiming Jin , Mingming Pan , Wei Luo","doi":"10.1016/j.cjsc.2025.100760","DOIUrl":"10.1016/j.cjsc.2025.100760","url":null,"abstract":"<div><div>Addressing the CO-sensitive and catalytic efficiency issues of noble metal-based electrocatalysts towards alkaline hydrogen oxidation reaction (HOR) is indispensable for the practical commercialization of advanced anion exchange membrane fuel cells (AEMFCs). Here, Ni–N–C supported Ir catalysts denoted as Ir/Ni–N–C have been constructed and demonstrated greatly improved resistance towards CO impurities compared to conventional N–C or pure C anchored Ir nanoparticles after long-term CO poisoning. Besides, Ir/Ni–N–C possesses superior specific and mass activity of 0.557 mA cm<sup>−2</sup> and 1.15 mA μg<sub>PGM</sub><sup>−1</sup>, which is approximately 2-times higher than that of Ir/C and even outperforms the state-of-the-art commercial Pt/C catalysts. Combining <em>in-situ</em> surface-enhanced infrared absorption spectroscopy and density functional calculation, the band structure modulation and coordination effect of Ni–N–C supports lead to strengthened hydroxyl binding energy, promoted CO oxidative desorption under working potential, and lowered activation barrier of the rate-determining process of alkaline HOR. This work sheds light on the importance of metal–N–C substrates for solving the CO-tolerance and intrinsic activity challenges, and provides new insights for noble-metal based catalysts designing.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100760"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100763
Piao Tang , Xin Wen , Jindong Chen , Ning Ye , Guang Peng
Based on a functional group composite strategy, the first Ag-containing phosphate-tellurite nonlinear optical (NLO) crystal, Ag(Te2O3)(PO4), was synthesized via a subcritical hydrothermal method. This crystal crystallizes in the noncentrosymmetric space group Pmn21, featuring a unique zigzag two-dimensional [(Te2O3)(PO4)]∞ layer. It possesses the strongest powder second-harmonic generation (SHG) response among all reported phosphate-tellurite compounds, reaching 2.1 × KH2PO4, along with a moderate birefringence of 0.045@546 nm. Theoretical calculations indicate that the TeO4 group with stereochemically active lone-pair electrons, together with AgO7 polyhedra and PO4 group, synergistically contributes to its optical properties. This functional group composite strategy not only facilitates the integration of phosphate and tellurite units with Ag+ cations, but also offers a versatile route for designing NLO materials across diverse inorganic systems.
{"title":"Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure","authors":"Piao Tang , Xin Wen , Jindong Chen , Ning Ye , Guang Peng","doi":"10.1016/j.cjsc.2025.100763","DOIUrl":"10.1016/j.cjsc.2025.100763","url":null,"abstract":"<div><div>Based on a functional group composite strategy, the first Ag-containing phosphate-tellurite nonlinear optical (NLO) crystal, Ag(Te<sub>2</sub>O<sub>3</sub>)(PO<sub>4</sub>), was synthesized <em>via</em> a subcritical hydrothermal method. This crystal crystallizes in the noncentrosymmetric space group <em>Pmn</em>2<sub>1</sub>, featuring a unique zigzag two-dimensional [(Te<sub>2</sub>O<sub>3</sub>)(PO<sub>4</sub>)]<sub>∞</sub> layer. It possesses the strongest powder second-harmonic generation (SHG) response among all reported phosphate-tellurite compounds, reaching 2.1 × KH<sub>2</sub>PO<sub>4</sub>, along with a moderate birefringence of 0.045@546 nm. Theoretical calculations indicate that the TeO<sub>4</sub> group with stereochemically active lone-pair electrons, together with AgO<sub>7</sub> polyhedra and PO<sub>4</sub> group, synergistically contributes to its optical properties. This functional group composite strategy not only facilitates the integration of phosphate and tellurite units with Ag<sup>+</sup> cations, but also offers a versatile route for designing NLO materials across diverse inorganic systems.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100763"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Separation of ternary cyclic C6 hydrocarbons, i.e., the mixture of benzene (Bz), cyclohexene (Cye), and cyclohexane (Cya), is one of the critical chemical processes but challenging in the petrochemical industry. Here, we design and synthesize a stable Al-based metal-organic framework with high-quality single crystals, which exhibits excellent thermal stability (up to 300 °C), acid-base stability (within a pH range of 2–12) and boiling-water stability. Interestingly, by virtue of multiple gates controlled by organic fragments and/or inorganic clusters in the quasi-three-dimensional pores, the framework exhibits not only ultrahigh Bz/Cya (180) and Bz/Cye (66) selectivities, but also ultrahigh Bz selectivity (118) from the ternary Bz/Cye/Cya mixture. Notably, all the above selectivities rank in the top three in all porous materials, and the Bz/Cye selectivity is the highest to date. Single-crystal X-ray diffraction analyses and computational simulations revealed that the multiple types of gating play the crucial role in the adsorption and separation of Bz/Cye/Cya mixture.
{"title":"An Al-based metal-organic framework with multiple gates for highly efficient separation of benzene/cyclohexene/cyclohexane","authors":"Wen-Yu Su , Fang-Di Dong , Zi-Luo Fang, Zhi-Shuo Wang, Mu-Yang Zhou, Xi Feng, Xiao-Tong Lu, Rong-Hua Wang, Xing-Yu Li, Dong-Dong Zhou","doi":"10.1016/j.cjsc.2025.100766","DOIUrl":"10.1016/j.cjsc.2025.100766","url":null,"abstract":"<div><div>Separation of ternary cyclic C<sub>6</sub> hydrocarbons, <em>i.e</em>., the mixture of benzene (Bz), cyclohexene (Cye), and cyclohexane (Cya), is one of the critical chemical processes but challenging in the petrochemical industry. Here, we design and synthesize a stable Al-based metal-organic framework with high-quality single crystals, which exhibits excellent thermal stability (up to 300 °C), acid-base stability (within a pH range of 2–12) and boiling-water stability. Interestingly, by virtue of multiple gates controlled by organic fragments and/or inorganic clusters in the quasi-three-dimensional pores, the framework exhibits not only ultrahigh Bz/Cya (180) and Bz/Cye (66) selectivities, but also ultrahigh Bz selectivity (118) from the ternary Bz/Cye/Cya mixture. Notably, all the above selectivities rank in the top three in all porous materials, and the Bz/Cye selectivity is the highest to date. Single-crystal X-ray diffraction analyses and computational simulations revealed that the multiple types of gating play the crucial role in the adsorption and separation of Bz/Cye/Cya mixture.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100766"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100761
Fan Yang , Guan-Huang Zhang , Hai-Ling Wang , Wen-Wen Qin , Zhong-Hong Zhu , Fu-Pei Liang , Hua-Hong Zou
In this work, an ultrasonic tailoring strategy was used to obtain nanosized one-dimensional chain-like lanthanide metal-organic frameworks (Ln-MOFs) with excellent photophysical properties for the first time, and high-resolution bio-optical imaging applications were achieved. As the ambient temperature gradually increases, the chain-like Ln-MOFs do not show obvious thermal quenching of luminescence. It is worth noting that when the ambient temperature exceeds 300 K, the departure of the terminal-coordinated H2O molecules within the Ln-MOFs structure induces significant thermally enhanced luminescence. Furthermore, by regulating the energy transfer pathways of bimetallic-doped TbxEu(1−x)-MOFs, a series of luminescence changes from yellow-green to red were achieved. Based on the multiple excitation, thermally enhanced luminescence, and multicolor luminescence properties of Ln-MOFs, a complex anti-counterfeiting system was constructed. More noteworthy is that the Ln-MOFs nanochains obtained using the ultrasonic cutting strategy have high-resolution optical imaging effects on HeLa, MCF-7, MDA-MB-231 cells and living zebrafish, and can specifically label the lysosomes of living cells. This work opens up new horizons for the application of multidimensional lanthanide complex emitters in high-resolution bio-optical imaging and opens a new blueprint for constructing lanthanide complex emitters with “all-in-one” functions.
{"title":"Ultrasonic cutting strategy yields lanthanide organic nanochains with bright emission: Thermally enhanced luminescence and bio-optical imaging","authors":"Fan Yang , Guan-Huang Zhang , Hai-Ling Wang , Wen-Wen Qin , Zhong-Hong Zhu , Fu-Pei Liang , Hua-Hong Zou","doi":"10.1016/j.cjsc.2025.100761","DOIUrl":"10.1016/j.cjsc.2025.100761","url":null,"abstract":"<div><div>In this work, an ultrasonic tailoring strategy was used to obtain nanosized one-dimensional chain-like lanthanide metal-organic frameworks (<strong>Ln-MOFs</strong>) with excellent photophysical properties for the first time, and high-resolution bio-optical imaging applications were achieved. As the ambient temperature gradually increases, the chain-like <strong>Ln-MOFs</strong> do not show obvious thermal quenching of luminescence. It is worth noting that when the ambient temperature exceeds 300 K, the departure of the terminal-coordinated H<sub>2</sub>O molecules within the <strong>Ln-MOFs</strong> structure induces significant thermally enhanced luminescence. Furthermore, by regulating the energy transfer pathways of bimetallic-doped <strong>Tb<sub><em>x</em></sub>Eu<sub>(1</sub></strong><em><sub>−</sub></em><strong><sub><em>x</em>)</sub>-MOFs</strong>, a series of luminescence changes from yellow-green to red were achieved. Based on the multiple excitation, thermally enhanced luminescence, and multicolor luminescence properties of <strong>Ln-MOFs</strong>, a complex anti-counterfeiting system was constructed. More noteworthy is that the <strong>Ln-MOFs</strong> nanochains obtained using the ultrasonic cutting strategy have high-resolution optical imaging effects on HeLa, MCF-7, MDA-MB-231 cells and living zebrafish, and can specifically label the lysosomes of living cells. This work opens up new horizons for the application of multidimensional lanthanide complex emitters in high-resolution bio-optical imaging and opens a new blueprint for constructing lanthanide complex emitters with “all-in-one” functions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100761"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100765
Chaochao Fan , Yue Wang , Dan Zhang , Wei Zuo , Wenxiong Zhang , Chuandong Jia
Anthracene group features fluorescence, π conjugation, and stimulus-responsive characteristics, and therefore, anthracene-containing supramolecular assemblies have attracted much more extensive attention from supramolecular chemists. Anthracene moiety is susceptible to attack by singlet oxygen (1O2), and it undergoes [4 + 2] photooxygenation via capturing 1O2 under 365 nm irradiation, generating endoperoxide photoproducts that could release 1O2 through heat. A variety of anthracene-based supramolecular assemblies are elegantly designed and synthesized to further explore their properties. In the past few decades, numerous articles and few reviews about the [4 + 4] photodimerization of anthracene moiety have been published. Howerer, to the best of our knowledge, very few reviews focusing on anthracene-based supramolecular systems and their reversible [4 + 2] photochemical oxidation have hardly been reported. The minor review primarily highlights typical examples of anthracene-containing supramolecular assemblies in terms of construction strategy, properties, and the [4 + 2] photooxygenation. In this review, the main content will be classified into four categories: (I) chirality in anthracene-based supramolecular assemblies; (II) luminescence regulation in anthracene-containing supramolecular assemblies; (III) π···π interactions in anthracene-based supramolecular assemblies; (IV) [4 + 2] photooxygenation in anthracene-based supramolecular assemblies including discrete, polymeric, and anion-directed structures. We wish this mini-review could provide fundamental inspiration for supramolecular scientists to further develop novel anthracene-containing assemblies based on coordination-driven self-assembly and study their photochemical reactions, which is showing potential for application in smart materials.
{"title":"Exploration and development of anthracene-containing supramolecular assemblies and their [4 + 2] photooxygenation","authors":"Chaochao Fan , Yue Wang , Dan Zhang , Wei Zuo , Wenxiong Zhang , Chuandong Jia","doi":"10.1016/j.cjsc.2025.100765","DOIUrl":"10.1016/j.cjsc.2025.100765","url":null,"abstract":"<div><div>Anthracene group features fluorescence, π conjugation, and stimulus-responsive characteristics, and therefore, anthracene-containing supramolecular assemblies have attracted much more extensive attention from supramolecular chemists. Anthracene moiety is susceptible to attack by singlet oxygen (<sup>1</sup>O<sub>2</sub>), and it undergoes [4 + 2] photooxygenation via capturing <sup>1</sup>O<sub>2</sub> under 365 nm irradiation, generating endoperoxide photoproducts that could release <sup>1</sup>O<sub>2</sub> through heat. A variety of anthracene-based supramolecular assemblies are elegantly designed and synthesized to further explore their properties. In the past few decades, numerous articles and few reviews about the [4 + 4] photodimerization of anthracene moiety have been published. Howerer, to the best of our knowledge, very few reviews focusing on anthracene-based supramolecular systems and their reversible [4 + 2] photochemical oxidation have hardly been reported. The minor review primarily highlights typical examples of anthracene-containing supramolecular assemblies in terms of construction strategy, properties, and the [4 + 2] photooxygenation. In this review, the main content will be classified into four categories: (I) chirality in anthracene-based supramolecular assemblies; (II) luminescence regulation in anthracene-containing supramolecular assemblies; (III) π···π interactions in anthracene-based supramolecular assemblies; (IV) [4 + 2] photooxygenation in anthracene-based supramolecular assemblies including discrete, polymeric, and anion-directed structures. We wish this mini-review could provide fundamental inspiration for supramolecular scientists to further develop novel anthracene-containing assemblies based on coordination-driven self-assembly and study their photochemical reactions, which is showing potential for application in smart materials.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100765"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01DOI: 10.1016/j.cjsc.2025.100767
Pan Gao , Qingzheng Kong , Ying Sun , Qian Ma , Qi Wang , Zeyu Guo , Ledi Li , Bingbing Li , Jingwei Xu , Xiaomei Jiang , Zhaolai Chen
X-ray detectors, as crucial elements in medical imaging and industrial fields, can be categorized into direct and indirect types. Direct detectors, which directly convert X-ray photons into electrical signals, exhibit high sensitivity and low detection limits, enabling the capture of high-resolution images and reducing radiation exposure to patients. Organic copper halides, recognized as potential active materials for X-ray detection, have been widely explored in the indirect scintillation field but remain under-explored in direct X-ray detector applications. In this work, (C12H12N)3Cu3I6 is demonstrated as an efficient semiconductor for direct X-ray detection with excellent stability. A lateral-structured X-ray detector was fabricated with gold electrodes, which exhibits a maximum sensitivity of 1464.14 μC·Gy−1·cm−2, a lowest detection limit of 19.8 nGy·s−1, a high on-off ratio of 2140, and an excellent operational stability of retaining 96% performance after 600 s continuous X-ray radiation. Furthermore, the detector successfully imaged a 0.1 mm “F”-shaped lead sheet, validating its capacity for X-ray imaging. This study highlights the potential of (C12H12N)3Cu3I6 as a promising semiconductor for high-performance direct X-ray detection, expanding the application scope of organic copper halides in this critical field.
x射线探测器是医学成像和工业领域的重要组成部分，可分为直接型和间接型。直接探测器直接将x射线光子转换为电信号，具有高灵敏度和低检测极限，可以捕获高分辨率图像并减少对患者的辐射暴露。有机卤化铜作为一种潜在的x射线探测活性材料，在间接闪烁领域得到了广泛的探索，但在直接x射线探测领域的应用还不够充分。在这项工作中，（C12H12N）3Cu3I6被证明是一种有效的半导体，用于直接x射线检测，具有优异的稳定性。采用金电极制备了一种横向结构的x射线探测器，最大灵敏度为1464.14 μC·Gy−1·cm−2，最低检出限为19.8 nGy·s−1，通断比为2140，在连续600 s x射线照射后仍能保持96%的性能。此外，该探测器还成功地对0.1 mm“F”形铅片进行了成像，验证了其x射线成像能力。该研究突出了（C12H12N）3Cu3I6作为高性能直接x射线探测半导体的潜力，扩大了有机卤化铜在这一关键领域的应用范围。
{"title":"One-dimensional (C12H12N)3Cu3I6 for high-performance direct X-ray detection","authors":"Pan Gao , Qingzheng Kong , Ying Sun , Qian Ma , Qi Wang , Zeyu Guo , Ledi Li , Bingbing Li , Jingwei Xu , Xiaomei Jiang , Zhaolai Chen","doi":"10.1016/j.cjsc.2025.100767","DOIUrl":"10.1016/j.cjsc.2025.100767","url":null,"abstract":"<div><div>X-ray detectors, as crucial elements in medical imaging and industrial fields, can be categorized into direct and indirect types. Direct detectors, which directly convert X-ray photons into electrical signals, exhibit high sensitivity and low detection limits, enabling the capture of high-resolution images and reducing radiation exposure to patients. Organic copper halides, recognized as potential active materials for X-ray detection, have been widely explored in the indirect scintillation field but remain under-explored in direct X-ray detector applications. In this work, (C<sub>12</sub>H<sub>12</sub>N)<sub>3</sub>Cu<sub>3</sub>I<sub>6</sub> is demonstrated as an efficient semiconductor for direct X-ray detection with excellent stability. A lateral-structured X-ray detector was fabricated with gold electrodes, which exhibits a maximum sensitivity of 1464.14 μC·Gy<sup>−1</sup>·cm<sup>−2</sup>, a lowest detection limit of 19.8 nGy·s<sup>−1</sup>, a high on-off ratio of 2140, and an excellent operational stability of retaining 96% performance after 600 s continuous X-ray radiation. Furthermore, the detector successfully imaged a 0.1 mm “F”-shaped lead sheet, validating its capacity for X-ray imaging. This study highlights the potential of (C<sub>12</sub>H<sub>12</sub>N)<sub>3</sub>Cu<sub>3</sub>I<sub>6</sub> as a promising semiconductor for high-performance direct X-ray detection, expanding the application scope of organic copper halides in this critical field.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 1","pages":"Article 100767"},"PeriodicalIF":10.3,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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