Short-wavelength nonlinear optical (NLO) crystals can convert a specific wavelength of light to ultraviolet (UV) and deep-UV region. To date, most of the commercialized UV and deep-UV NLO materials are borate crystals. By combining the merits of borates and silicates, borosilicates exhibit some unique advantages of rich structural types, moderate second harmonic generation (SHG) response, and high UV transmittance. This paper summarizes the known NLO borosilicates which can be grouped into two types according to the linkage modes of B–O and Si–O units: (1) borosilicates with B–O–Si covalent bond, and (2) borosilicates with isolated B–O and Si–O units. The structural features, SHG intensities, and UV cutoff edges of these borosilicates are discussed. Finally, future perspectives in this field are presented.
{"title":"Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions","authors":"Yangfeifei Ou, Xiao-Liang Zhou, You-Zhao Lan, Jian-Wen Cheng","doi":"10.1016/j.cjsc.2025.100708","DOIUrl":"10.1016/j.cjsc.2025.100708","url":null,"abstract":"<div><div>Short-wavelength nonlinear optical (NLO) crystals can convert a specific wavelength of light to ultraviolet (UV) and deep-UV region. To date, most of the commercialized UV and deep-UV NLO materials are borate crystals. By combining the merits of borates and silicates, borosilicates exhibit some unique advantages of rich structural types, moderate second harmonic generation (SHG) response, and high UV transmittance. This paper summarizes the known NLO borosilicates which can be grouped into two types according to the linkage modes of B–O and Si–O units: (1) borosilicates with B–O–Si covalent bond, and (2) borosilicates with isolated B–O and Si–O units. The structural features, SHG intensities, and UV cutoff edges of these borosilicates are discussed. Finally, future perspectives in this field are presented.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100708"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289733","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 : 2025-09-01DOI: 10.1016/j.cjsc.2025.100653
Matvey K. Shurikov , Yuliana A. Kolesnikova , Darya E. Votkina , Pavel A. Abramov , Taisiya S. Sukhikh , Galina V. Romanenko , Sergey L. Veber , Dmitry E. Gorbunov , Nina P. Gritsan , Giuseppe Resnati , Evgeny V. Tretyakov , Vadim Yu. Kukushkin , Pavel S. Postnikov , Pavel V. Petunin
Six aryl- and pyridine-substituted nitronyl-nitroxide radicals were synthesized and characterized to investigate their optical anisotropic properties. Single-crystal X-ray diffraction analysis revealed molecular packing organized by either halogen and hydrogen bonding or hydrogen bonding alone. Single-crystal electronic absorption spectra in the visible region of three studied radicals exhibit pronounced linear dichroism, while single crystals of other radicals do not demonstrate this property. Time-dependent DFT and ab initio calculations were employed to determine the transition dipole moment (TDM) vectors corresponding to the long-wavelength absorption bands. For all radicals, these vectors are found to be practically parallel to the O⋯O direction of the nitronyl-nitroxide chromophore. Correlation between the dichroic properties and crystal structure was established through comprehensive analysis of TDM vector orientations relative to the crystal surface. The strongest dichroic effect was observed in crystals where all projections of the TDM vectors onto the illuminated face are parallel to each other, while weaker or absent effects correspond to non-parallel arrangements. This study constitutes the first systematic investigation of linear dichroism in paramagnetic organic crystals, thereby establishing new avenues for developing multifunctional materials that respond to both optical and magnetic stimuli.
{"title":"Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals","authors":"Matvey K. Shurikov , Yuliana A. Kolesnikova , Darya E. Votkina , Pavel A. Abramov , Taisiya S. Sukhikh , Galina V. Romanenko , Sergey L. Veber , Dmitry E. Gorbunov , Nina P. Gritsan , Giuseppe Resnati , Evgeny V. Tretyakov , Vadim Yu. Kukushkin , Pavel S. Postnikov , Pavel V. Petunin","doi":"10.1016/j.cjsc.2025.100653","DOIUrl":"10.1016/j.cjsc.2025.100653","url":null,"abstract":"<div><div><span>Six aryl- and pyridine-substituted nitronyl-nitroxide radicals were synthesized and characterized to investigate their optical anisotropic properties. Single-crystal X-ray diffraction analysis revealed molecular packing organized by either halogen and hydrogen bonding<span><span> or hydrogen bonding alone. Single-crystal electronic </span>absorption spectra<span> in the visible region of three studied radicals exhibit pronounced linear dichroism, while single crystals of other radicals do not demonstrate this property. Time-dependent DFT and </span></span></span><em>ab initio</em><span><span> calculations were employed to determine the transition dipole moment<span> (TDM) vectors corresponding to the long-wavelength absorption bands. For all radicals, these vectors are found to be practically parallel to the O⋯O direction of the nitronyl-nitroxide chromophore. Correlation between the dichroic properties and crystal structure was established through comprehensive analysis of TDM vector orientations relative to the </span></span>crystal surface. The strongest dichroic effect was observed in crystals where all projections of the TDM vectors onto the illuminated face are parallel to each other, while weaker or absent effects correspond to non-parallel arrangements. This study constitutes the first systematic investigation of linear dichroism in paramagnetic organic crystals, thereby establishing new avenues for developing multifunctional materials that respond to both optical and magnetic stimuli.</span></div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100653"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289738","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 : 2025-09-01DOI: 10.1016/j.cjsc.2025.100660
Yuhao Jin, Zheng Zhou, Haixiang Han
The synthesized molecular clusters featuring the cubic [4Fe–4S] core have been studied for several decades, as they serve as true analogs of the active components in ferritin within biological systems. Such a model cluster has been extensively investigated in various fields, including structural modulation, catalysis, and self-assembly under laboratory conditions, with the aim of gaining an in-depth understanding of their roles in biological functions. Herein, we revisited three well-known [Fe4S4(SR)4]2– molecules, namely [Me4N]2[Fe4S4(SR)4] (R = o-MBT, m-MBT, p-MBT), and successfully established their single crystal structures that remain unknown prior to this work. Interestingly, it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the [4Fe–4S] core, which further influences their overall packing patterns in single crystals. In addition, this work unveils two new structure transformation behaviors for the [Fe4S4(SR)4]2– system: i) the monomeric [Fe(SR)4]2– and tetrameric [Fe4S4(SR)4]2– can be interconverted, and ii) [Fe4S4(SR)4]2– can be transferred into an intriguing iron-oxide complex Na2Fe6O(OMe)18·6MeOH in a well-controlled oxidizing environment.
{"title":"Revisit the classical [Fe4S4(SR)4]2– molecular clusters: The steric effects of ligands and their structural transformations","authors":"Yuhao Jin, Zheng Zhou, Haixiang Han","doi":"10.1016/j.cjsc.2025.100660","DOIUrl":"10.1016/j.cjsc.2025.100660","url":null,"abstract":"<div><div>The synthesized molecular clusters featuring the cubic [4Fe–4S] core have been studied for several decades, as they serve as true analogs of the active components in ferritin within biological systems. Such a model cluster has been extensively investigated in various fields, including structural modulation, catalysis, and self-assembly under laboratory conditions, with the aim of gaining an in-depth understanding of their roles in biological functions. Herein, we revisited three well-known [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> molecules, namely [Me<sub>4</sub>N]<sub>2</sub>[Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>] (R = <em>o</em>-MBT, <em>m</em>-MBT, <em>p</em>-MBT), and successfully established their single crystal structures that remain unknown prior to this work. Interestingly, it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the [4Fe–4S] core, which further influences their overall packing patterns in single crystals. In addition, this work unveils two new structure transformation behaviors for the [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> system: i) the monomeric [Fe(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> and tetrameric [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> can be interconverted, and ii) [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> can be transferred into an intriguing iron-oxide complex Na<sub>2</sub>Fe<sub>6</sub>O(OMe)<sub>18</sub>·6MeOH in a well-controlled oxidizing environment.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100660"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289743","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 : 2025-09-01DOI: 10.1016/j.cjsc.2025.100661
Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge
Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination, yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear. Herein, density functional theory (DFT) calculations first reveal the modulation of sulfur vacancy concentrations on Co9S8 electronic structures, predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting. Experimentally fabricated Co9S8 with appropriate sulfur vacancies exhibits superior bifunctional activity (HER: 164 mV@η10; OER: 297 mV@η100). The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V (10 mA cm−2) for over 60 h. Experimental studies illustrate that sulfur vacancies preferentially adsorb OH− during reactions, inducing the formation of CoOOH active phases. DFT analysis further indicates that OH− adsorption weakens d-p orbital hybridization, optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance. This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics, electronic structures and catalytic performance.
缺陷工程通过调节电子结构和界面配位显著提高电催化性能，但反应过程中缺陷演化与催化活性之间的动态关系尚不清楚。在此，密度泛函理论（DFT）计算首次揭示了硫空位浓度对Co9S8电子结构的调制，预测优化的空位浓度可以实现高效的电催化水分解。实验制备的具有适当硫空位的Co9S8具有优异的双功能活性（HER: 164 mV@η10; OER: 297 mV@η100）。mcs组装的整体水分解系统在1.57 V （10 mA cm−2）下稳定运行超过60小时。实验研究表明，硫空位在反应过程中优先吸附OH -，诱导CoOOH活性相的形成。DFT分析进一步表明，OH -吸附减弱了d-p轨道杂化，优化了氢/氧中间体吸附能垒，最终提高了催化性能。这项工作通过对缺陷动力学、电子结构和催化性能的协同分析，为催化剂的系统开发建立了新的范例。
{"title":"Dynamic tuning of d-p orbital hybridization during sulfur vacancy evolution in Co9S8 toward efficient overall water splitting","authors":"Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge","doi":"10.1016/j.cjsc.2025.100661","DOIUrl":"10.1016/j.cjsc.2025.100661","url":null,"abstract":"<div><div>Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination, yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear. Herein, density functional theory (DFT) calculations first reveal the modulation of sulfur vacancy concentrations on Co<sub>9</sub>S<sub>8</sub> electronic structures, predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting. Experimentally fabricated Co<sub>9</sub>S<sub>8</sub> with appropriate sulfur vacancies exhibits superior bifunctional activity (HER: 164 mV@<em>η</em><sub>10</sub>; OER: 297 mV@<em>η</em><sub>100</sub>). The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V (10 mA cm<sup>−2</sup>) for over 60 h. Experimental studies illustrate that sulfur vacancies preferentially adsorb OH<sup>−</sup> during reactions, inducing the formation of CoOOH active phases. DFT analysis further indicates that OH<sup>−</sup> adsorption weakens <em>d-p</em> orbital hybridization, optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance. This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics, electronic structures and catalytic performance.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100661"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289744","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 : 2025-09-01DOI: 10.1016/j.cjsc.2025.100651
Qimeng Zhu , Juan Xiao , Changyi Deng , Tingting Huang , Hui Ding , Li Zhang , Guancheng Xu
In recent years, the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health. In this context, the urea oxidation reaction (UOR) has attracted significant attention due to its low thermodynamic potential of 0.37 V (vs. RHE). Compared with oxygen evolution reaction (OER), this reaction can significantly reduce the energy consumption of electrolysis while realizing wastewater treatment, and has the dual functions of hydrogen energy preparation and wastewater purification. However, UOR involves complex six-electron transfer and intermediate adsorption/desorption processes, resulting in slow reaction kinetics. Therefore, the development of economical and efficient catalysts has become a research focus, among which transition metal phosphides (TMPs) stand out due to their low cost, excellent activity and adjustable electronic structure. Compared with other non-noble metal systems, TMPs have unique electronic structure and surface properties that can adsorb and activate urea molecules more efficiently. However, there is still a lack of systematic reviews on TMP catalysts at present. Therefore, this review aims to deeply and systematically elaborate the design strategies of TMP catalysts and their applications in UOR, thoroughly discuss the current progress, challenges and future directions, and provide theoretical support and design ideas for the development of a new generation of efficient and stable UOR catalysts.
{"title":"Highly active transition metal phosphides for urea oxidation: Design strategies, application advances, and perspectives","authors":"Qimeng Zhu , Juan Xiao , Changyi Deng , Tingting Huang , Hui Ding , Li Zhang , Guancheng Xu","doi":"10.1016/j.cjsc.2025.100651","DOIUrl":"10.1016/j.cjsc.2025.100651","url":null,"abstract":"<div><div><span>In recent years, the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health. In this context, the urea oxidation reaction (UOR) has attracted significant attention due to its low thermodynamic potential of 0.37 V (</span><em>vs.</em><span> RHE). Compared with oxygen evolution reaction (OER), this reaction can significantly reduce the energy consumption of electrolysis while realizing wastewater treatment, and has the dual functions of hydrogen energy preparation and wastewater purification. However, UOR involves complex six-electron transfer and intermediate adsorption/desorption processes, resulting in slow reaction kinetics. Therefore, the development of economical and efficient catalysts has become a research focus, among which transition metal phosphides (TMPs) stand out due to their low cost, excellent activity and adjustable electronic structure. Compared with other non-noble metal systems, TMPs have unique electronic structure and surface properties that can adsorb and activate urea molecules more efficiently. However, there is still a lack of systematic reviews on TMP catalysts at present. Therefore, this review aims to deeply and systematically elaborate the design strategies of TMP catalysts and their applications in UOR, thoroughly discuss the current progress, challenges and future directions, and provide theoretical support and design ideas for the development of a new generation of efficient and stable UOR catalysts.</span></div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100651"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289798","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 : 2025-09-01DOI: 10.1016/j.cjsc.2025.100676
Malaika Arshad , Zia Ul Haq Khan , Swera Talib , Sana Sabahat , Noor Samad Shah , Huma Ajab , Farooq Ahmad , Syed Khasim , M.A. Diab , Heba A. El-Sabban
An expanding human population and technological progress demand clean and effective energy-storing systems. Within the realm of energy-storing devices, supercapacitors (SCs) have grabbed huge focus owing to their high-power density, unique cycling stability, and fast charging discharging capabilities. Electrode material has a prominent impact on the effectiveness of SCs. Several types of electrode materials have been used, encompassing varied metal oxides, activated carbon, conducting polymers, and MOFs. Metal organic frameworks (MOFs) are considered emerging electrode candidates, which could be ascribed to the tunable porosity, large surface areas, and designed morphology. This review shows a detailed analysis of various mono-, bi-, and tri-metallic MOFs along with derivatives in SC applications, their structural characteristics, and synthetic strategies. It also critically evaluates MOFs potential to boost the SC's energy density, power density, stability, and conductivity. Also, it underscores their significance in the establishment of future-oriented energy storage applications.
{"title":"A comprehensive review: MOFs and their derivatives as high-performance supercapacitor electrodes","authors":"Malaika Arshad , Zia Ul Haq Khan , Swera Talib , Sana Sabahat , Noor Samad Shah , Huma Ajab , Farooq Ahmad , Syed Khasim , M.A. Diab , Heba A. El-Sabban","doi":"10.1016/j.cjsc.2025.100676","DOIUrl":"10.1016/j.cjsc.2025.100676","url":null,"abstract":"<div><div>An expanding human population and technological progress demand clean and effective energy-storing systems. Within the realm of energy-storing devices, supercapacitors (SCs) have grabbed huge focus owing to their high-power density, unique cycling stability, and fast charging discharging capabilities. Electrode material has a prominent impact on the effectiveness of SCs. Several types of electrode materials have been used, encompassing varied metal oxides, activated carbon, conducting polymers, and MOFs. Metal organic frameworks (MOFs) are considered emerging electrode candidates, which could be ascribed to the tunable porosity, large surface areas, and designed morphology. This review shows a detailed analysis of various mono-, bi-, and tri-metallic MOFs along with derivatives in SC applications, their structural characteristics, and synthetic strategies. It also critically evaluates MOFs potential to boost the SC's energy density, power density, stability, and conductivity. Also, it underscores their significance in the establishment of future-oriented energy storage applications.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100676"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289732","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号