Pub Date : 2025-10-01DOI: 10.1016/j.cjsc.2025.100719
Pengfu Gao, Yuan Geng, Wei Gong
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
{"title":"Homochiral metal-organic frameworks bearing privileged ligands for heterogeneous asymmetric catalysis","authors":"Pengfu Gao, Yuan Geng, Wei Gong","doi":"10.1016/j.cjsc.2025.100719","DOIUrl":"10.1016/j.cjsc.2025.100719","url":null,"abstract":"<div><div>Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100719"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398059","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100712
Xing-Cheng Hu , Qiu-Shui Mu , Shu-Jin Bao , Yan Zou , Xin-Yu Wang , Guo-Xin Jin
Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl)phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1–C1–C2–N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units Rh–B1, Rh–B2, Rh–B3, and Rh–B4 featuring Cp∗RhIII (Cp∗ = η5-pentamethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh-3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through programming different combination of noncovalent interactions (π-π stacking, CH⋯π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp∗IrIII analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.
{"title":"Ligand conformational adaptability modulated self-assembly of Solomon links (412) and trefoil knots (31)","authors":"Xing-Cheng Hu , Qiu-Shui Mu , Shu-Jin Bao , Yan Zou , Xin-Yu Wang , Guo-Xin Jin","doi":"10.1016/j.cjsc.2025.100712","DOIUrl":"10.1016/j.cjsc.2025.100712","url":null,"abstract":"<div><div>Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl)phenyl) benzo[c][1,2,5]thiadiazole (<strong>L1</strong>) with a tunable torsional angle <em>θ</em> of N1–C1–C2–N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, <strong>L1</strong> selectively assembles with binuclear half-sandwich units <strong>Rh–B1</strong>, <strong>Rh–B2</strong>, <strong>Rh–B3</strong>, and <strong>Rh–B4</strong> featuring Cp∗Rh<sup>III</sup> (Cp∗ = <em>η</em><sup>5</sup>-pentamethylcyclopentadienyl) into distinct topologies: Solomon links <strong>Rh-1</strong>, trefoil knots <strong>Rh-2</strong>, molecular tweezers <strong>Rh-3</strong>, and <strong>Rh-4</strong>, respectively. Crucially, the self-adaptability of ligand <strong>L1</strong> directs topology formation through programming different combination of noncovalent interactions (π-π stacking, CH⋯π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp∗Ir<sup>III</sup> analogs (Solomon links <strong>Ir-1</strong>, trefoil knots <strong>Ir-2</strong>, molecular tweezers <strong>Ir-3</strong> and <strong>Ir-4</strong>), demonstrating metal-independent control and achieving intricate topologies in a high yield.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100712"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398055","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100681
Lingyue Liu , Jie Ding
{"title":"Atomic design of SACs directs PMS activation through ETP","authors":"Lingyue Liu , Jie Ding","doi":"10.1016/j.cjsc.2025.100681","DOIUrl":"10.1016/j.cjsc.2025.100681","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100681"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398173","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100705
Xiao-Qian Wan , Ya-Ning Xu , Jian-Xin Yang , Dan Tian , Li-Long Dang , Feng Bai , Lu-Fang Ma
The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists. Nevertheless, the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce. Here, four organometallic cages 1, 2, 3 and 4 with different functional sites are synthesized via reasonably selecting different building units E1, E2, E3 and E4 based on a tetradentate pyridyl ligand L1. These complexes are characterized by single-crystal X-ray diffraction analysis, nuclear magnetic resonance (NMR) spectroscopy and ESI-TOF-MS analysis. Notably, they exhibit different near-infrared (NIR) photothermal conversion properties due to variations in their size, conjugated area, and electron-withdrawing characteristic of halogen atoms in building units. Compound 4 shows the optimal photothermal performance among this series, with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency. The radical effect of the building unit plays an important role in photothermal conversion ability, as evidenced by the significant EPR signal changes. Therefore, compound 4 is used to construct new membrane 1′, achieving a solar power-induced water steam generation rate of 1.92 kg·m−2·h−1, demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment. This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.
{"title":"Structural optimization of organometallic cages for enhanced photothermal solar water evaporation","authors":"Xiao-Qian Wan , Ya-Ning Xu , Jian-Xin Yang , Dan Tian , Li-Long Dang , Feng Bai , Lu-Fang Ma","doi":"10.1016/j.cjsc.2025.100705","DOIUrl":"10.1016/j.cjsc.2025.100705","url":null,"abstract":"<div><div>The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists. Nevertheless, the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce. Here, four organometallic cages <strong>1</strong>, <strong>2</strong>, <strong>3</strong> and <strong>4</strong> with different functional sites are synthesized via reasonably selecting different building units <strong>E1</strong>, <strong>E2</strong>, <strong>E3</strong> and <strong>E4</strong> based on a tetradentate pyridyl ligand <strong>L1</strong>. These complexes are characterized by single-crystal X-ray diffraction analysis, nuclear magnetic resonance (NMR) spectroscopy and ESI-TOF-MS analysis. Notably, they exhibit different near-infrared (NIR) photothermal conversion properties due to variations in their size, conjugated area, and electron-withdrawing characteristic of halogen atoms in building units. Compound <strong>4</strong> shows the optimal photothermal performance among this series, with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency. The radical effect of the building unit plays an important role in photothermal conversion ability, as evidenced by the significant EPR signal changes. Therefore, compound <strong>4</strong> is used to construct new membrane <strong>1′</strong>, achieving a solar power-induced water steam generation rate of 1.92 kg·m<sup>−2</sup>·h<sup>−1</sup>, demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment. This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100705"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398053","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100707
Xiaodong Zhang , Bohui Xu , Deshuai Xiao , Xinyuan Zhang , Pifu Gong , Zheshuai Lin
Non-centrosymmetric (NCS) crystalline structures, critical for second harmonic generation (SHG) in all-solid-state lasers, are far less prevalent than their centrosymmetric (CS) counterparts. In this study, we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation, as illustrated by the transition in the newly discovered CN3H6C6H5SO3 (CS) and CN3H6C6H4SO3(OH) (NCS). The introduced hydroxyl groups induce hydrogen bond reconstruction, effectively breaking the original centrosymmetry. The resulting NCS compound exhibits remarkable nonlinear optical (NLO) properties, including a strong SHG response (1.6 × KDP with the particle sizes of 200–250 μm), a wide bandgap (UV cutoff at 290 nm, corresponding band gap is 4.37 eV), and a large birefringence (0.21@1064 nm), demonstrating excellent potential as an UV NLO crystal material.
{"title":"From centrosymmetric CN3H6C6H5SO3 to non-centrosymmetric CN3H6C6H4SO3(OH): Hydroxyl introduced hydrogen bond reconstruction to realize strong second harmonic generation","authors":"Xiaodong Zhang , Bohui Xu , Deshuai Xiao , Xinyuan Zhang , Pifu Gong , Zheshuai Lin","doi":"10.1016/j.cjsc.2025.100707","DOIUrl":"10.1016/j.cjsc.2025.100707","url":null,"abstract":"<div><div>Non-centrosymmetric (NCS) crystalline structures, critical for second harmonic generation (SHG) in all-solid-state lasers, are far less prevalent than their centrosymmetric (CS) counterparts. In this study, we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation, as illustrated by the transition in the newly discovered CN<sub>3</sub>H<sub>6</sub>C<sub>6</sub>H<sub>5</sub>SO<sub>3</sub> (CS) and CN<sub>3</sub>H<sub>6</sub>C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>(OH) (NCS). The introduced hydroxyl groups induce hydrogen bond reconstruction, effectively breaking the original centrosymmetry. The resulting NCS compound exhibits remarkable nonlinear optical (NLO) properties, including a strong SHG response (1.6 × KDP with the particle sizes of 200–250 μm), a wide bandgap (UV cutoff at 290 nm, corresponding band gap is 4.37 eV), and a large birefringence (0.21@1064 nm), demonstrating excellent potential as an UV NLO crystal material.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100707"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398054","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100678
Hua Tong, Haibo Li, Wei Liu, Gangfeng Ouyang
Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (0D) organic antimony halide (1-BMP)5(SbCl5)2SbCl4 with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl5]2– and the fluorescence of organic cations 1-BMP+, respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.
{"title":"Lead-free organic antimony halide with dual-band intrinsic white light emission for warm WLED directly","authors":"Hua Tong, Haibo Li, Wei Liu, Gangfeng Ouyang","doi":"10.1016/j.cjsc.2025.100678","DOIUrl":"10.1016/j.cjsc.2025.100678","url":null,"abstract":"<div><div>Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (0D) organic antimony halide (1-BMP)<sub>5</sub>(SbCl<sub>5</sub>)<sub>2</sub>SbCl<sub>4</sub> with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl<sub>5</sub>]<sup>2</sup><sup>–</sup> and the fluorescence of organic cations 1-BMP<sup>+</sup>, respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100678"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398092","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 : 2025-10-01DOI: 10.1016/j.cjsc.2025.100704
Yijia Chen , Wendan Luo , Ke Liu , Taihong Liu , Liping Ding , Yu Fang
Correlation between tunable optical properties and push-pull structural characters has attracted extensive attention in material science and nonlinear optics. Here, several indacenodithiophene (IDT) derivatives denoted as IDT-2NA, NA-IDT-CN, and IDT-2CN with different terminal substituents are investigated comparatively to demonstrate their intrinsic structure-property relationships. Interestingly, the IDT core acts diverse roles as acceptor (A) and donor (D) in the obtained three derivatives. Symmetric IDT-2NA with a D-A-D architecture shows an absorption maximum around 459 nm in THF. Contrary to the symmetric analog IDT-2CN with a reverse A-D-A feature, NA-IDT-CN with a different D-D′-A motif characterizes an obvious solvent polarity effect. Theoretical calculation and electrostatic potential results confirm the terminal substituents with different electronic conjugation play vital roles in affecting the resultant photophysical properties. Utilizing the femtosecond open-aperture Z-scan technique, significant two-photon absorption (2PA) capabilities are obtained ranging from 540 to 900 nm. The 2PA cross section (δ2PA) maximum about 5390 GM of centrosymmetric IDT-2CN exhibits at 600 nm. Distinct excited-state dynamics with the help of femtosecond transition absorption supports the effective intramolecular charge transfer which accounts for enhancing the δ2PA values. Their potential optical power limiting applications based on the 2PA mechanism were further evaluated. The limiting thresholds were found to be 2.79–3.35 mJ/cm2 for the three IDT derivatives with a sequence of IDT-2CN < IDT-2NA < NA-IDT-CN. The distinct structural motifs and effective 2PA capabilities in the current work may provide reliable insights into the push-pull IDT chromophores for advanced nonlinear optical applications.
{"title":"Diverse roles of indacenodithiophene in push-pull chromophores for enhanced two-photon absorption and efficient nonlinear optical limiting","authors":"Yijia Chen , Wendan Luo , Ke Liu , Taihong Liu , Liping Ding , Yu Fang","doi":"10.1016/j.cjsc.2025.100704","DOIUrl":"10.1016/j.cjsc.2025.100704","url":null,"abstract":"<div><div>Correlation between tunable optical properties and push-pull structural characters has attracted extensive attention in material science and nonlinear optics. Here, several indacenodithiophene (IDT) derivatives denoted as IDT-2NA, NA-IDT-CN, and IDT-2CN with different terminal substituents are investigated comparatively to demonstrate their intrinsic structure-property relationships. Interestingly, the IDT core acts diverse roles as acceptor (A) and donor (D) in the obtained three derivatives. Symmetric IDT-2NA with a D-A-D architecture shows an absorption maximum around 459 nm in THF. Contrary to the symmetric analog IDT-2CN with a reverse A-D-A feature, NA-IDT-CN with a different D-D′-A motif characterizes an obvious solvent polarity effect. Theoretical calculation and electrostatic potential results confirm the terminal substituents with different electronic conjugation play vital roles in affecting the resultant photophysical properties. Utilizing the femtosecond open-aperture Z-scan technique, significant two-photon absorption (2PA) capabilities are obtained ranging from 540 to 900 nm. The 2PA cross section (<em>δ</em><sub>2PA</sub>) maximum about 5390 GM of centrosymmetric IDT-2CN exhibits at 600 nm. Distinct excited-state dynamics with the help of femtosecond transition absorption supports the effective intramolecular charge transfer which accounts for enhancing the <em>δ</em><sub>2PA</sub> values. Their potential optical power limiting applications based on the 2PA mechanism were further evaluated. The limiting thresholds were found to be 2.79–3.35 mJ/cm<sup>2</sup> for the three IDT derivatives with a sequence of IDT-2CN < IDT-2NA < NA-IDT-CN. The distinct structural motifs and effective 2PA capabilities in the current work may provide reliable insights into the push-pull IDT chromophores for advanced nonlinear optical applications.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 10","pages":"Article 100704"},"PeriodicalIF":10.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398094","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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