Login In
2026 Volume 45 Issue 1
2026, 45(1): 100698
doi: 10.1016/j.cjsc.2025.100698
Abstract:
The polymeric semiconductor photocatalyst graphitic carbon nitride (g-C3N4) has attracted considerable attention due to its visible-light responsiveness and excellent biocompatibility. However, the photocatalytic efficiency of bulk g-C3N4 (CNB) remains insufficient for pratical applications, primarily due to its limited light absorption range and the rapid charge carrier recombination. In this study, K+-doped crystalline g-C3N4 with cyano defects (CNK) was synthesized by the calcination of dicyandiamide in the presence of KCl. The addition of KCl promoted the formation of K+-doped crystalline g-C3N4 with cyano defects. The optimized photocatalyst (CNK2) exhibited the highest photocatalytic activity for NO oxidation, achieving a removal rate of 47.40%, which is 2.1 times higher than that of CNB. This enhancement is mainly attributed to the increased generation of reactive oxygen species (ROS), particularly superoxide radicals (·O2-) and singlet oxygen (1O2). Furthermore, improved performance in photocatalytic CO2-to-CH4 conversion was also observed, which is attributed to the formation of a build-in electric field (BIEF) induced by K+ ion doping and the introduction of cyano defects.
The polymeric semiconductor photocatalyst graphitic carbon nitride (g-C3N4) has attracted considerable attention due to its visible-light responsiveness and excellent biocompatibility. However, the photocatalytic efficiency of bulk g-C3N4 (CNB) remains insufficient for pratical applications, primarily due to its limited light absorption range and the rapid charge carrier recombination. In this study, K+-doped crystalline g-C3N4 with cyano defects (CNK) was synthesized by the calcination of dicyandiamide in the presence of KCl. The addition of KCl promoted the formation of K+-doped crystalline g-C3N4 with cyano defects. The optimized photocatalyst (CNK2) exhibited the highest photocatalytic activity for NO oxidation, achieving a removal rate of 47.40%, which is 2.1 times higher than that of CNB. This enhancement is mainly attributed to the increased generation of reactive oxygen species (ROS), particularly superoxide radicals (·O2-) and singlet oxygen (1O2). Furthermore, improved performance in photocatalytic CO2-to-CH4 conversion was also observed, which is attributed to the formation of a build-in electric field (BIEF) induced by K+ ion doping and the introduction of cyano defects.
2026, 45(1): 100730
doi: 10.1016/j.cjsc.2025.100730
Abstract:
2026, 45(1): 100731
doi: 10.1016/j.cjsc.2025.100731
Abstract:
Covalent organic frameworks (COFs), as a burgeoning type of porous material, have attracted significant attention due to their intriguing structural characteristics and customizable functionalities. Particularly COFs that exhibit luminescent properties have garnered significant attention in fields like chemical sensing, biosensing, photocatalysis, optoelectronics applications and so on. This article systematically examines the synthetic strategies for luminescent covalent organic frameworks (LCOFs) and provides a comprehensive summary based on linkage-type classification. This article further provides a comprehensive summary and emphasizes the broad and notable applications of LCOFs across multiple areas, such as luminescent applications, circularly polarized luminescence, fluorescent imaging, biomedicine, and chemical and biological sensing. Finally, the primary challenges and future directions of LCOFs concerning their synthetic method, structural design and optical properties are discussed. This review helps relevant researchers quickly understand the current research status in this field, and point out the direction for subsequent related research work. It is expected to promote the further development and application expansion of LCOFs synthesis technology, which has important academic value.
Covalent organic frameworks (COFs), as a burgeoning type of porous material, have attracted significant attention due to their intriguing structural characteristics and customizable functionalities. Particularly COFs that exhibit luminescent properties have garnered significant attention in fields like chemical sensing, biosensing, photocatalysis, optoelectronics applications and so on. This article systematically examines the synthetic strategies for luminescent covalent organic frameworks (LCOFs) and provides a comprehensive summary based on linkage-type classification. This article further provides a comprehensive summary and emphasizes the broad and notable applications of LCOFs across multiple areas, such as luminescent applications, circularly polarized luminescence, fluorescent imaging, biomedicine, and chemical and biological sensing. Finally, the primary challenges and future directions of LCOFs concerning their synthetic method, structural design and optical properties are discussed. This review helps relevant researchers quickly understand the current research status in this field, and point out the direction for subsequent related research work. It is expected to promote the further development and application expansion of LCOFs synthesis technology, which has important academic value.
2026, 45(1): 100732
doi: 10.1016/j.cjsc.2025.100732
Abstract:
2026, 45(1): 100760
doi: 10.1016/j.cjsc.2025.100760
Abstract:
Addressing the CO-sensitive and catalytic efficiency issues of noble metal-based electrocatalysts towards alkaline hydrogen oxidation reaction (HOR) are 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 mgPGM-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, provides new insights for noble-metal based catalysts designing.
Addressing the CO-sensitive and catalytic efficiency issues of noble metal-based electrocatalysts towards alkaline hydrogen oxidation reaction (HOR) are 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 mgPGM-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, provides new insights for noble-metal based catalysts designing.
2026, 45(1): 100761
doi: 10.1016/j.cjsc.2025.100761
Abstract:
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.
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.
2026, 45(1): 100762
doi: 10.1016/j.cjsc.2025.100762
Abstract:
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, time-resolved fluorescence decay spectra, attenuated total reflection Fourier transform infrared spectroscopy, and spin polarized density functional theory calculations. The results reveal that, upon photoexcitation, electrons in the 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 the 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.
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, time-resolved fluorescence decay spectra, attenuated total reflection Fourier transform infrared spectroscopy, and spin polarized density functional theory calculations. The results reveal that, upon photoexcitation, electrons in the 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 the 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.
2026, 45(1): 100763
doi: 10.1016/j.cjsc.2025.100763
Abstract:
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 contribute 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.
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 contribute 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.
2026, 45(1): 100764
doi: 10.1016/j.cjsc.2025.100764
Abstract:
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 octahedral and five-coordinate trigonal bipyramidal. 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.
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 octahedral and five-coordinate trigonal bipyramidal. 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.
2026, 45(1): 100765
doi: 10.1016/j.cjsc.2025.100765
Abstract:
Anthracene group features fluorescence, π conjugation, and stimulus-responsive characteristics, therefore, anthracene-containing supramolecular assemblies have attracted much more extensive attention from supramolecular chemists. Anthracene moiety is easily be attacked by singlet oxygen (1O2) to take place the [4 + 2] photooxygenation via capturing 1O2 after irradiation at 365 nm, generating endoperoxides 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, but very few reviews focusing on anthracene-based supramolecular systems and their reversible [4 + 2] photochemical oxidation, have hardly been reported, to our best knowledge. 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.
Anthracene group features fluorescence, π conjugation, and stimulus-responsive characteristics, therefore, anthracene-containing supramolecular assemblies have attracted much more extensive attention from supramolecular chemists. Anthracene moiety is easily be attacked by singlet oxygen (1O2) to take place the [4 + 2] photooxygenation via capturing 1O2 after irradiation at 365 nm, generating endoperoxides 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, but very few reviews focusing on anthracene-based supramolecular systems and their reversible [4 + 2] photochemical oxidation, have hardly been reported, to our best knowledge. 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.
2026, 45(1): 100766
doi: 10.1016/j.cjsc.2025.100766
Abstract:
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 the ultrahigh Bz/Cya (180) and Bz/Cye (66) selectivities, but also ultrahigh Bz selectivity (118) from the ternary Bz/Cye/Cya mixtures. Notably, all the above selectivities rank in the top three in all porous materials, and the Bz/Cye selectivity is the highest value 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.
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 the ultrahigh Bz/Cya (180) and Bz/Cye (66) selectivities, but also ultrahigh Bz selectivity (118) from the ternary Bz/Cye/Cya mixtures. Notably, all the above selectivities rank in the top three in all porous materials, and the Bz/Cye selectivity is the highest value 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.
2026, 45(1): 100767
doi: 10.1016/j.cjsc.2025.100767
Abstract:
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-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.
2026, 45(1): 100768
doi: 10.1016/j.cjsc.2025.100768
Abstract:
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 in-situ 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.
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 in-situ 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.
2026, 45(1): 100769
doi: 10.1016/j.cjsc.2025.100769
Abstract:
Coordination-directed synthesis has emerged as an effective and versatile approach for constructing mechanically interlocked molecules (MIMs). This field has long been dominated by Werner-type complexes featuring oxygen and/or nitrogen donors, whereas assemblies incorporating N-heterocyclic carbene (NHC) donors remain underexplored. This Review provides a comprehensive overview of the rapidly developing field of MIMs constructed from poly-NHC-based building blocks. By highlighting representative recent examples, this Review focuses on the pivotal role of NHC ligands and the robustness of the metal–CNHC bond in the construction of metallosupramolecular interlocked structures. In addition, this Review summarizes contemporary strategies for achieving efficient assembly, analyzes defining structural attributes of the resulting architectures, and outlines current challenges and emerging opportunities for future developments in NHC-based MIMs.
Coordination-directed synthesis has emerged as an effective and versatile approach for constructing mechanically interlocked molecules (MIMs). This field has long been dominated by Werner-type complexes featuring oxygen and/or nitrogen donors, whereas assemblies incorporating N-heterocyclic carbene (NHC) donors remain underexplored. This Review provides a comprehensive overview of the rapidly developing field of MIMs constructed from poly-NHC-based building blocks. By highlighting representative recent examples, this Review focuses on the pivotal role of NHC ligands and the robustness of the metal–CNHC bond in the construction of metallosupramolecular interlocked structures. In addition, this Review summarizes contemporary strategies for achieving efficient assembly, analyzes defining structural attributes of the resulting architectures, and outlines current challenges and emerging opportunities for future developments in NHC-based MIMs.
