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2025 Volume 41 Issue 1
2025, 41(1): 1-13
doi: 10.11862/CJIC.20240355
Abstract:
Using efficient and green materials to capture carbon dioxide will be beneficial to reducing artificial emissions of carbon dioxide into the atmosphere. The design and synthesis of high-performance metal-organic frameworks (MOFs) for capturing carbon dioxide from flue gas has entered a new stage driven by the application. Developing MOFs for carbon dioxide capture with superior comprehensive performance is challenging. This review focuses on the current research on such MOFs with low-cost ligands. Furthermore, their structures, water/thermal/chemical stability, adsorption capacity and selectivity, adsorption behaviors affected by moisture, multi-cycle usability, regeneration, and macroscopic preparation were discussed.
Using efficient and green materials to capture carbon dioxide will be beneficial to reducing artificial emissions of carbon dioxide into the atmosphere. The design and synthesis of high-performance metal-organic frameworks (MOFs) for capturing carbon dioxide from flue gas has entered a new stage driven by the application. Developing MOFs for carbon dioxide capture with superior comprehensive performance is challenging. This review focuses on the current research on such MOFs with low-cost ligands. Furthermore, their structures, water/thermal/chemical stability, adsorption capacity and selectivity, adsorption behaviors affected by moisture, multi-cycle usability, regeneration, and macroscopic preparation were discussed.
2025, 41(1): 14-34
doi: 10.11862/CJIC.20240388
Abstract:
Metal-organic frameworks are porous crystalline materials with a high specific surface area. The poor electrical conductivity of the traditional metal-organic frameworks limits their applications on electrical devices. Recent studies have shown that metal-organic framework materials with high electrical conductivity can be prepared by utilizing design strategies such as ligands containing specific conjugated structures, and further to expand their applications. Herein, the design strategies, characterization methods, the latest research progress, and applications of conductive metal-organic frameworks have been summarized, and the existing problems and potential tendencies are looked ahead to in this article as well.
Metal-organic frameworks are porous crystalline materials with a high specific surface area. The poor electrical conductivity of the traditional metal-organic frameworks limits their applications on electrical devices. Recent studies have shown that metal-organic framework materials with high electrical conductivity can be prepared by utilizing design strategies such as ligands containing specific conjugated structures, and further to expand their applications. Herein, the design strategies, characterization methods, the latest research progress, and applications of conductive metal-organic frameworks have been summarized, and the existing problems and potential tendencies are looked ahead to in this article as well.
2025, 41(1): 35-44
doi: 10.11862/CJIC.20240364
Abstract:
As the global economy develops rapidly, the consumption of traditional fossil fuels has significantly increased, leading to a substantial emission of carbon dioxide (CO2), which has a noticeable impact on the natural ecosystem. In recent years, the third-generation green bio-manufacturing technology, driven by solar energy and using atmospheric CO2 as raw material, has gained widespread global attention. Over the past several years, researchers have conducted extensive studies in solar-driven inorganic semiconductor-microorganism hybrid systems, which have profound implications for CO2 fixation and bio-manufacturing. This review comprehensively examines how to construct high-performance inorganic semiconductor-microorganism hybrid systems by focusing on three dimensions: the optimization of inorganic semiconductor material structures and properties, the construction of inorganic semiconductor-microorganism interfaces, and the targeted reconstruction of microorganism metabolic pathways. Finally, this review outlines the developmental trends in the field of inorganic semiconductor-microorganism hybrid systems.
As the global economy develops rapidly, the consumption of traditional fossil fuels has significantly increased, leading to a substantial emission of carbon dioxide (CO2), which has a noticeable impact on the natural ecosystem. In recent years, the third-generation green bio-manufacturing technology, driven by solar energy and using atmospheric CO2 as raw material, has gained widespread global attention. Over the past several years, researchers have conducted extensive studies in solar-driven inorganic semiconductor-microorganism hybrid systems, which have profound implications for CO2 fixation and bio-manufacturing. This review comprehensively examines how to construct high-performance inorganic semiconductor-microorganism hybrid systems by focusing on three dimensions: the optimization of inorganic semiconductor material structures and properties, the construction of inorganic semiconductor-microorganism interfaces, and the targeted reconstruction of microorganism metabolic pathways. Finally, this review outlines the developmental trends in the field of inorganic semiconductor-microorganism hybrid systems.
2025, 41(1): 45-58
doi: 10.11862/CJIC.20240365
Abstract:
Abstracts: Many second and third-row transition-metal complexes with d6 and d8 electronic configurations possess long-lived metal-to-ligand charge-transfer (MLCT) excited states, endowing them with excellent photochemical and photophysical properties. However, these metals are typically expensive and have a low abundance in the earth′s crust. Therefore, it is significant to develop inexpensive and high earth-abundant first-row transition-metal complexes as new photo-functional materials. Among them, Fe(Ⅱ) complexes with a 3d6 electronic configuration and Fe(Ⅲ) complexes with a 3d5 electronic configuration are the subject of particular interest. The main challenges are to modulate the MLCT excited state of Fe(Ⅱ) complexes through efficient ligand design and to achieve the ligand-to-metal charge transfer (LMCT) luminescence of Fe(Ⅲ) complexes. In recent years, significant progress were made in the studies of Fe(Ⅱ) complexes with relatively long MLCT excited-state lifetimes and Fe(Ⅲ) complexes with efficient LMCT luminescence. These complexes have been successfully applied in different aspects of photochemistry. This review summarizes the recent advances in modulating the excited-state properties of photofunctional Fe(Ⅱ) and Fe(Ⅲ) complexes, focusing on the molecular designs of metal complexes and ligands. In addition, the potential developments and applications in the photochemistry of Fe(Ⅱ)/Fe(Ⅲ) complexes are discussed.
Abstracts: Many second and third-row transition-metal complexes with d6 and d8 electronic configurations possess long-lived metal-to-ligand charge-transfer (MLCT) excited states, endowing them with excellent photochemical and photophysical properties. However, these metals are typically expensive and have a low abundance in the earth′s crust. Therefore, it is significant to develop inexpensive and high earth-abundant first-row transition-metal complexes as new photo-functional materials. Among them, Fe(Ⅱ) complexes with a 3d6 electronic configuration and Fe(Ⅲ) complexes with a 3d5 electronic configuration are the subject of particular interest. The main challenges are to modulate the MLCT excited state of Fe(Ⅱ) complexes through efficient ligand design and to achieve the ligand-to-metal charge transfer (LMCT) luminescence of Fe(Ⅲ) complexes. In recent years, significant progress were made in the studies of Fe(Ⅱ) complexes with relatively long MLCT excited-state lifetimes and Fe(Ⅲ) complexes with efficient LMCT luminescence. These complexes have been successfully applied in different aspects of photochemistry. This review summarizes the recent advances in modulating the excited-state properties of photofunctional Fe(Ⅱ) and Fe(Ⅲ) complexes, focusing on the molecular designs of metal complexes and ligands. In addition, the potential developments and applications in the photochemistry of Fe(Ⅱ)/Fe(Ⅲ) complexes are discussed.
2025, 41(1): 59-78
doi: 10.11862/CJIC.20240406
Abstract:
近年来，手性无机纳米材料在传感、催化、生物医学和光子学等领域显现出了巨大应用潜力。具有本征手性结构的等离激元纳米材料因其等离激元光学特性与手性的精妙融合，展现出了高度可调且极为优越的手性光学特质。近年来，手性无机纳米材料在合成及结构调控方面取得了大量成果，有力地推动了其在众多新兴技术领域广泛应用的进程，从而衍生出大量前所未有的机遇与可能。本文介绍了手性无机纳米材料在生物传感方面的最新研究进展，其中特别关注了电化学和酶模拟催化方法。首先本文回顾了手性纳米催化剂的基本原理，包括手性配体诱导机制和固有手性纳米结构。其次，文中分别系统地介绍了手性纳米催化剂在电化学和酶模拟催化生物传感中的应用。最后，展望了将手性纳米探针用于新兴生物传感应用的挑战和机遇。通过合理设计手性纳米探针，可以实现单分子水平的灵敏度和分辨率不断提高的生物传感，这将大大促进许多新兴跨学科领域的传感应用。
2025, 41(1): 79-87
doi: 10.11862/CJIC.20240184
Abstract:
The precursor cluster [Et4N][Tp*WS3(CuCl)3] was treated with silver trifluoromethane sulfonate (AgOTf), followed by the assembly with three bridging ligands 2, 5-di(pyridin-4-yl)thiophene (L1), 5, 5'-bis(4-pyridinyl)-2, 2'-bi- thiophene (L2), and 2, 7-di(4-pyridinyl)pyrene (L3), resulting in three cationic W/Cu/S cluster-based supramolecular macrocycles [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L1)]2(OTf)2(1), [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L2)]2(OTf)2·2CHCl3(2·2CHCl3), and [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L3)]2(OTf)2·2DMF (3·2DMF), respectively. Structural characterizations including single-crystal X-ray diffraction, NMR spectroscopy, mass spectrometry, IR spectroscopy, UV-Vis spectroscopy, and elemental analysis were carried out for these compounds. X-ray analysis revealed that the main backbones of the three macrocycles are composed of a pair of L1, L2, or L3 ligands and three chlorine-bridged [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2+ cationic cluster cores. And they form 3D structures by stacking in different ways. The 1H NMR and electrospray ionization time- of-flight mass spectrometry (ESI-TOF MS) results indicated their good stability in solution. These three compounds exhibited enhanced third-order nonlinear optical properties in DMF compared to the precursor [Et4N][Tp*WS3(CuCl)3].
The precursor cluster [Et4N][Tp*WS3(CuCl)3] was treated with silver trifluoromethane sulfonate (AgOTf), followed by the assembly with three bridging ligands 2, 5-di(pyridin-4-yl)thiophene (L1), 5, 5'-bis(4-pyridinyl)-2, 2'-bi- thiophene (L2), and 2, 7-di(4-pyridinyl)pyrene (L3), resulting in three cationic W/Cu/S cluster-based supramolecular macrocycles [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L1)]2(OTf)2(1), [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L2)]2(OTf)2·2CHCl3(2·2CHCl3), and [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L3)]2(OTf)2·2DMF (3·2DMF), respectively. Structural characterizations including single-crystal X-ray diffraction, NMR spectroscopy, mass spectrometry, IR spectroscopy, UV-Vis spectroscopy, and elemental analysis were carried out for these compounds. X-ray analysis revealed that the main backbones of the three macrocycles are composed of a pair of L1, L2, or L3 ligands and three chlorine-bridged [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2+ cationic cluster cores. And they form 3D structures by stacking in different ways. The 1H NMR and electrospray ionization time- of-flight mass spectrometry (ESI-TOF MS) results indicated their good stability in solution. These three compounds exhibited enhanced third-order nonlinear optical properties in DMF compared to the precursor [Et4N][Tp*WS3(CuCl)3].
2025, 41(1): 88-96
doi: 10.11862/CJIC.20240342
Abstract:
In this study, we utilized a polynuclear lanthanide complex [Ce4ⅢCe6Ⅳ(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH (Ce10) constructed with acetylacetone (Hacac) as a Lewis acid catalyst to achieve an efficient borohydride reduction of amides, with yields ranging from 50% to 99%. Additionally, this method was successfully applied for the gram-scale synthesis of the antidepressant drug phenylethylamine. The catalytic mechanism was investigated using NMR and single-crystal X-ray diffraction analysis.
In this study, we utilized a polynuclear lanthanide complex [Ce4ⅢCe6Ⅳ(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH (Ce10) constructed with acetylacetone (Hacac) as a Lewis acid catalyst to achieve an efficient borohydride reduction of amides, with yields ranging from 50% to 99%. Additionally, this method was successfully applied for the gram-scale synthesis of the antidepressant drug phenylethylamine. The catalytic mechanism was investigated using NMR and single-crystal X-ray diffraction analysis.
2025, 41(1): 97-104
doi: 10.11862/CJIC.20240350
Abstract:
Two kinds of CuBi double perovskite modified Cu-metal-organic framework (CuBi@Cu-MOF) were prepared using a simple stirring method. The product selectivity and Faraday efficiency (FE) of the two composite materials as electrocatalysts for CO2 reduction were systematically evaluated in an alkaline system. The results demonstrated that CuBi@Cu-MOFs exhibited significantly enhanced HCOOH selectivity, the maximum FE of CuBi-MOF reached 56% which was better than the FE of Cu MOF catalyst itself (15%). The surface modification reduces the charge transfer resistance and increases the active sites, thus improving the electrocatalytic performance.
Two kinds of CuBi double perovskite modified Cu-metal-organic framework (CuBi@Cu-MOF) were prepared using a simple stirring method. The product selectivity and Faraday efficiency (FE) of the two composite materials as electrocatalysts for CO2 reduction were systematically evaluated in an alkaline system. The results demonstrated that CuBi@Cu-MOFs exhibited significantly enhanced HCOOH selectivity, the maximum FE of CuBi-MOF reached 56% which was better than the FE of Cu MOF catalyst itself (15%). The surface modification reduces the charge transfer resistance and increases the active sites, thus improving the electrocatalytic performance.
2025, 41(1): 105-113
doi: 10.11862/CJIC.20240360
Abstract:
An imidazolium-functionalized carboxylic acid ligand (H2L)Cl (1, 3-bis[4′-carboxy-3, 5-dimethyl-(1, 1′-biphenyl)-4-yl]-imidazolium chloride) was designed and synthesized. An imidazolium-functionalized zirconium metal-organic cage [(Cp3Zr3)2(L)3]Cl5 (MOC-1), where Cp3Zr3=(CpZr)3(μ3-O)(μ2-OH)3 and Cp=η5-C5H5, was prepared by the reaction of (H2L)Cl with bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2). MOC-1 was characterized by single-crystal X-ray diffraction, 1H NMR, electrospray ionization-mass spectrometry, UV-Vis absorption spectrum, IR spectroscopy, thermogravimetric analysis, and other test methods. Single-crystal X-ray diffraction analysis demonstrates the cationic skeleton of MOC-1 consists of two Cp3Zr3 units and three L- ligands. The three imidazole groups are located in the middle of the cage and point towards the inside. MOC-1 exhibits a cavity in an irregular pentagonal bipyramidal shape. The host-guest properties between MOC-1 and aryl sulfonate anions of different sizes were studied by 1H NMR. The results show that the host-guest interaction between MOC-1 and G1-G3 (benzenesulfonate, p-chlorophenyl sulfonate, and p-methyl benzenesulfonate, respectively) with better cavity matching was stronger than that between the larger aryl sulfonate anions G4 (p-ethyl benzenesulfonate) and G5 (p-isopropyl benzenesulfonate).
An imidazolium-functionalized carboxylic acid ligand (H2L)Cl (1, 3-bis[4′-carboxy-3, 5-dimethyl-(1, 1′-biphenyl)-4-yl]-imidazolium chloride) was designed and synthesized. An imidazolium-functionalized zirconium metal-organic cage [(Cp3Zr3)2(L)3]Cl5 (MOC-1), where Cp3Zr3=(CpZr)3(μ3-O)(μ2-OH)3 and Cp=η5-C5H5, was prepared by the reaction of (H2L)Cl with bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2). MOC-1 was characterized by single-crystal X-ray diffraction, 1H NMR, electrospray ionization-mass spectrometry, UV-Vis absorption spectrum, IR spectroscopy, thermogravimetric analysis, and other test methods. Single-crystal X-ray diffraction analysis demonstrates the cationic skeleton of MOC-1 consists of two Cp3Zr3 units and three L- ligands. The three imidazole groups are located in the middle of the cage and point towards the inside. MOC-1 exhibits a cavity in an irregular pentagonal bipyramidal shape. The host-guest properties between MOC-1 and aryl sulfonate anions of different sizes were studied by 1H NMR. The results show that the host-guest interaction between MOC-1 and G1-G3 (benzenesulfonate, p-chlorophenyl sulfonate, and p-methyl benzenesulfonate, respectively) with better cavity matching was stronger than that between the larger aryl sulfonate anions G4 (p-ethyl benzenesulfonate) and G5 (p-isopropyl benzenesulfonate).
2025, 41(1): 114-122
doi: 10.11862/CJIC.20240382
Abstract:
Using adenine (HA) and isophthalic acid (H2IP) as ligands, a bimetallic organic framework, (C2H8N)(NH4)[Zn4Co2(μ⁃O)(IP)4(A)4]·1.25H2O (ZnCoIPA), was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis revealed that the 3D ZnCoIPA retains the Watson-Crick sites of HA, with sinusoidal channels along the a⁃axis direction having diameters of approximately 0.42-0.49 nm and a narrow pore size distribution of about 0.07 nm. The channel diameters along the b⁃axis vary from 0.38 to 0.50 nm with a relatively wider pore size distribution of around 0.12 nm. X-ray photoelectron spectroscopy demonstrated the valence-varying nature of cobalt ions in ZnCoIPA, combined with its unique confined space, enabling selective recognition of sulfur- containing amino acids. UV-Vis absorption spectroscopy indicated the electronic transfer between the host and guest, resulting in a color change from colorless to yellow in solution, providing a visual recognition effect. Furthermore, time-dependent UV-Vis absorption spectroscopy tests on reduced and oxidized forms of glutathione (GSH) showed that the absorption peak intensity of the smaller-sized reduced GSH increased gradually over time, while the larger-sized oxidized GSH exhibited a slower change, enhancing only after a delay of approximately 16 min, further demonstrating the influence of the channel properties on the color change behavior of sulfur-containing amino acids.
Using adenine (HA) and isophthalic acid (H2IP) as ligands, a bimetallic organic framework, (C2H8N)(NH4)[Zn4Co2(μ⁃O)(IP)4(A)4]·1.25H2O (ZnCoIPA), was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis revealed that the 3D ZnCoIPA retains the Watson-Crick sites of HA, with sinusoidal channels along the a⁃axis direction having diameters of approximately 0.42-0.49 nm and a narrow pore size distribution of about 0.07 nm. The channel diameters along the b⁃axis vary from 0.38 to 0.50 nm with a relatively wider pore size distribution of around 0.12 nm. X-ray photoelectron spectroscopy demonstrated the valence-varying nature of cobalt ions in ZnCoIPA, combined with its unique confined space, enabling selective recognition of sulfur- containing amino acids. UV-Vis absorption spectroscopy indicated the electronic transfer between the host and guest, resulting in a color change from colorless to yellow in solution, providing a visual recognition effect. Furthermore, time-dependent UV-Vis absorption spectroscopy tests on reduced and oxidized forms of glutathione (GSH) showed that the absorption peak intensity of the smaller-sized reduced GSH increased gradually over time, while the larger-sized oxidized GSH exhibited a slower change, enhancing only after a delay of approximately 16 min, further demonstrating the influence of the channel properties on the color change behavior of sulfur-containing amino acids.
2025, 41(1): 123-130
doi: 10.11862/CJIC.20240362
Abstract:
A series of neutral boron-containing radical dimers were prepared directly from diketone compounds with KC8 and BCl(C6F5)2 through one pot method under an inert atmosphere. The 1H NMR signal shows the formation of sp3-hybrid carbon atoms while the single crystal X-ray diffraction data demonstrate σ-dimerization structures. A tetra-coordinated boron center was formed on each diketon skeleton. Three compounds crystallize in triclinic space system, space group P1 with a=0.914 93(3) nm, b=1.292 24(4) nm, c=1.526 46(6) nm for 1, a=1.197 14(5) nm, b=1.352 20(6) nm, c=1.352 20(6) nm for 2, and a=1.190 50(15) nm, b=1.362 4(2) nm, c=1.848 3(3) nm for 3. The dimerization mechanism was investigated by density functional theory calculation, revealing the effects between steric hindrance, electron effects, and dimerization carbon-carbon length. Three compounds have a similar UV-Vis absorption peak at 414 nm. Dimer 2 has fluorescence luminescence property at 480 nm and the wavelength redshift slightly with increasing concentration.
A series of neutral boron-containing radical dimers were prepared directly from diketone compounds with KC8 and BCl(C6F5)2 through one pot method under an inert atmosphere. The 1H NMR signal shows the formation of sp3-hybrid carbon atoms while the single crystal X-ray diffraction data demonstrate σ-dimerization structures. A tetra-coordinated boron center was formed on each diketon skeleton. Three compounds crystallize in triclinic space system, space group P1 with a=0.914 93(3) nm, b=1.292 24(4) nm, c=1.526 46(6) nm for 1, a=1.197 14(5) nm, b=1.352 20(6) nm, c=1.352 20(6) nm for 2, and a=1.190 50(15) nm, b=1.362 4(2) nm, c=1.848 3(3) nm for 3. The dimerization mechanism was investigated by density functional theory calculation, revealing the effects between steric hindrance, electron effects, and dimerization carbon-carbon length. Three compounds have a similar UV-Vis absorption peak at 414 nm. Dimer 2 has fluorescence luminescence property at 480 nm and the wavelength redshift slightly with increasing concentration.
2025, 41(1): 131-140
doi: 10.11862/CJIC.20240379
Abstract:
Based on the chiral ligand-induced strategy, three pairs of green-emitting chiral alkynyl silver chains {[Ag10(bpy)10(L/D-1)4](ClO4)6·H2O]}n (L/D-Ag10-1), {[Ag10(bpy)10(L/D-2)4](ClO4)6·3CH3OH}n (L/D-Ag10-2), and {[Ag10(bpy)10(L/D-3)4](ClO4)6}n (L/D-Ag10-3) were successfully obtained by reacting three pairs of aromatic alkyne ligands with different terminal groups [4-ethynyl-2R-isoindoline-1, 3-dione, R=1-hydroxy-2-propyl (L/D-1), 1-hydroxy-3-methyl-2-butyl (L/D-2), 2-hydroxy-1-phenylethyl (L/D-3)], and 2, 2′-bipyridine (bpy) with silver perchlorate (AgClO4). The crystal structure was determined by single-crystal X-ray diffraction (SCXRD), and the molecular formula composition was demonstrated by thermogravimetric analysis (TGA), elemental analysis (EA), and 1H NMR. By circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, it was demonstrated that the design approach using a chiral alkyne-based ligand in combination with an Ag(Ⅰ) was effective in inducing chirality in the polymer. Interestingly, the degree of distortion of the polymer backbone as well as the interchain interactions were significantly increased with the increase of the spatial site resistance of the terminal group of the alkyne-based ligand, which was accompanied by a gradual increase in the values of the absorption asymmetry factor (gabs) and the luminescence asymmetry factor (glum). In addition, L/D-Ag10-2 exhibited obvious aggregation-induced luminescence in the DMF-H2O system through the dissolution-reassembly strategy, and the new aggregates showed obvious enhancement of the chiral optical properties, with the |gabs| and |glum| values of the aggregates being 74.6 times and 12.5 times higher than those of the crystalline state.
Based on the chiral ligand-induced strategy, three pairs of green-emitting chiral alkynyl silver chains {[Ag10(bpy)10(L/D-1)4](ClO4)6·H2O]}n (L/D-Ag10-1), {[Ag10(bpy)10(L/D-2)4](ClO4)6·3CH3OH}n (L/D-Ag10-2), and {[Ag10(bpy)10(L/D-3)4](ClO4)6}n (L/D-Ag10-3) were successfully obtained by reacting three pairs of aromatic alkyne ligands with different terminal groups [4-ethynyl-2R-isoindoline-1, 3-dione, R=1-hydroxy-2-propyl (L/D-1), 1-hydroxy-3-methyl-2-butyl (L/D-2), 2-hydroxy-1-phenylethyl (L/D-3)], and 2, 2′-bipyridine (bpy) with silver perchlorate (AgClO4). The crystal structure was determined by single-crystal X-ray diffraction (SCXRD), and the molecular formula composition was demonstrated by thermogravimetric analysis (TGA), elemental analysis (EA), and 1H NMR. By circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, it was demonstrated that the design approach using a chiral alkyne-based ligand in combination with an Ag(Ⅰ) was effective in inducing chirality in the polymer. Interestingly, the degree of distortion of the polymer backbone as well as the interchain interactions were significantly increased with the increase of the spatial site resistance of the terminal group of the alkyne-based ligand, which was accompanied by a gradual increase in the values of the absorption asymmetry factor (gabs) and the luminescence asymmetry factor (glum). In addition, L/D-Ag10-2 exhibited obvious aggregation-induced luminescence in the DMF-H2O system through the dissolution-reassembly strategy, and the new aggregates showed obvious enhancement of the chiral optical properties, with the |gabs| and |glum| values of the aggregates being 74.6 times and 12.5 times higher than those of the crystalline state.
2025, 41(1): 141-148
doi: 10.11862/CJIC.20240393
Abstract:
1, 1, 2, 2-Tetra(pyridin-4-yl)ethene (TEPE) was chosen as a bridging ligand to assemble with Ag(Ⅰ) ions to form the cationic frameworks. And, the pentafluoro-benzoate anions (PFB-) and the benzoate (Bz-) anions as guests were introduced respectively to generate two new coordination compounds: [Ag(TEPE)(H2O)](PFB)·7H2O·3EtOH (1) and [Ag(TEPE)](Bz)·4H2O·2EtOH (2). The compositions and structures of complexes 1 and 2 were characterized using the thermogravimetric analysis, IR spectra, and single-crystal X-ray diffraction analysis. 1 possesses a 2D brick-like coordination layer structure with the classical hcb topology, each Ag(Ⅰ) center is coordinated with an aqua ligand and three N atoms from three TEPE ligands respectively, forming the distorted tetrahedral coordination geometry. The PFB- guests are distributed between the 2D layers to form diverse interactions with the main framework. 2 presents a 3D coordination network structure with the sqc8116 topology, in which each Ag(Ⅰ) center is coordinated in a tetrahedral geometry with four N atoms from four TEPE ligands respectively, and Bz- guests are located at the larger channels along the c-axis. Interestingly, two complexes showed the characteristic fluorescent properties regulated by photoactive guests. Excited by UV light, 1 exhibited a red emission while 2 showed a blue emission.
1, 1, 2, 2-Tetra(pyridin-4-yl)ethene (TEPE) was chosen as a bridging ligand to assemble with Ag(Ⅰ) ions to form the cationic frameworks. And, the pentafluoro-benzoate anions (PFB-) and the benzoate (Bz-) anions as guests were introduced respectively to generate two new coordination compounds: [Ag(TEPE)(H2O)](PFB)·7H2O·3EtOH (1) and [Ag(TEPE)](Bz)·4H2O·2EtOH (2). The compositions and structures of complexes 1 and 2 were characterized using the thermogravimetric analysis, IR spectra, and single-crystal X-ray diffraction analysis. 1 possesses a 2D brick-like coordination layer structure with the classical hcb topology, each Ag(Ⅰ) center is coordinated with an aqua ligand and three N atoms from three TEPE ligands respectively, forming the distorted tetrahedral coordination geometry. The PFB- guests are distributed between the 2D layers to form diverse interactions with the main framework. 2 presents a 3D coordination network structure with the sqc8116 topology, in which each Ag(Ⅰ) center is coordinated in a tetrahedral geometry with four N atoms from four TEPE ligands respectively, and Bz- guests are located at the larger channels along the c-axis. Interestingly, two complexes showed the characteristic fluorescent properties regulated by photoactive guests. Excited by UV light, 1 exhibited a red emission while 2 showed a blue emission.
2025, 41(1): 149-154
doi: 10.11862/CJIC.20240407
Abstract:
Two examples of copper-iodine cluster-based boron imidazolate framework (BIFs) were obtained using cuprous iodide, pre-synthesized boron imidazolate ligands, and quaternary ammonium salts. Their structures and properties were characterized. X-ray single crystal diffraction results show that [N(C4H9)4]{Cu6I6[BH(im)3]Cu[BH(im)3]}·0.5CH3OH (BIF-155, im=imidazolate) is a (3, 4)-connected two-dimensional layer network formed by alternately connecting four-connected Cu6I6 clusters, single core Cu atoms and triple-connected boron imidazolate ligands BH(im)3-. [N(C4H9)4]{Cu3I3 [BH(im)3]} (BIF-156) is a 3-connected two-dimensional layer network with fes topology obtained by connecting Cu3I3 clusters and BH(im)3- boronazole ligands. The corresponding crystals of the two compounds had good crystallinity. Under ultraviolet lamp illumination, the two showed different fluorescence properties, that is, BIF-155 emited red light and BIF-156 emited yellow light.
Two examples of copper-iodine cluster-based boron imidazolate framework (BIFs) were obtained using cuprous iodide, pre-synthesized boron imidazolate ligands, and quaternary ammonium salts. Their structures and properties were characterized. X-ray single crystal diffraction results show that [N(C4H9)4]{Cu6I6[BH(im)3]Cu[BH(im)3]}·0.5CH3OH (BIF-155, im=imidazolate) is a (3, 4)-connected two-dimensional layer network formed by alternately connecting four-connected Cu6I6 clusters, single core Cu atoms and triple-connected boron imidazolate ligands BH(im)3-. [N(C4H9)4]{Cu3I3 [BH(im)3]} (BIF-156) is a 3-connected two-dimensional layer network with fes topology obtained by connecting Cu3I3 clusters and BH(im)3- boronazole ligands. The corresponding crystals of the two compounds had good crystallinity. Under ultraviolet lamp illumination, the two showed different fluorescence properties, that is, BIF-155 emited red light and BIF-156 emited yellow light.
2025, 41(1): 155-164
doi: 10.11862/CJIC.20240408
Abstract:
Using machine learning for high-throughput screening is a new material screening method. The gas adsorption on zeolite molecular sieves was studied using the grand canonical Monte Carlo (GCMC) simulation and machine learning methods. The GCMC simulation method was used to calculate the absolute adsorption capacity of 12 types of electron gases on 240 varieties of silica zeolite molecular sieves. In comparison, the Zeo++ program was employed to analyze 17 types of structural characteristics of these zeolite molecular sieves. On this basis, multiple linear regression and random forest regression were established to predict the adsorption capacity of zeolite molecular sieves for electronic gases. Through correlation analysis and model performance evaluation, the impact degree of different structural characteristics on gas adsorption capacity was revealed, and the stability and prediction accuracy of the model were discussed.
Using machine learning for high-throughput screening is a new material screening method. The gas adsorption on zeolite molecular sieves was studied using the grand canonical Monte Carlo (GCMC) simulation and machine learning methods. The GCMC simulation method was used to calculate the absolute adsorption capacity of 12 types of electron gases on 240 varieties of silica zeolite molecular sieves. In comparison, the Zeo++ program was employed to analyze 17 types of structural characteristics of these zeolite molecular sieves. On this basis, multiple linear regression and random forest regression were established to predict the adsorption capacity of zeolite molecular sieves for electronic gases. Through correlation analysis and model performance evaluation, the impact degree of different structural characteristics on gas adsorption capacity was revealed, and the stability and prediction accuracy of the model were discussed.
2025, 41(1): 165-173
doi: 10.11862/CJIC.20240409
Abstract:
A 2D metal-organic framework (Zn-MOF, {[Zn(btz)2]·DMF·CH3OH}n, Hbtz=benzotriazole, DMF=N, N- dimethylformamide) was synthesized, exhibiting high stability in solvents, acid-base, and thermal conditions. The stable structure and uncoordinated nitrogen atoms enable Zn-MOF to effectively enrich silver ions, which can be converted into silver nanoparticles anchored on the MOF (Ag@Zn-MOF) through heat treatment. The silver nanoparticle loading (mass fraction) of the Ag@Zn-MOF composite reached 1.84%. The Zn-MOF framework remained stable after pyrolytic reduction. Electrocatalytic CO2 reduction performance tests demonstrated that, compared to Zn-MOF, the Faraday efficiency of Ag@Zn-MOF for CO production increased from 59.6% to 92.1%, with a current density of 30.3 mA·cm-2 at -1.34 V (vs RHE), highlighting its superior electrocatalytic performance.
A 2D metal-organic framework (Zn-MOF, {[Zn(btz)2]·DMF·CH3OH}n, Hbtz=benzotriazole, DMF=N, N- dimethylformamide) was synthesized, exhibiting high stability in solvents, acid-base, and thermal conditions. The stable structure and uncoordinated nitrogen atoms enable Zn-MOF to effectively enrich silver ions, which can be converted into silver nanoparticles anchored on the MOF (Ag@Zn-MOF) through heat treatment. The silver nanoparticle loading (mass fraction) of the Ag@Zn-MOF composite reached 1.84%. The Zn-MOF framework remained stable after pyrolytic reduction. Electrocatalytic CO2 reduction performance tests demonstrated that, compared to Zn-MOF, the Faraday efficiency of Ag@Zn-MOF for CO production increased from 59.6% to 92.1%, with a current density of 30.3 mA·cm-2 at -1.34 V (vs RHE), highlighting its superior electrocatalytic performance.
2025, 41(1): 174-182
doi: 10.11862/CJIC.20240305
Abstract:
A gold catalyst of Au/ pyrenyl-graphdiyne (Pyr-GDY) was prepared by anchoring small size of gold nanoparticles (Au NPs) on the surface of Pyr-GDY for electrocatalytic nitrogen reduction reaction (eNRR), in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy-like porous Pyr-GDY. The catalyst exhibited a good electrocatalytic activity for N2 reduction in a nitrogen-saturated electrolyte, with an ammonia yield of 32.1 μg·h-1·mgcat-1 at -0.3 V (vs RHE), 3.5 times higher than that of Au/C (Au NPs anchored on carbon black). In addition, Au/Pyr-GDY showed a Faraday efficiency (FE) of 26.9% for eNRR, and a good catalysis durability for over 22 h.
A gold catalyst of Au/ pyrenyl-graphdiyne (Pyr-GDY) was prepared by anchoring small size of gold nanoparticles (Au NPs) on the surface of Pyr-GDY for electrocatalytic nitrogen reduction reaction (eNRR), in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy-like porous Pyr-GDY. The catalyst exhibited a good electrocatalytic activity for N2 reduction in a nitrogen-saturated electrolyte, with an ammonia yield of 32.1 μg·h-1·mgcat-1 at -0.3 V (vs RHE), 3.5 times higher than that of Au/C (Au NPs anchored on carbon black). In addition, Au/Pyr-GDY showed a Faraday efficiency (FE) of 26.9% for eNRR, and a good catalysis durability for over 22 h.
2025, 41(1): 183-192
doi: 10.11862/CJIC.20240232
Abstract:
To address the lack of systematic studies on heavy metal fluorescent probes in typical buffer solutions, this study developed a Fe3+ and Cu2+ fluorescent probe, DHU-NP-4, based on a naphthalimide fluorophore. Comparative analysis of the probe's performance in various buffer systems revealed that buffers with high organic content are unsuitable for evaluating such probes. Furthermore, the pH of the solvent system was found to significantly influence the probe's behavior. Under highly acidic conditions (pH≥2), DHU-NP-4 exhibited exceptional specificity for Fe3+, while in alkaline conditions, it demonstrated high specificity for Cu2+. Leveraging these properties, the probe enabled the quantitative detection of Fe3+ and Cu2+ in solution.
To address the lack of systematic studies on heavy metal fluorescent probes in typical buffer solutions, this study developed a Fe3+ and Cu2+ fluorescent probe, DHU-NP-4, based on a naphthalimide fluorophore. Comparative analysis of the probe's performance in various buffer systems revealed that buffers with high organic content are unsuitable for evaluating such probes. Furthermore, the pH of the solvent system was found to significantly influence the probe's behavior. Under highly acidic conditions (pH≥2), DHU-NP-4 exhibited exceptional specificity for Fe3+, while in alkaline conditions, it demonstrated high specificity for Cu2+. Leveraging these properties, the probe enabled the quantitative detection of Fe3+ and Cu2+ in solution.
2025, 41(1): 193-200
doi: 10.11862/CJIC.20240341
Abstract:
An aluminoborate, Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O (1), was synthesized under hydrothermal condition, which was built by mixed oxoboron clusters and AlO4 tetrahedra. In the structure, the [B5O10]5- and [B3O7]5- clusters are alternately connected to form 1D [B8O15]n6n- chains, which are further linked by AlO4 units to form a 2D monolayer with 7-membered ring and 10-membered ring windows. Two adjacent monolayers with opposite orientations further form a porous-layered structure with six channels through B—O—Al bonds. Compound 1 was characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy, UV-Vis diffuse reflection spectroscopy, and thermogravimetric analysis (TGA), respectively. UV-Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm, suggesting it may have potential application in UV regions.
An aluminoborate, Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O (1), was synthesized under hydrothermal condition, which was built by mixed oxoboron clusters and AlO4 tetrahedra. In the structure, the [B5O10]5- and [B3O7]5- clusters are alternately connected to form 1D [B8O15]n6n- chains, which are further linked by AlO4 units to form a 2D monolayer with 7-membered ring and 10-membered ring windows. Two adjacent monolayers with opposite orientations further form a porous-layered structure with six channels through B—O—Al bonds. Compound 1 was characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy, UV-Vis diffuse reflection spectroscopy, and thermogravimetric analysis (TGA), respectively. UV-Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm, suggesting it may have potential application in UV regions.
Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects
2025, 41(1): 201-212
doi: 10.11862/CJIC.20240356
Abstract:
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd-based catalysts that were co-modified with organic and inorganic ligands. It was demonstrated that the catalysts contained Pd species in mixed valence states, with high valence Pd at the metal-support interface and zero valence Pd at the metal surface. While the strong coordination of triphenylphosphine (PPh3) to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation, the coordination of sodium metavanadate (NaVO3) to high-valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro-groups. The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd-based catalysts that were co-modified with organic and inorganic ligands. It was demonstrated that the catalysts contained Pd species in mixed valence states, with high valence Pd at the metal-support interface and zero valence Pd at the metal surface. While the strong coordination of triphenylphosphine (PPh3) to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation, the coordination of sodium metavanadate (NaVO3) to high-valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro-groups. The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
2025, 41(1): 213-224
doi: 10.11862/CJIC.20240359
Abstract:
To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects, the new anthraquinone derivatives, 9-pyridylanthrahydrazone (9-PAH) and 9, 10-bispyridylanthrahydrazone (9, 10-PAH) were designed and synthesized. Utilizing 9-PAH and 9, 10-PAH as promising anticancer ligands, their respective copper complexes, namely [Cu(L1)Cl2]Cl (1) and {[Cu4(μ2-Cl)3Cl4(9, 10-PAH)2(DMSO)2]Cl2}n (2), were subsequently synthesized, where the new ligand L1 is formed by coupling two 9-PAH ligands in the coordination reaction. The chemical and crystal structures of 1 and 2 were elucidated by IR, MS, elemental analysis, and single-crystal X-ray diffraction. Complex 1 forms a mononuclear structure. L1 coordinates with Cu through its three N atoms, together with two Cl atoms, to form a five-coordinated square pyramidal geometry. Complex 2 constitutes a polymeric structure, wherein each structural unit centrosymmetrically encompasses two five-coordinated binuclear copper complexes (Cu1, Cu2) of 9, 10-PAH, with similar square pyramidal geometry. A chlorine atom (Cl2), located at the symmetry center, bridges Cu1 and Cu1A to connect the two binuclear copper structures. Meanwhile, the two five-coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom, respectively, thus forming a 1D chain-like polymeric structure. In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin. Specifically, the IC50 values of 2 against HeLa-229 and SK-OV-3 cancer cell lines were determined to be (5.92±0.32) μmol·L-1 and (6.48±0.39) μmol·L-1, respectively. 2 could also block the proliferation of HeLa-229 cells in S phase and significantly induce cell apoptosis. In addition, fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode, offering insights into its underlying anticancer mechanism.
To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects, the new anthraquinone derivatives, 9-pyridylanthrahydrazone (9-PAH) and 9, 10-bispyridylanthrahydrazone (9, 10-PAH) were designed and synthesized. Utilizing 9-PAH and 9, 10-PAH as promising anticancer ligands, their respective copper complexes, namely [Cu(L1)Cl2]Cl (1) and {[Cu4(μ2-Cl)3Cl4(9, 10-PAH)2(DMSO)2]Cl2}n (2), were subsequently synthesized, where the new ligand L1 is formed by coupling two 9-PAH ligands in the coordination reaction. The chemical and crystal structures of 1 and 2 were elucidated by IR, MS, elemental analysis, and single-crystal X-ray diffraction. Complex 1 forms a mononuclear structure. L1 coordinates with Cu through its three N atoms, together with two Cl atoms, to form a five-coordinated square pyramidal geometry. Complex 2 constitutes a polymeric structure, wherein each structural unit centrosymmetrically encompasses two five-coordinated binuclear copper complexes (Cu1, Cu2) of 9, 10-PAH, with similar square pyramidal geometry. A chlorine atom (Cl2), located at the symmetry center, bridges Cu1 and Cu1A to connect the two binuclear copper structures. Meanwhile, the two five-coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom, respectively, thus forming a 1D chain-like polymeric structure. In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin. Specifically, the IC50 values of 2 against HeLa-229 and SK-OV-3 cancer cell lines were determined to be (5.92±0.32) μmol·L-1 and (6.48±0.39) μmol·L-1, respectively. 2 could also block the proliferation of HeLa-229 cells in S phase and significantly induce cell apoptosis. In addition, fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode, offering insights into its underlying anticancer mechanism.
