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无机化学学报
Chinese Journal of Inorganic Chemistry
主管 : 中国科学技术协会
刊期 : 月刊主编 : 游效曾
语种 : 中文主办 : 中国化学会
ISSN : 1001-4861 CN : 32-1185/O6展开 >《无机化学学报》由中国化学会主办，是展示我国无机化学研究成果的学术性期刊，月刊。1985年由化学前辈戴安邦院士（发起）创刊，现任主编游效曾院士。编辑部设在南京大学化学化工学院化学楼。报道我国无机化学领域的基础研究和应用基础研究的创新成果，内容涉及固体无机化学、配位化学、无机材料化学、生物无机化学、有机金属化学、理论无机化学、超分子化学和应用无机化学、催化等，着重报道新的和已知化合物的合成、热力学、动力学性质、谱学、结构和成键等。设有综述、研究快报及论文等栏目。
本刊所刊论文均为美国《科学引文索引》（SCI）网络版、美国《化学文摘》(CA)、《中国学术期刊文摘》（中、英文版）、《中国科技论文与引文数据库（CSTPCD）》、《中国科学引文数据库》、《中文科技期刊数据库》、《中国期刊全文数据库》、《中国核心期刊（遴选）数据库》、中国台湾华艺《中文电子期刊服务》等国内外多种著名检索刊物和文献数据库摘引和收录。
《无机化学学报》2011年每期200页，定价28.00元、全年定价336.00元。本刊由各地邮局征订，邮发代号28-133。也可直接向编辑部订阅。
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2026, 42(11): 2259-2274
doi: 10.11862/CJIC.20260125
摘要:
有机发光二极管(organic light-emitting diodes，OLEDs)凭借其低能耗、宽视角、响应速度快、驱动电压低以及可柔性化等诸多优势，持续成为学术界和产业界的研究热点。其中，溶液加工型OLEDs具有工艺简单、成本低廉、材料利用率高以及大面积制备等特点，被视为突破其规模产业化应用瓶颈的核心技术路径。金属配合物因其在发光效率、激发态可调性及稳定性方面的综合优势，成为实现高性能溶液加工型OLEDs的核心候选材料之一。本文系统综述了溶液加工型金属配合物电致发光材料(主要包括铱、铂以及金等配合物)的设计策略及其在常规与大面积OLEDs器件中的应用进展，深入剖析了该领域的研究现状、存在的问题以及未来发展方向，以期为今后溶液加工型金属配合物电致发光材料的设计、合成及其OLEDs应用提供参考与借鉴。
有机发光二极管(organic light-emitting diodes，OLEDs)凭借其低能耗、宽视角、响应速度快、驱动电压低以及可柔性化等诸多优势，持续成为学术界和产业界的研究热点。其中，溶液加工型OLEDs具有工艺简单、成本低廉、材料利用率高以及大面积制备等特点，被视为突破其规模产业化应用瓶颈的核心技术路径。金属配合物因其在发光效率、激发态可调性及稳定性方面的综合优势，成为实现高性能溶液加工型OLEDs的核心候选材料之一。本文系统综述了溶液加工型金属配合物电致发光材料(主要包括铱、铂以及金等配合物)的设计策略及其在常规与大面积OLEDs器件中的应用进展，深入剖析了该领域的研究现状、存在的问题以及未来发展方向，以期为今后溶液加工型金属配合物电致发光材料的设计、合成及其OLEDs应用提供参考与借鉴。
2026, 42(11): 2290-2310
doi: 10.11862/CJIC.20260187
摘要:
N2O2二吡咯甲烯型金属配合物因其兼具母体骨架的高效吸光特性与多齿配位诱导的结构稳定性，正逐渐发展为一类功能独特的金属平台。相较于传统N，N-二齿二吡咯甲烯配体，N2O2四齿配体通过2个吡咯氮和2个酚氧供体构筑潜在三阴离子配位环境，在增强分子骨架刚性的同时保留轴向配位和金属中心调控空间，由此显著拓展配合物的结构与功能多样性。近年来，该领域已由早期的Al、Si、Ge、Sn等主族金属配位体系，逐步拓展至Ga、In、Sb、Bi等重主族金属，以及Mn、Co、Ni、Cu、Pt、Au等过渡金属氧化还原活性体系。本文以N2O2四齿配体为主线，按金属中心和功能类型系统梳理相关研究，并进一步比较不同体系中金属半径、轴向配体、取代基电子效应和配体非无辜性对光物理、电化学和催化行为的影响。通过归纳代表性光物理和电化学参数，本文强调该类配合物从刚性化发光骨架向可调控金属-配体协同平台的发展趋势，并讨论当前在近红外效率、结构稳定性、可比较电化学数据、生物应用验证和催化机制阐明等方面的关键瓶颈，以期为后续分子设计与功能应用提供更具针对性的参考。
N2O2二吡咯甲烯型金属配合物因其兼具母体骨架的高效吸光特性与多齿配位诱导的结构稳定性，正逐渐发展为一类功能独特的金属平台。相较于传统N，N-二齿二吡咯甲烯配体，N2O2四齿配体通过2个吡咯氮和2个酚氧供体构筑潜在三阴离子配位环境，在增强分子骨架刚性的同时保留轴向配位和金属中心调控空间，由此显著拓展配合物的结构与功能多样性。近年来，该领域已由早期的Al、Si、Ge、Sn等主族金属配位体系，逐步拓展至Ga、In、Sb、Bi等重主族金属，以及Mn、Co、Ni、Cu、Pt、Au等过渡金属氧化还原活性体系。本文以N2O2四齿配体为主线，按金属中心和功能类型系统梳理相关研究，并进一步比较不同体系中金属半径、轴向配体、取代基电子效应和配体非无辜性对光物理、电化学和催化行为的影响。通过归纳代表性光物理和电化学参数，本文强调该类配合物从刚性化发光骨架向可调控金属-配体协同平台的发展趋势，并讨论当前在近红外效率、结构稳定性、可比较电化学数据、生物应用验证和催化机制阐明等方面的关键瓶颈，以期为后续分子设计与功能应用提供更具针对性的参考。
2026, 42(11): 2311-2325
doi: 10.11862/CJIC.20260196
摘要:
二阶非线性光学(nonlinear optical，NLO)材料是实现光能量与光场信息转换的核心功能材料，在可调谐光源、光学开关、精密检测和非线性成像等领域具有重要应用。目前，如何通过结构设计实现对宏观二阶非线性响应的可预测调控，仍是该领域的核心问题。金属有机框架(metal-organic frameworks，MOFs)由金属或金属节点与有机配体通过配位键周期性组装而成，为构建非中心对称结构、组织局域极性单元、调节发色团取向以及引入可响应孔道环境提供了独特平台。在本综述中，我们讨论了二阶NLO MOF材料的研究进展，包括二阶非线性的微观光学起源、表征方法、结构设计、响应调控及功能应用。最后，我们还总结并展望了该领域面临的问题及挑战。
二阶非线性光学(nonlinear optical，NLO)材料是实现光能量与光场信息转换的核心功能材料，在可调谐光源、光学开关、精密检测和非线性成像等领域具有重要应用。目前，如何通过结构设计实现对宏观二阶非线性响应的可预测调控，仍是该领域的核心问题。金属有机框架(metal-organic frameworks，MOFs)由金属或金属节点与有机配体通过配位键周期性组装而成，为构建非中心对称结构、组织局域极性单元、调节发色团取向以及引入可响应孔道环境提供了独特平台。在本综述中，我们讨论了二阶NLO MOF材料的研究进展，包括二阶非线性的微观光学起源、表征方法、结构设计、响应调控及功能应用。最后，我们还总结并展望了该领域面临的问题及挑战。
2026, 42(11): 2275-2289
doi: 10.11862/CJIC.20260185
摘要:
Magnetic resonance (MR) imaging is a real-time, noninvasive, and indispensable modality in biomedical research and clinical diagnosis. Due to the limited intrinsic sensitivity of MR imaging, 30%-50% of clinical MR imaging scans require the administration of paramagnetic Gd(Ⅲ)-based contrast agents (GBCAs) to enhance the MR signal intensity. All currently clinically approved GBCAs are “always-on” contrast-enhanced Gd(Ⅲ) agents, which do not respond to specific biological species. The development of bioresponsive GBCAs to improve the specificity of MR imaging has attracted considerable effort over the past three decades. Among these advances, many galactosyl-conjugated Gd(Ⅲ) agents have been developed as model bioresponsive molecular scaffolds for visualizing β-galactosidase activity, gene expression, gene therapy, senescence, and tumors. This review focuses on the structural designs and the diagnostic applications of β-galactosidase-responsive Gd(Ⅲ) MR agents. According to the unique coordination environment changes upon enzymatic activation, we classified these chelates into two major categories: the number of water molecules that directly bind to Gd(Ⅲ) (q)-modulated and the rotational tumbling rate of Gd(Ⅲ) complexes (τr)-modulated Gd(Ⅲ) complexes.
Magnetic resonance (MR) imaging is a real-time, noninvasive, and indispensable modality in biomedical research and clinical diagnosis. Due to the limited intrinsic sensitivity of MR imaging, 30%-50% of clinical MR imaging scans require the administration of paramagnetic Gd(Ⅲ)-based contrast agents (GBCAs) to enhance the MR signal intensity. All currently clinically approved GBCAs are “always-on” contrast-enhanced Gd(Ⅲ) agents, which do not respond to specific biological species. The development of bioresponsive GBCAs to improve the specificity of MR imaging has attracted considerable effort over the past three decades. Among these advances, many galactosyl-conjugated Gd(Ⅲ) agents have been developed as model bioresponsive molecular scaffolds for visualizing β-galactosidase activity, gene expression, gene therapy, senescence, and tumors. This review focuses on the structural designs and the diagnostic applications of β-galactosidase-responsive Gd(Ⅲ) MR agents. According to the unique coordination environment changes upon enzymatic activation, we classified these chelates into two major categories: the number of water molecules that directly bind to Gd(Ⅲ) (q)-modulated and the rotational tumbling rate of Gd(Ⅲ) complexes (τr)-modulated Gd(Ⅲ) complexes.
2026, 42(11): 2326-2334
doi: 10.11862/CJIC.20260119
摘要:
In this work, a pair of iron(Ⅱ) spin-crossover complexes derived from chiral ligands, [Fe(L-R)(NCS)2] (1-R; L-R=(R)-N1,N2-bis(pyridin-2-ylmethyl)propane-1,2-diamine) and [Fe(L-S)(NCS)2] (1-S; L-S=(S)-N1,N2-bis(pyridin-2-ylmethyl)propane-1,2-diamine), together with their racemic analogue [Fe(L)(NCS)2] (1-rac; where L represents an equimolar mixture of L-R and L-S), were synthesized, and the influence of chirality on molecular packing and spin-crossover behavior was investigated. Structural and circular dichroism analyses reveal a hierarchical transfer of chirality from the ligands to the coordination metal centers, which is ultimately amplified into the supramolecular single-crystal architecture. Consequently, 1-R and 1-S crystallize in the enantiomorphic tetragonal space groups P41212 and P43212, respectively, forming opposite-handed quadruple-helical networks, whereas 1-rac adopts the achiral space group Aea2. Magnetic and calorimetric measurements demonstrate that both enantiopure complexes undergo a complete, reversible one-step SCO transition with T1/2 (spin-transition temperature) of 158 K. In contrast, 1-rac remains trapped in the high-spin state across the entire investigated temperature range.
In this work, a pair of iron(Ⅱ) spin-crossover complexes derived from chiral ligands, [Fe(L-R)(NCS)2] (1-R; L-R=(R)-N1,N2-bis(pyridin-2-ylmethyl)propane-1,2-diamine) and [Fe(L-S)(NCS)2] (1-S; L-S=(S)-N1,N2-bis(pyridin-2-ylmethyl)propane-1,2-diamine), together with their racemic analogue [Fe(L)(NCS)2] (1-rac; where L represents an equimolar mixture of L-R and L-S), were synthesized, and the influence of chirality on molecular packing and spin-crossover behavior was investigated. Structural and circular dichroism analyses reveal a hierarchical transfer of chirality from the ligands to the coordination metal centers, which is ultimately amplified into the supramolecular single-crystal architecture. Consequently, 1-R and 1-S crystallize in the enantiomorphic tetragonal space groups P41212 and P43212, respectively, forming opposite-handed quadruple-helical networks, whereas 1-rac adopts the achiral space group Aea2. Magnetic and calorimetric measurements demonstrate that both enantiopure complexes undergo a complete, reversible one-step SCO transition with T1/2 (spin-transition temperature) of 158 K. In contrast, 1-rac remains trapped in the high-spin state across the entire investigated temperature range.
2026, 42(11): 2343-2352
doi: 10.11862/CJIC.20260105
摘要:
Herein, we report the solvothermal synthesis of two distinct Anderson-type heptanuclear cobalt clusters, 1-BzO [Co7(L)2(acac)4(BzO)4(iPrO)2][Co(acac)2]·8CH3CN and 1-OAc [Co7(L)2(acac)4(OAc)4(MeO)2][Co(acac)2]·9CH3CN, utilizing 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol (H3L), benzoic acid (BzOH)/salicylic acid, and cobalt acetylacetonate(Co(acac)2). Despite sharing identical metallic skeletons, variations in their peripheral ligands significantly govern their electrocatalytic behavior. Electrochemical evaluations demonstrated that 1-OAc exhibited markedly superior catalytic activity for the hydrogen evolution reaction (HER) in neutral electrolyte, achieving an overpotential of only 303 mV at a current density of 10 mA·cm-2 with a Tafel slope of 184 mV·dec-1.
Herein, we report the solvothermal synthesis of two distinct Anderson-type heptanuclear cobalt clusters, 1-BzO [Co7(L)2(acac)4(BzO)4(iPrO)2][Co(acac)2]·8CH3CN and 1-OAc [Co7(L)2(acac)4(OAc)4(MeO)2][Co(acac)2]·9CH3CN, utilizing 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol (H3L), benzoic acid (BzOH)/salicylic acid, and cobalt acetylacetonate(Co(acac)2). Despite sharing identical metallic skeletons, variations in their peripheral ligands significantly govern their electrocatalytic behavior. Electrochemical evaluations demonstrated that 1-OAc exhibited markedly superior catalytic activity for the hydrogen evolution reaction (HER) in neutral electrolyte, achieving an overpotential of only 303 mV at a current density of 10 mA·cm-2 with a Tafel slope of 184 mV·dec-1.
2026, 42(11): 2362-2370
doi: 10.11862/CJIC.20260178
摘要:
A novel manganese-based hybrid material (TMBE)2[MnBr4] (1) was successfully synthesized via the slow evaporation method, using (2-bromoethyl)trimethylammonium bromide ((TMBE)Br) and MnBr2·4H2O. Single-crystal structural analysis reveals that 1 crystallizes in the Pca21 space group, with Mn2+ coordinating with Br- to form isolated tetrahedra, while the organic cation separates the inorganic anions, resulting in a zero-dimensional crystal structure. Differential scanning calorimetry measurements demonstrate that compound 1 undergoes a reversible first-order phase transition with a maximum phase transition temperature of 413 K. Dielectric, variable-temperature fluorescence, and magnetic measurements showed that compound 1 exhibited synchronous switching behavior of dielectric constant, luminous intensity, and magnetization near 344 K. These results indicate that halogen substitution on organic cations is an effective strategy for constructing high-temperature phase-transition materials that integrate dielectric, optical, and magnetic synergistic responses triggered by structural phase transitions.
A novel manganese-based hybrid material (TMBE)2[MnBr4] (1) was successfully synthesized via the slow evaporation method, using (2-bromoethyl)trimethylammonium bromide ((TMBE)Br) and MnBr2·4H2O. Single-crystal structural analysis reveals that 1 crystallizes in the Pca21 space group, with Mn2+ coordinating with Br- to form isolated tetrahedra, while the organic cation separates the inorganic anions, resulting in a zero-dimensional crystal structure. Differential scanning calorimetry measurements demonstrate that compound 1 undergoes a reversible first-order phase transition with a maximum phase transition temperature of 413 K. Dielectric, variable-temperature fluorescence, and magnetic measurements showed that compound 1 exhibited synchronous switching behavior of dielectric constant, luminous intensity, and magnetization near 344 K. These results indicate that halogen substitution on organic cations is an effective strategy for constructing high-temperature phase-transition materials that integrate dielectric, optical, and magnetic synergistic responses triggered by structural phase transitions.
2026, 42(11): 2371-2380
doi: 10.11862/CJIC.20260193
摘要:
The magnetic properties of two isostructural rare-earth borate compounds Cd4LnO(BO3)3 [Ln=Yb (1), Dy (2)], whose crystal structures have been previously reported, were investigated. Single crystals of compound 1 were obtained and structurally characterized by single-crystal X-ray diffraction. The phase purity and isostructural relationship of compounds 1 and 2 were confirmed by powder X-ray diffraction, together with infrared spectroscopy. Their band gaps and thermal stabilities were characterized by UV-Vis-NIR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction reveals that [YbO6] are connected via edge-sharing to form 1D chains of rare-earth magnetic ions in compound 1, and these chains are separated by borate groups and Cd2+ ions. Magnetic studies indicate that antiferromagnetic interactions dominate in both compounds 1 and 2, and no long-range magnetic order was observed down to 2 K.
The magnetic properties of two isostructural rare-earth borate compounds Cd4LnO(BO3)3 [Ln=Yb (1), Dy (2)], whose crystal structures have been previously reported, were investigated. Single crystals of compound 1 were obtained and structurally characterized by single-crystal X-ray diffraction. The phase purity and isostructural relationship of compounds 1 and 2 were confirmed by powder X-ray diffraction, together with infrared spectroscopy. Their band gaps and thermal stabilities were characterized by UV-Vis-NIR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction reveals that [YbO6] are connected via edge-sharing to form 1D chains of rare-earth magnetic ions in compound 1, and these chains are separated by borate groups and Cd2+ ions. Magnetic studies indicate that antiferromagnetic interactions dominate in both compounds 1 and 2, and no long-range magnetic order was observed down to 2 K.
2026, 42(11): 2399-2410
doi: 10.11862/CJIC.20260209
摘要:
We report a class of Au(Ⅰ)-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters designed for deep blue emission [(PzIPr)AuOBO and (SIPr)AuOBO], which exhibited a substantially shortened delayed lifetime and a narrow full width at half maximum (FWHM=40 nm). Remarkably, dual emission from both TADF and phosphorescence was observed in these MR-TADF complexes. The photoluminescence quantum yield (PLQY) of the emitters reached up to 0.99, a result attributed to the Au(Ⅰ)-activated triplet radiative transfer pathway. Solution-processed organic light-emitting diode (OLED) devices fabricated with (PzIPr)AuOBO delivered deep blue emission with CIE coordinates of (0.15, 0.07) and a maximum external quantum efficiency (EQE) of 7.0%.
We report a class of Au(Ⅰ)-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters designed for deep blue emission [(PzIPr)AuOBO and (SIPr)AuOBO], which exhibited a substantially shortened delayed lifetime and a narrow full width at half maximum (FWHM=40 nm). Remarkably, dual emission from both TADF and phosphorescence was observed in these MR-TADF complexes. The photoluminescence quantum yield (PLQY) of the emitters reached up to 0.99, a result attributed to the Au(Ⅰ)-activated triplet radiative transfer pathway. Solution-processed organic light-emitting diode (OLED) devices fabricated with (PzIPr)AuOBO delivered deep blue emission with CIE coordinates of (0.15, 0.07) and a maximum external quantum efficiency (EQE) of 7.0%.
2026, 42(11): 2411-2419
doi: 10.11862/CJIC.20260211
摘要:
Under ultra-high vacuum, surface synthesis of 2D conjugated metal-organic frameworks (MOFs) was carried out through molecular beam epitaxy (MBE) growth to address the challenge of traditional solvothermal methods in achieving large-scale, defect-free single-crystal synthesis. Here, we chose an iconic 2D conjugated MOF, Cu3(HOTP)2 (HOTP represents the deprotonated derivative of 2,3,6,7,10,11-hexahydroxytriphenylene), as a case study to investigate the diversified self-assembly of Cu atoms and HHTP ligands, as well as the synthesis mechanism of the MOF fragment on the surface with and without O2 annealing conditions by scanning tunneling microscopy. The results show that dumbbell-shaped [Cu(HOTP)2] complexes, the target fragment of MOFs, can be successfully generated in an O2 atmosphere, yet large-area extended MOFs remain elusive, highlighting oxidation and ligand deprotonation as two key factors that hinder the on-surface synthesis of Cu3(HOTP)2.
Under ultra-high vacuum, surface synthesis of 2D conjugated metal-organic frameworks (MOFs) was carried out through molecular beam epitaxy (MBE) growth to address the challenge of traditional solvothermal methods in achieving large-scale, defect-free single-crystal synthesis. Here, we chose an iconic 2D conjugated MOF, Cu3(HOTP)2 (HOTP represents the deprotonated derivative of 2,3,6,7,10,11-hexahydroxytriphenylene), as a case study to investigate the diversified self-assembly of Cu atoms and HHTP ligands, as well as the synthesis mechanism of the MOF fragment on the surface with and without O2 annealing conditions by scanning tunneling microscopy. The results show that dumbbell-shaped [Cu(HOTP)2] complexes, the target fragment of MOFs, can be successfully generated in an O2 atmosphere, yet large-area extended MOFs remain elusive, highlighting oxidation and ligand deprotonation as two key factors that hinder the on-surface synthesis of Cu3(HOTP)2.
2026, 42(11): 2459-2474
doi: 10.11862/CJIC.20260129
摘要:
A series of cyclopentadienyl iron(Ⅱ) complexes of bidentate phosphine ligands bearing pendant amine bases, R-N(CH2P(Ph)2)2 [Ln: n=1 (R=n-propyl), 2 (R=benzyl), 3 (R=o-CH2Py)], were synthesized: [CpFe(Ln)I] (1a-1c: n=1-3), [CpFe(Ln)(NCMe)]I (2a-2c: n=1-3), and [CpFe(Ln)(NCMe)]PF6 (3a-3c: n=1-3), to mimic the structure and function of the distal iron unit in the diiron active site of [FeFe]-hydrogenases. By varying the R substituents of pendant amines, we aimed to investigate how amine basicity regulates the reactivity of these iron complexes. The iodo complexes 1a-1c underwent facile ligand substitution by MeCN, affording iodide complexes 2a-2c. The returns from 2a-2c to 1a-1c in chloroform were spectroscopically probed to demonstrate a linear correlation between rate constants and the pKa values of the pendant amines. Nevertheless, the returns were completely inhibited in the hexafluorophosphate (PF6-) complexes 3a-3c. Further insights from electrochemical investigations revealed that one-electron reduction of the Fe(Ⅱ) complexes leads to the formation of 17-electron Fe(Ⅰ) species, whereby an additional chemical process should be involved to liberate the labile ligand (I- or MeCN) from the metal centre to result in a precious vacancy. The observation was corroborated by density functional theory (DFT) calculations, which predicted the creation of a vacant site at the intermediate upon reduction. Particularly, the electrocatalytic activity of these iron complexes towards proton reduction was found to be significantly influenced by the basicity of the pendant amine, whereas low basic amines generally result in high efficiency. Our results revealed the crucial role of the substituent on the pendant amine in manipulating the chemistry of metal-based ligand exchange as well as electrocatalytic proton reduction.
A series of cyclopentadienyl iron(Ⅱ) complexes of bidentate phosphine ligands bearing pendant amine bases, R-N(CH2P(Ph)2)2 [Ln: n=1 (R=n-propyl), 2 (R=benzyl), 3 (R=o-CH2Py)], were synthesized: [CpFe(Ln)I] (1a-1c: n=1-3), [CpFe(Ln)(NCMe)]I (2a-2c: n=1-3), and [CpFe(Ln)(NCMe)]PF6 (3a-3c: n=1-3), to mimic the structure and function of the distal iron unit in the diiron active site of [FeFe]-hydrogenases. By varying the R substituents of pendant amines, we aimed to investigate how amine basicity regulates the reactivity of these iron complexes. The iodo complexes 1a-1c underwent facile ligand substitution by MeCN, affording iodide complexes 2a-2c. The returns from 2a-2c to 1a-1c in chloroform were spectroscopically probed to demonstrate a linear correlation between rate constants and the pKa values of the pendant amines. Nevertheless, the returns were completely inhibited in the hexafluorophosphate (PF6-) complexes 3a-3c. Further insights from electrochemical investigations revealed that one-electron reduction of the Fe(Ⅱ) complexes leads to the formation of 17-electron Fe(Ⅰ) species, whereby an additional chemical process should be involved to liberate the labile ligand (I- or MeCN) from the metal centre to result in a precious vacancy. The observation was corroborated by density functional theory (DFT) calculations, which predicted the creation of a vacant site at the intermediate upon reduction. Particularly, the electrocatalytic activity of these iron complexes towards proton reduction was found to be significantly influenced by the basicity of the pendant amine, whereas low basic amines generally result in high efficiency. Our results revealed the crucial role of the substituent on the pendant amine in manipulating the chemistry of metal-based ligand exchange as well as electrocatalytic proton reduction.
2026, 42(11): 2335-2342
doi: 10.11862/CJIC.20260074
摘要:
本研究以光活性配体9-蒽甲酸(9-HAc)为构筑单元，采用溶剂热法合成了2例双核Dy3+配合物[Dy2(9-Ac)6(DMA)2] (1)和[Dy2(9-Ac)6(NMP)2] (2)(DMA=N，N-二甲基乙酰胺，NMP=N-甲基吡咯烷酮)。单晶X射线衍射结果表明，1和2均为双核结构，其中Dy3+离子呈现八配位的三角十二面体构型。在300 W氙灯照射下，1和2的粉末样品分别由淡粉色和淡黄色转变为棕色/深棕色，同时发光强度显著降低。时间依赖紫外可见吸收光谱显示，在光照过程中，可见光区出现宽吸收带并逐渐增强；电子顺磁共振波谱在g=2.002处检测到自由基信号，表明光照诱导电子转移并生成稳定自由基。红外光谱和粉末X射线衍射结果表明，光照前后配位骨架保持稳定。
本研究以光活性配体9-蒽甲酸(9-HAc)为构筑单元，采用溶剂热法合成了2例双核Dy3+配合物[Dy2(9-Ac)6(DMA)2] (1)和[Dy2(9-Ac)6(NMP)2] (2)(DMA=N，N-二甲基乙酰胺，NMP=N-甲基吡咯烷酮)。单晶X射线衍射结果表明，1和2均为双核结构，其中Dy3+离子呈现八配位的三角十二面体构型。在300 W氙灯照射下，1和2的粉末样品分别由淡粉色和淡黄色转变为棕色/深棕色，同时发光强度显著降低。时间依赖紫外可见吸收光谱显示，在光照过程中，可见光区出现宽吸收带并逐渐增强；电子顺磁共振波谱在g=2.002处检测到自由基信号，表明光照诱导电子转移并生成稳定自由基。红外光谱和粉末X射线衍射结果表明，光照前后配位骨架保持稳定。
2026, 42(11): 2353-2361
doi: 10.11862/CJIC.20260137
摘要:
为满足对全氟烷基物质(PFAS)快速且灵敏的检测需求，以2-氨基对苯二甲酸为配体，通过溶剂热法合成了2例不同金属中心的同构金属有机框架(MOFs)UiO-66-NH2(Ce)和UiO-66-NH2(Zr)，研究了它们对PFAS的荧光传感性质。通过粉末X射线衍射、傅里叶变换红外光谱和热重分析等表征验证了所合成样品具有较高的相纯度、良好的酸碱稳定性以及热稳定性。这2例MOFs对全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)均表现出增强型荧光响应，其中传感效果更好的UiO-66-NH2(Ce)对PFOS的检测限低至0.17 μmol·L-1，且具有快速的响应以及良好的抗干扰能力。机理研究表明，这2例MOFs主要通过氨基与PFAS酸性基团间的静电相互作用以实现增强型荧光响应，而不同的金属中心通过极化能力调节框架中的主体-客体作用强度，从而调控了传感性能。
为满足对全氟烷基物质(PFAS)快速且灵敏的检测需求，以2-氨基对苯二甲酸为配体，通过溶剂热法合成了2例不同金属中心的同构金属有机框架(MOFs)UiO-66-NH2(Ce)和UiO-66-NH2(Zr)，研究了它们对PFAS的荧光传感性质。通过粉末X射线衍射、傅里叶变换红外光谱和热重分析等表征验证了所合成样品具有较高的相纯度、良好的酸碱稳定性以及热稳定性。这2例MOFs对全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)均表现出增强型荧光响应，其中传感效果更好的UiO-66-NH2(Ce)对PFOS的检测限低至0.17 μmol·L-1，且具有快速的响应以及良好的抗干扰能力。机理研究表明，这2例MOFs主要通过氨基与PFAS酸性基团间的静电相互作用以实现增强型荧光响应，而不同的金属中心通过极化能力调节框架中的主体-客体作用强度，从而调控了传感性能。
2026, 42(11): 2381-2388
doi: 10.11862/CJIC.20260207
摘要:
为探索配位构型对铂炔配合物分子内电荷传输特性的调控规律，我们合成了铂炔配合物的顺反异构体trans-/cis-Pt(PEt3)2 (C≡CPhSMe)2(1-t和1-c，PhSMe=4-甲硫基苯基)，通过扫描隧道显微镜断裂结(STM-BJ)技术测量了2种异构体的单分子电导。我们发现1-t在10-4.5G0(G0是量子电导，约77 500 nS)处呈现清晰的电导峰值，而1-c的电导降低至仪器检测限(约10-6.0G0)以下。结合非平衡格林函数(NEGF)与密度泛函理论(DFT)的理论计算和转变电压谱共同表明，2个因素协同造成了这种超过一个数量级的电导差异。首先，顺式异构体的垂直几何构型导致前线轨道在2个炔基配体上的空间分布不对称，与金电极形成不对称耦合。其次，2个炔基配体的距离缩小诱发空间电子传输，导致铂炔配位键上出现反向环形电流，进而引发相消量子干涉，在透射系数曲线上形成尖锐的反共振凹陷。
为探索配位构型对铂炔配合物分子内电荷传输特性的调控规律，我们合成了铂炔配合物的顺反异构体trans-/cis-Pt(PEt3)2 (C≡CPhSMe)2(1-t和1-c，PhSMe=4-甲硫基苯基)，通过扫描隧道显微镜断裂结(STM-BJ)技术测量了2种异构体的单分子电导。我们发现1-t在10-4.5G0(G0是量子电导，约77 500 nS)处呈现清晰的电导峰值，而1-c的电导降低至仪器检测限(约10-6.0G0)以下。结合非平衡格林函数(NEGF)与密度泛函理论(DFT)的理论计算和转变电压谱共同表明，2个因素协同造成了这种超过一个数量级的电导差异。首先，顺式异构体的垂直几何构型导致前线轨道在2个炔基配体上的空间分布不对称，与金电极形成不对称耦合。其次，2个炔基配体的距离缩小诱发空间电子传输，导致铂炔配位键上出现反向环形电流，进而引发相消量子干涉，在透射系数曲线上形成尖锐的反共振凹陷。
2026, 42(11): 2389-2398
doi: 10.11862/CJIC.20260208
摘要:
探究了2-溴异丁酸配位锆氧簇——即Zr5O4[BrC(CH3)2COO]10(OnPr)2(nPrOH)4(命名为Zr5Br10)和Zr6O4(OH)4(OOCC(CH3)2Br)12(命名为Zr6Br12)的晶体结构与其溶解特性的关系，并首次评估了Zr5Br10的电子束光刻性能。分析发现，簇分子的结构对称性对其溶解行为具有重要影响：低对称性的Zr5Br10成膜能力优异，而高对称性的Zr6Br12则极难溶解。在图案化过程中，Zr5Br10薄膜的光刻性能高度依赖显影动力学。在低极性“弱溶剂”正庚烷体系下，薄膜展现出超高灵敏度(38.1 μC·cm-2)与优异对比度(12.5)。X射线光电子能谱(X-ray photoelectron spectroscopy，XPS)表征进一步揭示了该光刻胶的负性交联机理，即电子束诱发配体脱羧及C—Br键断裂，随后形成的活性金属中心原位重组，生成难溶的Zr—O—Zr三维网络。
探究了2-溴异丁酸配位锆氧簇——即Zr5O4[BrC(CH3)2COO]10(OnPr)2(nPrOH)4(命名为Zr5Br10)和Zr6O4(OH)4(OOCC(CH3)2Br)12(命名为Zr6Br12)的晶体结构与其溶解特性的关系，并首次评估了Zr5Br10的电子束光刻性能。分析发现，簇分子的结构对称性对其溶解行为具有重要影响：低对称性的Zr5Br10成膜能力优异，而高对称性的Zr6Br12则极难溶解。在图案化过程中，Zr5Br10薄膜的光刻性能高度依赖显影动力学。在低极性“弱溶剂”正庚烷体系下，薄膜展现出超高灵敏度(38.1 μC·cm-2)与优异对比度(12.5)。X射线光电子能谱(X-ray photoelectron spectroscopy，XPS)表征进一步揭示了该光刻胶的负性交联机理，即电子束诱发配体脱羧及C—Br键断裂，随后形成的活性金属中心原位重组，生成难溶的Zr—O—Zr三维网络。
2026, 42(11): 2420-2428
doi: 10.11862/CJIC.20260235
摘要:
以含双键π-π共轭的桥联氮配体(bpen)与双膦配体(POP)为功能配体，成功合成了3种橙黄色发光Cu(Ⅰ)配合物，即[Cu2I2(bpen)(POP)2] (1)、[Cu2Br2(bpen)(POP)2]·2CH2Cl2 (2)与[Cu2Cl2(bpen)(POP)2] (3)。采用X射线单晶衍射、1H NMR、红外光谱、紫外可见吸收光谱及荧光光谱，对3种目标配合物的晶体结构与光物理性质进行了全面系统的表征。荧光测试显示，3种配合物的最大发射波长分别为592、598和599 nm，均表现出优异的橙黄色发光特性。机理分析表明，通过调控配体共轭效应、优化配体构象及桥联配位方式，可有效调控配合物的激发态行为，实现其发光性能的精准调控。
以含双键π-π共轭的桥联氮配体(bpen)与双膦配体(POP)为功能配体，成功合成了3种橙黄色发光Cu(Ⅰ)配合物，即[Cu2I2(bpen)(POP)2] (1)、[Cu2Br2(bpen)(POP)2]·2CH2Cl2 (2)与[Cu2Cl2(bpen)(POP)2] (3)。采用X射线单晶衍射、1H NMR、红外光谱、紫外可见吸收光谱及荧光光谱，对3种目标配合物的晶体结构与光物理性质进行了全面系统的表征。荧光测试显示，3种配合物的最大发射波长分别为592、598和599 nm，均表现出优异的橙黄色发光特性。机理分析表明，通过调控配体共轭效应、优化配体构象及桥联配位方式，可有效调控配合物的激发态行为，实现其发光性能的精准调控。
2026, 42(11): 2429-2437
doi: 10.11862/CJIC.20260223
摘要:
引入1，5-萘二磺酸(1，5-H2NDS)作为结构导向剂，与四甲基六元瓜环(TMeQ[6])在水热条件下反应，成功制备出了一种新颖的TMeQ[6]基超分子自组装体：(H3O)(1，5-NDS)0.5·TMeQ[6]·13H2O (1)。根据单晶X射线衍射(SCXRD)测试结果可知，自组装体1中TMeQ[6]分子通过氢键作用形成了一维“Z”形超分子链和二维波浪形超分子层。这些二维层通过TMeQ[6]分子外壁与1，5-NDS2-客体阴离子形成C—H…O氢键，TMeQ[6]外壁还与1，5-NDS2-的萘环形成C—H…π作用，最终组装成三维超分子结构。由于自组装体1的晶体结构中未配位的“自由”羰基端口的存在，该位点可以通过配位作用实现对Cs+的特异性捕获。SCXRD测试结果进一步证实，负载Cs+后的自组装体2的晶体结构除了在TMeQ[6]分子的一个端口处多了一个配位的Cs+外，其余结构参数未发生显著改变。这一结果直接证明，自组装体1可以通过TMeQ[6]端口羰基与Cs+的配位作用实现对Cs+的捕获。此外，荧光识别实验显示，自组装体1的荧光发射峰可作为比率型荧光探针选择性识别磺胺嘧啶(SD)、环丙沙星(CFX)和左氧氟沙星(LFX)。
引入1，5-萘二磺酸(1，5-H2NDS)作为结构导向剂，与四甲基六元瓜环(TMeQ[6])在水热条件下反应，成功制备出了一种新颖的TMeQ[6]基超分子自组装体：(H3O)(1，5-NDS)0.5·TMeQ[6]·13H2O (1)。根据单晶X射线衍射(SCXRD)测试结果可知，自组装体1中TMeQ[6]分子通过氢键作用形成了一维“Z”形超分子链和二维波浪形超分子层。这些二维层通过TMeQ[6]分子外壁与1，5-NDS2-客体阴离子形成C—H…O氢键，TMeQ[6]外壁还与1，5-NDS2-的萘环形成C—H…π作用，最终组装成三维超分子结构。由于自组装体1的晶体结构中未配位的“自由”羰基端口的存在，该位点可以通过配位作用实现对Cs+的特异性捕获。SCXRD测试结果进一步证实，负载Cs+后的自组装体2的晶体结构除了在TMeQ[6]分子的一个端口处多了一个配位的Cs+外，其余结构参数未发生显著改变。这一结果直接证明，自组装体1可以通过TMeQ[6]端口羰基与Cs+的配位作用实现对Cs+的捕获。此外，荧光识别实验显示，自组装体1的荧光发射峰可作为比率型荧光探针选择性识别磺胺嘧啶(SD)、环丙沙星(CFX)和左氧氟沙星(LFX)。
2026, 42(11): 2438-2450
doi: 10.11862/CJIC.20260226
摘要:
通过简便的一步配位驱动自组装法制备聚乙烯吡咯烷酮(PVP-K30)修饰的Cu-IR808纳米粒子(NPs)。该纳米平台集成了IR808(一种近红外七甲川花菁类染料)与Cu2+，实现了光动力治疗(PDT)、光热治疗(PTT)与化学动力学治疗(CDT)模块的高效整合。系统表征表明，所制备的NPs呈类球形，粒径约150.0 nm，并在808 nm处具有较强的近红外吸收。性能研究显示，该Cu-IR808 NPs在808 nm激光照射下表现出显著的光热转换能力(光热转换效率为29.9%)、光诱导活性氧(ROS)生成能力以及光热增强的类芬顿催化活性(45.0 ℃下对亚甲蓝的降解效率较常温提升约2.4倍)。体外细胞实验证实，Cu-IR808 NPs介导的联合治疗能有效抑制肿瘤细胞活力，同时生物安全性评估表明其具有良好的细胞相容性和血液相容性(溶血率低于5.0%)。
通过简便的一步配位驱动自组装法制备聚乙烯吡咯烷酮(PVP-K30)修饰的Cu-IR808纳米粒子(NPs)。该纳米平台集成了IR808(一种近红外七甲川花菁类染料)与Cu2+，实现了光动力治疗(PDT)、光热治疗(PTT)与化学动力学治疗(CDT)模块的高效整合。系统表征表明，所制备的NPs呈类球形，粒径约150.0 nm，并在808 nm处具有较强的近红外吸收。性能研究显示，该Cu-IR808 NPs在808 nm激光照射下表现出显著的光热转换能力(光热转换效率为29.9%)、光诱导活性氧(ROS)生成能力以及光热增强的类芬顿催化活性(45.0 ℃下对亚甲蓝的降解效率较常温提升约2.4倍)。体外细胞实验证实，Cu-IR808 NPs介导的联合治疗能有效抑制肿瘤细胞活力，同时生物安全性评估表明其具有良好的细胞相容性和血液相容性(溶血率低于5.0%)。
2026, 42(11): 2451-2458
doi: 10.11862/CJIC.20260166
摘要:
通过功能耦合策略，将光敏Ru中心与催化活性Au位点精准集成至共价有机框架(COF)中，成功构筑了Ru-Au双金属COF(Ru-Au-COF)，并系统研究了其光催化N2还原性能。由于集成了光敏Ru中心，该材料表现出优异的光捕获能力，同时，高密度负载的催化活性Au中心为N2活化提供了有效功能位点。光催化研究表明Ru-Au-COF具有优异的光催化固氮活性，产氨速率达231.7 μmol·g-1·h-1，相较于不含Au位点的材料(Ru-COF)，提升了近4倍。
通过功能耦合策略，将光敏Ru中心与催化活性Au位点精准集成至共价有机框架(COF)中，成功构筑了Ru-Au双金属COF(Ru-Au-COF)，并系统研究了其光催化N2还原性能。由于集成了光敏Ru中心，该材料表现出优异的光捕获能力，同时，高密度负载的催化活性Au中心为N2活化提供了有效功能位点。光催化研究表明Ru-Au-COF具有优异的光催化固氮活性，产氨速率达231.7 μmol·g-1·h-1，相较于不含Au位点的材料(Ru-COF)，提升了近4倍。
2026, 42(11): 2475-2492
doi: 10.11862/CJIC.20260044
摘要:
以包含金纳米粒子(AuNP)、二氧化硅(SiO2)、石墨烯量子点(GQD)和介孔二氧化硅(mSiO2)的核壳结构纳米复合物(AuNP@SiO2@GQD/mSiO2)为载体，构建了一种以壳聚糖(CTS)为成膜剂，涂覆于玻碳电极(GCE)表面，并固定葡萄糖氧化酶(GOx)的光电化学传感器AuNP@SiO2@GQD/mSiO2/GOx/CTS/GCE。实验结果表明，GOx与核壳结构纳米复合物的mSiO2外壳间有相对较弱的相互作用，主要包括静电作用、弱键合与氢键作用。这些作用有利于维持GOx分子固有的化学微环境，从而促进其对底物的催化氧化效能。在固酶光电化学传感器上，不仅观察到GQD表面电活性基团引发的不可逆氧化反应，还检测到一个典型的准可逆、涉及2个质子和2个电子转移的表面控制型电化学反应。该反应展现出优异的异相电荷转移性能，归一化速率常数达255.5 s-1。当溶液中存在共反应物时，GQD基电极在约-2.1 V处呈现出明显的电化学发光峰。优化该光电化学传感器的工作参数(包括共反应物浓度、溶液pH及扫描速率)后，评估了其对葡萄糖的传感性能。结果显示，该光电化学传感器具有较强且稳定的电化学发光信号，对底物呈现出较宽的线性响应范围(10-10~10-4 mol·L-1)和极低的检测限(8.55×10-11 mol·L-1)。
以包含金纳米粒子(AuNP)、二氧化硅(SiO2)、石墨烯量子点(GQD)和介孔二氧化硅(mSiO2)的核壳结构纳米复合物(AuNP@SiO2@GQD/mSiO2)为载体，构建了一种以壳聚糖(CTS)为成膜剂，涂覆于玻碳电极(GCE)表面，并固定葡萄糖氧化酶(GOx)的光电化学传感器AuNP@SiO2@GQD/mSiO2/GOx/CTS/GCE。实验结果表明，GOx与核壳结构纳米复合物的mSiO2外壳间有相对较弱的相互作用，主要包括静电作用、弱键合与氢键作用。这些作用有利于维持GOx分子固有的化学微环境，从而促进其对底物的催化氧化效能。在固酶光电化学传感器上，不仅观察到GQD表面电活性基团引发的不可逆氧化反应，还检测到一个典型的准可逆、涉及2个质子和2个电子转移的表面控制型电化学反应。该反应展现出优异的异相电荷转移性能，归一化速率常数达255.5 s-1。当溶液中存在共反应物时，GQD基电极在约-2.1 V处呈现出明显的电化学发光峰。优化该光电化学传感器的工作参数(包括共反应物浓度、溶液pH及扫描速率)后，评估了其对葡萄糖的传感性能。结果显示，该光电化学传感器具有较强且稳定的电化学发光信号，对底物呈现出较宽的线性响应范围(10-10~10-4 mol·L-1)和极低的检测限(8.55×10-11 mol·L-1)。
2026, 42(11): 2493-2503
doi: 10.11862/CJIC.20260070
摘要:
构建了一种集T1加权磁共振成像(MRI)与声动力-化学动力协同治疗于一体的诊疗一体化纳米探针(HA-Mn-MOF)。该探针以透明质酸(HA)修饰的锰卟啉金属有机框架(MOF)为核心，利用HA介导的主动靶向作用实现肿瘤特异性富集，卟啉单元作为声敏剂增强声动力治疗(SDT)效应；锰中心不仅能清除肿瘤微环境(TME)中过表达的谷胱甘肽(GSH)，还能与TME中的H2O2发生类芬顿反应，原位生成羟基自由基(·OH)和O2，在实现化学动力治疗(CDT)的同时缓解肿瘤乏氧，显著增强SDT疗效，从而高效杀伤乳腺癌细胞。此外，HA-Mn-MOF表现出pH和GSH双响应的MRI激活特性，其T1弛豫率达4.16 L·mmol-1·s-1，是生理条件下的2.7倍。
构建了一种集T1加权磁共振成像(MRI)与声动力-化学动力协同治疗于一体的诊疗一体化纳米探针(HA-Mn-MOF)。该探针以透明质酸(HA)修饰的锰卟啉金属有机框架(MOF)为核心，利用HA介导的主动靶向作用实现肿瘤特异性富集，卟啉单元作为声敏剂增强声动力治疗(SDT)效应；锰中心不仅能清除肿瘤微环境(TME)中过表达的谷胱甘肽(GSH)，还能与TME中的H2O2发生类芬顿反应，原位生成羟基自由基(·OH)和O2，在实现化学动力治疗(CDT)的同时缓解肿瘤乏氧，显著增强SDT疗效，从而高效杀伤乳腺癌细胞。此外，HA-Mn-MOF表现出pH和GSH双响应的MRI激活特性，其T1弛豫率达4.16 L·mmol-1·s-1，是生理条件下的2.7倍。
2026, 42(11): 2504-2514
doi: 10.11862/CJIC.20260008
摘要:
通过溶剂热法合成了一例新型Cd(Ⅱ)配合物[Cd(4，4′-bipy)(H2O)4] (4-MBS)2，用于Fe3+的检测。利用傅里叶变换红外光谱和热重分析对其进行了表征，并对配合物的荧光性能进行了考察。固态荧光结果表明，配合物的荧光发射来自4，4′-bipy的π*→π跃迁；荧光传感实验表明配合物对Fe3+表现出高灵敏度的识别响应，检出限为0.27 μmol·L-1；循环传感实验表明配合物具有良好的循环稳定性。经单晶X射线衍射分析确定了配合物的晶体结构，证明存在大量的O—H…O和C—H…π相互作用；Hirshfeld表面分析进一步证明了配合物中O—H…O和C—H…π相互作用的存在，同时在配合物结构中还存在H…H等相互作用。这些作用相互协同，增强了配合物的结构稳定性和荧光传感能力。机理研究结果表明Fe3+与O原子的相互作用和Fe3+与配合物的能量竞争吸收共同导致了配合物的荧光猝灭。
通过溶剂热法合成了一例新型Cd(Ⅱ)配合物[Cd(4，4′-bipy)(H2O)4] (4-MBS)2，用于Fe3+的检测。利用傅里叶变换红外光谱和热重分析对其进行了表征，并对配合物的荧光性能进行了考察。固态荧光结果表明，配合物的荧光发射来自4，4′-bipy的π*→π跃迁；荧光传感实验表明配合物对Fe3+表现出高灵敏度的识别响应，检出限为0.27 μmol·L-1；循环传感实验表明配合物具有良好的循环稳定性。经单晶X射线衍射分析确定了配合物的晶体结构，证明存在大量的O—H…O和C—H…π相互作用；Hirshfeld表面分析进一步证明了配合物中O—H…O和C—H…π相互作用的存在，同时在配合物结构中还存在H…H等相互作用。这些作用相互协同，增强了配合物的结构稳定性和荧光传感能力。机理研究结果表明Fe3+与O原子的相互作用和Fe3+与配合物的能量竞争吸收共同导致了配合物的荧光猝灭。
2026, 42(5): 897-905
doi: 10.11862/CJIC.20250358
摘要:
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
2026, 42(5): 906-916
doi: 10.11862/CJIC.20250348
摘要:
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
2026, 42(5): 917-924
doi: 10.11862/CJIC.20260357
摘要:
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
2026, 42(5): 925-932
doi: 10.11862/CJIC.20250352
摘要:
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
2026, 42(5): 933-943
doi: 10.11862/CJIC.20250334
摘要:
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
2026, 42(5): 944-958
doi: 10.11862/CJIC.20250323
摘要:
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
2026, 42(5): 959-968
doi: 10.11862/CJIC.20250320
摘要:
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
2026, 42(5): 969-979
doi: 10.11862/CJIC.20250317
摘要:
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
2026, 42(5): 980-990
doi: 10.11862/CJIC.20250304
摘要:
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
2026, 42(5): 991-1002
doi: 10.11862/CJIC.20250302
摘要:
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
2026, 42(5): 1003-1014
doi: 10.11862/CJIC.20250238
摘要:
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
2026, 42(5): 1015-1025
doi: 10.11862/CJIC.20250366
摘要:
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
2026, 42(5): 1026-1038
doi: 10.11862/CJIC.20250364
摘要:
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
2026, 42(5): 1039-1047
doi: 10.11862/CJIC.20250353
摘要:
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
2026, 42(5): 1048-1062
doi: 10.11862/CJIC.20250330
摘要:
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
2026, 42(5): 1063-1072
doi: 10.11862/CJIC.20250345
摘要:
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
2026, 42(5): 1073-1084
doi: 10.11862/CJIC.20250328
摘要:
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
2026, 42(5): 1085-1095
doi: 10.11862/CJIC.20250321
摘要:
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
2026, 42(5): 1096-1112
doi: 10.11862/CJIC.20250311
摘要:
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
2026, 42(5): 1113-1120
doi: 10.11862/CJIC.20250298
摘要:
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
