Table of Content

10 January 2022, Volume 43 Issue 1

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Content

Cover and Content of Chemical Journal of Chinese Universities Vol.43 No.1(2022)

2022, 43(1):  1-6. 

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Review

Research Advance of Polyoxoniobate-based 3-Dimensional Framework Materials

CHEN Huina, LI Xinxiong, ZHENG Shoutian

2022, 43(1):  20210625.  doi:10.7503/cjcu20210625

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Recently， polyoxoniobate-based three-dimensional framework materials have been a research hotspot in the fields of inorganic synthetic chemistry and material chemistry. Such materials can not only combine the excellent properties of polyoxoniobate with the advantages of the frameworks， but also exhibit important applications in photocatalysis， host-guest chemistry， energy conversion and so on. In this review， the recent development of polyoxoniobate-based three-dimensional framework materials is summarized， including their assembly methodologies， structure regulation， properties， and related applications. Moreover， the current challenges and the prospects of these materials are also discussed.



Progress of the Synthesis of High-Nuclearity Ag/S Nanoclusters

TAN Yuling, YANG Ling, YU Hong, NI Chunyan, LANG Jianping

2022, 43(1):  20210476.  doi:10.7503/cjcu20210476

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The high-nuclearity silver nanoclusters protected by thiol ligands not only have beautiful structures and attractive functionalities， but also have broad application prospects in photoluminescence， biosensing and imaging， nanomaterials etc. However， the precise control of the size and structure of high-nuclearity Ag/S nanoclusters remains a great challenge. Therefore， feasible synthetic strategies to construct high-nuclearity Ag/S nanoclusters have always been the focus of attention. In recent years， with the development of synthetic approaches and characterization techniques， significant achievements have been made in the synthesis and functionality of high-nuclearity Ag/S nanoclusters. In this review， the general synthesis methods of high-nuclearity Ag/S nanoclusters containing 20 or more silver centers（direct reduction method， anion-templated method， ligand exchange method） were introduced and summarized， and structures of some high-nuclearity Ag/S nanoclusters were discussed. Finally， some prospects on the trend of future research in this respect are given.



Research Progress of Metal⁃organic Frameworks on Liquid Phase Catalytic Chemical Hydrogen Production

LI Shurong, WANG Lin, CHEN Yuzhen, JIANG Hailong

2022, 43(1):  20210575.  doi:10.7503/cjcu20210575

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Metal-organic frameworks（MOFs） as an emerging class of inorganic porous materials， are typical inorga? nicorganic hybrids composed of metal nodes and organic connectors. MOFs have shown broad application prospects in many fields， including industrial synthesis， energy development， environmental governance and biopharmaceutical due to their highly ordered porosity， structure tailorability， high specific surface area and flexible skeleton types. In this review， starting from the development and utilization of hydrogen energy， we summarize the recent progress on catalytic hydrogen production from chemical hydrogen storage materials by MOF?based nanocomposites. The hydrogen storage materials are common amino borane， formic acid and hydrazine hydrate with high hydrogen content. Catalysts are mainly MOF?based noble and non-noble metal composites， and MOF?based derived materials. Finally， the application prospect of MOFs?based materials in liquid phase catalytic chemical hydrogen storage is prospected.



Research Progress of Polyoxometalates-Cyclodextrin Supramolecular System

WEI Zheyu, WU Zhikang, RU Shi, NI Lubin, WEI Yongge

2022, 43(1):  20210665.  doi:10.7503/cjcu20210665

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This paper reviewed representative work on cyclodextrin-based polyoxometalates supramolecular systems in recent years. Based on the structural types of different polyoxometalates in the polyoxometalates/cyclodextrin supramolecular complex， the corresponding induction and overview were carried out. It is hoped that this paper can arouse readers’ interest in the research of polyoxometalate/cyclodextrin supramolecular system， and provide some new ideas and inspiration for researchers.



Research Status and Progress of MOFs with Application in Photoelectrochemical Water-splitting

SHI Xiaofan, ZHU Jian, BAI Tianyu, FU Zixuan, ZHANG Jijie, BU Xianhe

2022, 43(1):  20210613.  doi:10.7503/cjcu20210613

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Photoelectrochemical water-splitting has been considered as one of the most efficient methods to convert solar energy into chemical energy. Compared to the photocatalytic system with powder photocatalyst， the photoelectrochemical system using an H-type electrolytic cell possesses advantages of wider material selection range， higher charge transfer and separation efficiency， and easier ways to recycle photocatalysts. In recent years， more and more researches focus on applying metal-organic frameworks（MOFs） as the photoelectrodes in photoelectrochemical water-splitting reactions. Compared to inorganic photocatalysts， MOFs semiconductors exhibit large surface areas and tunable structures， which are beneficial to photocatalysis. In this review， we summarized research status and progress of MOFs in photoelectrochemical water-splitting applications according to the classification of MOF-based photoelectrode， including MOFs photoelectrode， MOFs-based heterostructure photoelectrode and MOFs-derived photoelectrode. This review also covers some typical research cases in the field of photocatalysis， which provides references for the research of MOFs in the field of photoelectrochemical water-splitting. Finally， research trends and hotspots in this field are also discussed.



Article

Synthesis and Proton Conductivity of Polynuclear Polyoxothiomolybdate Compound

LI Bo, MENG Yuxi, WANG Wenwen, ZANG Hongying

2022, 43(1):  20210657.  doi:10.7503/cjcu20210657

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Proton exchange membrane fuel cell（PEMFC） is widely used for its high energy conversion rate， low pollution， low working temperature and fast start-up speed. The high cost and fuzzy structural characteristics of Nafion membranes hinder the further improvement of proton conduction performance and the accurate understanding of conduction mechanism. The development of crystalline materials with high proton conductivity with clear structures and clear conduction paths is of great significance to the field of fuel cells. Here， a novel polynuclear polyoxothiomolybdate cluster ［N（CH₃）₄］₂H₂［（Mo₂S₂O₂）₈（OH）₁₆（C₈O₅H₄）₂］·22H₂O（Mo₁₆） was got via using the organic ligand 5-hydroxyisophthalic acid as a template to induce the occurrence of self-assembly reaction of ［Mo₂S₂O₂］²⁺. The clear structure and the dense hydrogen bond network in the structure can be used for the study of proton conductivity. The alternating current（AC） impedance test results show that Mo₁₆ has high proton conductivity in a wide temperature range. Its proton conductivity can attain 1.9×10^-2 S/cm at 97% relative humidity（RH） and 85 ℃. It shows that the compound has good prospects as a high-efficiency proton conductor.



Zirconium-based Metal-Organic Framework with Naphthalene for Fluorescent Detection of Nitroaromatic Explosives in Water

LI Wen, QIAO Junyi, LIU Xinyao, LIU Yunling

2022, 43(1):  20210654.  doi:10.7503/cjcu20210654

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Guided by molecular building block（MBB） approach， a naphthalene-based linear organic ligand 4，4′-（9，10-naphthalenediyl）bis-benzoic acid（H₂NDBA） is designed and synthesized to build the oriented framework. By using the modulator method， the solvothermal reaction of ZrOCl₂·8H₂O and H₂NDBA ligand yields the ［Zr₆（μ₃-O）₄·（μ₃-OH）₄（NDBA）₆］·7DMF·4H₂O（JLU?MOF100） with anticipated fcu topology. JLU?MOF100 displays high porosity and good water stability. Benefiting from the naphthalene group in the ligand， JLU?MOF100 exhibits significant fluorescent properties. It shows good performance in the detection of different nitroaromatic explosives in water by quenching effect.



A Microporous Cationic Ga（III）-MOF with Fluorescence Properties for Selective sensing Fe³⁺ Ion and Nitroaromatic Compounds

WU Ji, ZHANG Hao, LUO Yuhui, GENG Wuyue, LAN Yaqian

2022, 43(1):  20210617.  doi:10.7503/cjcu20210617

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A new cationic gallium-organic framework， namely ［Ga₃O（H₂O）₃（TCA）₂］·NO₃·6DMF·2H₂O（JOU-27， H₃TCA=4，4′，4″-tricarboxyltriphenylamine）， has been synthesized by solvothermal method and characterized. Structural analyses show that JOU-27 is a three-dimensional microporous framework based on oxygen-core trinuclear gallium clusters. Due to the introduction of fluorescent ligand， JOU-27 shows strong fluorescence emission and was developed as a fluorescent sensor to detect Fe³⁺ ion and nitroaromatic compounds. The detection limit of Fe³⁺ is as low as 2.22×10^-6 mol/L（K_SV=52823 L/mol， K_SV is the Stern-Volmer constant）. When the nitrobenzene（NB） concentration is only 3.27×10^-3 mol/L， the quenching efficiency can reach 91%. In addition， further studies show that the quenching performance of JOU-27 may be due to the fluorescence resonance energy transfer（FRET） effect， the competition of excitation light absorption， and the electron transfer between the excited state of the framework and nitroaromatics.



Synthesis， Structure， and Allochroic Property of Two Hetro-arsenomolybdates Hybrid Polyoxometalates

WANG Jin, SHI Wenjie, JIN Linyu, MA Pengtao, WANG Jingping, NIU Jingyang

2022, 43(1):  20210600.  doi:10.7503/cjcu20210600

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Benzene-1，3-dicarboxylic acid（H₂BDC） and 5-hydroxy-1，3-benzene dicarboxylic acid（H₂OIP） have been employed to synthesis two organic-inorganic hybrid arsenomolybdates， （NH₄）₁₇H₄［（AsMo₆O₂₁）₂（AsMo₆O₂₃）（BDC）₄］·28H₂O（1） and （NH₄）₅Cs₈H₆［（AsMo₆O₂₁）₃（OIP）₅］·40H₂O（2）. X-Ray crystallographic study indicated that both of the two compounds are trimers. The photochromic properties have been studied. Under the irradiation of a Xe-lamp， the two compounds changed their colors within 5 min. The thermochromic study of the two compounds indicated that they changed color at 373 K， and their color deepened on the increase of temperature.



General Strategy for In situ Synthesis of NENU-n Series Polyoxometalate-based MOFs on Copper Foil

WANG Jie, HUO Haiyan, WANG Yang, ZHANG Zhong, LIU Shuxia

2022, 43(1):  20210557.  doi:10.7503/cjcu20210557

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The NENU-n series polyoxometalate-based metal-organic framework（POM@MOFs） are formed by encapsulating a series of excellent Keggin type polyoxometalates into Cu₃（BTC）₂ framework， showing excellent performance in the fields of catalysis and proton conduction. In this work， a new method of in situ synthesis of POM@MOFs on copper foil was developed on the basis of the previous work， that is， oxygen was added into the reaction solution， and the oxygen could oxidize Cu⁰ to Cu²⁺ under acidic conditions to provide copper ion source for the growth of the metal-organic framework. Thus， even though the oxidation capacity of Keggin tungsten polyoxometalates is weak， pure phase products of NENU-n series hybrids can also be synthesized in situ on copper substrates. The method is simple， rapid and high atomic economy at room temperature. Moreover， we found that POM@MOFs with controllable morphology can be generated by using this method without adding any regulator， and its morphology depends on the charge of heteropoly acid anions. The heteropoly anion with high charge can obtain the cubic morphology， while the heteropoly anion with low charge can obtain the octahedral shape. Catalytic oxidation of simulated mustard gas （2-chloroethylethyl sulfide， CEES） was studied by using the synthesized materials. The results showed that the NENU-40［K₅BW₁₂O₄₀/Cu₃（BTC）₂］ with cubic morphology exposed more active sites and showed a better catalytic activity. CEES can be completely converted to non-toxic CEESO within 10 min.



Separating Methyl Blue Selectively from the Mixture of Dyes by Europium Metal-organic Frameworks

LIU Xueguang, YANG Xiaoshan, MA Jingjing, LIU Weisheng

2022, 43(1):  20210715.  doi:10.7503/cjcu20210715

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Although Eu-based metal-organic frameworks as fluorescence sensors have been reported widely， they are rarely used to separate dyes selectively owing to the lack of water stability. Herein， we choose a reported Eu-MOF to separate MB（methylene blue） selectively from mixed dyes aqueous by ion exchanges between the cations in the pore channels of the Eu-MOF and MB. The results show that MB can be separated selectively and quickly from the mixture of dyes. Meanwhile， the Eu-MOF not only has the relatedly high absorbing capacity of ca. 20 mg/g in aqueous solution at room temperature， but also can be recycled for 3 times at least. Moreover， the mechanism of highly selective absorption was also discussed， and as a consequence， the charge interaction and size exclusion play a key role in the absorption progress.



Two B₅O_n（n=11， 12） Cluster-based Borates with Deep UV Cutoff Edge

CHEN Chongan, YANG Guoyu

2022, 43(1):  20210711.  doi:10.7503/cjcu20210711

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Two new borates Na₂Ba［B₅O₈（OH）］₂·2H₂O（1） and KSr［B₅O₈（OH）₂］（2）， with deep UV cutoff edges， were solvothermally made by using mixed alkali and alkaline-earth metal templates. They were further characterized by single-crystal XRD， powder XRD， IR spectra， UV-Vis absorption spectra and thermogravimetric analysis. Compound 1 crystalizes in the monoclinic space group P2/c. 4-connected B₅O₁₀（OH） cluster build 2D monolayer with two kinds of 9-MR windows via corner-sharing. Compound 2 crystalizes in the monoclinic space group C2/c. 4-connected B₅O₁₀（OH）₂ cluster construct 2D fluctuant layer with different 8- and 12-MR unclosed channels along two different directions. Both 1 and 2 exhibit the cutoff edge below 200 nm， indicating their potential applications in UV and deep UV regions.



A Multi-functional Zn（II） Coordination Polymer with Luminescence Sensing， Amperometric Sensing， and Dye Adsorption Performance

MA Jianxin, LIU Xiaodong, XU Na, LIU Guocheng, WANG Xiuli

2022, 43(1):  20210585.  doi:10.7503/cjcu20210585

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A porous coordination polymer Zn（4-bpft）（1，4-bdc）］（CP 1） was constructed from the N，N′-bis（4-pyridine formamide）-3，4-thiophene（4-bpft） and terephthalic acid （1，4-H₂bdc） mixed-ligand under hydrothermal condition. It’s structure and composition were characterized by means of single crystal X-ray diffraction， FTIR and PXRD techniques. The results show that CP 1 is a 2D network with 17.3% of solvent accessible void space by PLATON， which exhibits a 3-connected network with ｛6³｝ topology. CP 1 displays obvious fluorescent turning on sensing and can efficiently detect asparticacid（Asp）. It also exhibits electrochemically reversible redox behavior， and can be used as an amperometric sensor for detecting ascorbic acid（AA）. In addition， the adsorption behavior of CP 1 was evaluated with organic dyes methylene blue（MB）， gentian purple（GV）， and neutral red（NR）， implying it has potential application value in removing organic pollutants.



Guest-responses of A Porous Coordination Polymer Based on Synergistic Hydrogen Bonds

MO Zongwen, ZHANG Xuewen, ZHOU Haolong, ZHOU Dongdong, ZHANG Jiepeng

2022, 43(1):  20210576.  doi:10.7503/cjcu20210576

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Solvothermal reaction of Zn（NO₃）₂·6H₂O， pyrazole-3， 5-dicarboxylic acid （H₃pzdc） and 2-amino-1，4-benzenedicarboxylic acid （H₂abdc） in N，N-dimethylformamide（DMF） produced a porous coordination polymer（Me₂NH₂）［Zn₂（pzdc）（abdc）］·H₂O·DMF（1·g， g means guest molecules， H₂O and DMF）， in which Me₂NH₂⁺ was generated from the hydrolysis of the solvent DMF. The 3-dimensional porous coordination framework of 1 can be regarded as a pillared-ribbon structure consisting of parallelly-aligned flat ｛Zn₂（pzdc）｝⁺ ribbons and abdc^2- pillars. via desorption/adsorption of solvent molecules， centrosymmetric 1·g can reversibly transform to a chiral framework （Me₂NH₂）［Zn₂（pzdc）（abdc）］（1'）. Single-crystal X-ray diffraction analyses showed that， based on the competition and cooperation of hydrogen bonds among the host framework， counter cations， and neutral guest molecules， the counter cations underwent significant movement and rotation in the guest-responsive structural transformations， giving rise to the distortion and rotation of the ｛Zn₂（pzdc）｝⁺ ribbon， as well as more than 10% changes of the unit-cell volume and void ratio. Gas adsorption measurements of 1' showed different responses toward N₂ and CO₂.



Synthesis and Electrochemical Biosensing Properties of Pyridine Dicarboxylic Acid Decorated Rare-earth-incorporatedTellurotungstates

JIANG Jun, GONG Tiantian, ZHANG Chengpeng, LIU Xiaoqian, ZHAO Junwei

2022, 43(1):  20210561.  doi:10.7503/cjcu20210561

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A family of rare 2，6-pyridinedicarboxylic acid decorated rare-earth（RE）-incorporated Keggin-type tellurotungstates（TTs）（PTEA）₇H₃K［RE₂（B-α-TeW₉O₃₃）₃W₃O₅（H₂O）₃（HDPA）］·22H₂O［RE=Ce³⁺（1）， Pr³⁺（2）， Nd³⁺（3）， Sm³⁺（4）； H₂DPA=2，6-pyridinedicarboxylic acid； PTEA=protonated triethanolamine］ were synthesized by the one-step self-assembly strategy in NaAc aqueous solution via microwave heating method. The polyanion of isomorphic compounds 1—4 consists of three trivacant Keggin ［B-α-TeW₉O₃₃］^8- building blocks linked by a ｛RE₂W₃O₅（H₂O）₃（HDPA）｝¹³⁺ heterometallic cluster. In this heterometallic cluster， HDPA as quadridentate ligand coordinates with two RE ions（RE1 and RE2） to form planar tri-heterocycle structure， which is perpendicular to the planar constructed by W2， W2A and W16 centers. Additionally， compound 1 can combinate with carboxylic multi-walled carbon nanotube（CMWCNT） to produce the 1-CMWCNT composite， which was then used as electrode material to establish electrochemical biosensor for detecting sequence-specific DNA.



Synthesis and Supercapacitor Properties of Biimidazole-modified ｛SiW₁₂O₄₀｝ Hybrid

LIANG Yu, LIU Huan, GONG Lige, WANG Chunxiao, WANG Chunmei, YU Kai, ZHOU Baibin

2022, 43(1):  20210556.  doi:10.7503/cjcu20210556

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H₄SiW₁₂O₄₀ was used as a precursor to synthesize biimidazole-modified supramolecular hybrid under hydrothermal condition， and its chemical formula was determined to be ［Co（bim）₂（H₂O）₂］［H₂SiW₁₂O₄₀］·2H₂O（1）（bim=biimidazole） by elemental composition and thermal gravity（TG） analysis. Single-crystal diffraction analysis shows that， the compound is composed of ［H₂SiW₁₂O₄₀］^2?， ［Co（bim）₂（H₂O）₂］²⁺ and two H₂O. At the same time， the components form 1D to 3D structures through hydrogen bond and supramolecular interaction. Using glassy carbon， carbon cloth and nickel foam as the current collectors， when the current density is 1 A/g， in the three-electrode system， compound 1 shows the specific capacitance（350.09， 107.02 and 186.83 F/g）， better than most literature reports， and with capacitance retention of 94.5%， 92.8% and 95.1% after 5000 cycles. The kinetic analysis shows that the charge storage mechanism of the compound is dominated by surface-controlled electric charges. And simulataneously in the foamed nickel two-electrode system， the compound shows the specific capacitance 80.00 F/g at 1 A/g current density， an energy density of 9.41 W·h/kg for a power density of 130.83 W/kg in a voltage window of 0.75 V， and an outstanding cycle stability with 92.4% capacitance retention after 5000 cycles. It is shown that the synthetic hybrid is a better candidate material for supercapacitor electrodes.



Synthesis and Electroluminescence Properties of Two Iridium（Ⅲ） Complexes with Nitrogen Heterocycle Structures

ZHOU Yonghui, HUANG Rujun, YAN Jianyang, LI Yajun, QIU Huanhuan, YANG Jinxuan, ZHENG Youxuan

2022, 43(1):  20210415.  doi:10.7503/cjcu20210415

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Two main ligands were synthesized based on 2-（3，5-bis（trifluoromethyl）phenyl）-5-fluoropyrimidine （tfmphfppm） and 2-（2，6-bis（trifluoromethyl）pyridin-4-yl）-5-fluoropyrimidine（tfmpyfppm） cores with trifluoromethyl（CF₃） units. Then， two iridium（III） complexes［（Ir（tfmphfppm）₂（pop） and Ir（tfmpyfppm）₂（pop）］ were prepared using these two main ligands and 2-（5-phenyl-1，3，4-oxadiazol-2-yl）phenol（pop） ancillary ligand. The two Ir（III） complexes show blueish-green and green emissions peaking at 484 and 504 nm with photoluminescence quantum yields（PLQYs） of 76% and 89%， respectively. Due to the nitrogen heterocycle and oxadiazol units， both Ir（III） complexes have low LUMO levels and good electron mobilities. Using the two Ir（III） complexes as emitters， the organic light-emitting diodes（OLEDs） show good performances with a maximum luminance（L_max）， a maximum current efficiency（η_c，max）， a maximum power efficiency（η_p，max） and a maximum external efficiency（EQE_max） of 33379 cd/m²， 76.55 cd/A， 31.59 lm/W and 26.7%， respectively. Furthermore， both devices show low efficiency roll-off. And at the brightness of 1000 cd/m²， the η_c can still keep at 72.71 cd/A. The research results suggest that the nitrogen heterocycle， 2，5-phenyl-1，3，4-oxadiazol and CF₃ units in the ligands can improve the luminescence property， electron mobility of the Ir（III） complexes and their corresponding device performances.



A Rare Earth Metal-Organic Framework with H₆TTAB Ligand

HAN Zongsu, YU Xiaoyong, MIN Hui, SHI Wei, CHENG Peng

2022, 43(1):  20210342.  doi:10.7503/cjcu20210342

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A rare earth metal-organic framework（MOF）， Eu-TTAB， formed by the coordination of 1,2，3-tricarboxyl-（1′,2′,3′-tricarboxylazophenyl）-benzene（H₆TTAB） and linear tetranuclear europium coordination unit， with a ｛4¹⁴·6²⁰·8¹¹｝｛4³｝₂｛4⁵·6｝ topology， was synthesized by hydrothermal method. Eu-TTAB showed excellent thermal stability and solvent stability. Flourescence property of Eu-TTAB under UV excitation was studied. Furthermore， the fluorescence of Eu-TTAB can be tuned by terbium ions as the second emission center and silver ions to enhance the luminescence intensities.



Photochromism and Photomagnetism in Two Dinuclear Lanthanide Complexes

XU Fei, LI Gangmei, HAN Songde, WANG Guoming

2022, 43(1):  20210337.  doi:10.7503/cjcu20210337

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Photomagnetic materials have many potential applications in assorted domains because of the merge of molecular electronics and molecular magnetism in one material. Hitherto， most of these materials feature photomagnetic performance at low temperature， which heavily restrict their applications. Thus， it is necessary to enlarge the working temperature for practical application. Herein， we utilized the photoinduced electron transfer（ET） strategy in the photochromic material system to quest photomagnetic materials at ambient temperature， that is， coordination-driven assembly of lanthanide nitrates and 1，10-phenanthroline（phen）. The resultant complexes， ［Ln₂（NO₃）₆（phen）₂］（Ln=Gd for 1 and Dy for 2）， featured isostructural discrete dinuclear structure with electron donor-electron acceptor characteristic. Photogenerated radicals driven by ET from the electron-donating nitrate to electron-accepting phen were produced after photoirradiation. Besides the eye-detectable photochromism， the photomagnetism was also present at room temperature. This study provides a general method to synthesize hybrid materials bearing photochromic and photomagnetic performance via hybridizing paramagnetic metal salt with phenanthroline derivatives.



Construction of a Coronal Polyoxometalate-based Composite Film for Determination of Nitrite

CHU Mingyue, LI Fengbo, GAO Ning, YANG Xin, YU Tingting, MA Huiyuan, YANG Guixin, PANG Haijun

2022, 43(1):  20210579.  doi:10.7503/cjcu20210579

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A composite film based on a coronal phosphotungstate K₂₈Li₅H₇P₈W₄₈O₁₈₄·92H₂O（P₈W₄₈）， CNTs and Ni nanoparticles（Ni NPs） was successfully constructed on the glassy carbon electrode（GCE） by using layer-by-layer self-assembly in conjunction with electrodeposition for determination of NO₂^- . The conductivity and detection signal of NO₂^- of the composite film were greatly increased due to the synergistic effect of the three active components， P₈W₄₈， CNTs and Ni NPs in composite film. Under the optimized conditions， the as-prepared sensor exhibited impressive sensing performance with a widely linear range from 1.25 μmol/L to 2500 μmol/L and a low detection limit（LOD） of 0.02 μmol/L. The good selectivity was confirmd in presence of several possible co-existing substances. The applica-bility of the method was investigated by determination of NO₂^- in fruit juice with a satisfied recovery. This composite sensor is promising for highly sensitive determination of NO₂^- in real application.



A Chemiluminescent Zirconocene Coordination Tetrahedron

DU Shunfu, WANG Wenjing, EL⁃SAYED El⁃Sayed M., SU Kongzhao, YUAN Daqiang, HONG Maochun

2022, 43(1):  20210628.  doi:10.7503/cjcu20210628

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Peroxyoxalate chemiluminescence（POCL） is widely employed in practical applications. In particular， a stable and highly efficient POCL system is a key factor in advanced emergency lights. To improve POCL efficiency， metal-organic cages（MOCs） are considered an excellent platform to employ. For this purpose， this study presents the first successful case of MOC in POCL system. A gigantic zirconocene tetrahedron（ZrT-6） was successfully synthesized， outperforming the used ligand in luminescent intensity and lifetime. This cage can also maintain good stability during the POCL test.



Synthesis， N₂ Adsorption and Mixed-matrix Membrane Performance of Bimetal Isostructural CAU-21

ZHANG Chi, SUN Fuxing, ZHU Guangshan

2022, 43(1):  20210578.  doi:10.7503/cjcu20210578

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The preparation of bimetal isostructural metal-organic frameworks（MOFs）was achieved by doping metals， and the maximum metal doping amounts of CAU-21-Al/M that can maintain the original crystal configuration were obtained from powder X-ray diffraction（PXRD）patterns. Scanning electron microscopy（SEM）was used to observed the influence of doping metals on the morphology of materials， and thermogravimetric analysis（TGA）showed that CAU-21-Al/M（M=Fe， Ga， In， Gd） all had good thermal stability. The results of nitrogen gas adsorptions and the gas permeation experiments of mixed-matrix membranes with CAU-21-Al/M as fillers are inversely related to the size of doped metal ions， verifing that dopping metal can effectively control the pore structure of MOFs.



Fabrication of Electrochemical Sensor for Dopamine and Uric Acid Based on a Novel Dimeric Phthalocyanine-involved Quintuple-decker Modified Indium Tin Oxide Electrode

WEI Chuangyu, CHEN Yanli, JIANG Jianzhuang

2022, 43(1):  20210582.  doi:10.7503/cjcu20210582

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Combination between the extending π-conjugated system in the longitudinal and transverse directions of Pc macrocycles， sandwich-type ethylthio substituted phthalocyaninato europium complex ［Pc（SC₂H₅）₈］₂Eu₂· ［BiPc（SC₂H₅）₁₂］Eu₂［Pc（SC₂H₅）₈］₂ was synthesized. The self-assembled film of the complex was prepared by means of the solution-based Quasi-Langmuir-Shafer（QLS） method. The molecular arrangement of the complex in the film was characterized by various spectroscopic methods. It was found that the molecules of the complex in the film were arranged on the substrate surface in the J-aggregation mode and edge-on configuration. The film was revealed to be a good semiconductor with conductivity as high as 8.86×10^-5 S/cm. ITO electrode modified by the QLS film of the complex was successfully applied in electrochemical detection， resulting in sensitive detection of dopamine（DA） and uric acid（UA） with the good sensitivities of 110 and 185.6 mA·μL·mol^-1·cm^-2 and low detection limits of 1.35 and 1.64 μmol/L for DA and UA， respectively.