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Alkenyl-type ligands functionalized tin-lanthanide oxo nanoclusters as molecular lithography resists

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Science China Chemistry 2023年第6期66卷 1731-1736页

作者： Fang-Fang Liu Di Wang Guang-Hui Chen Yang Qiao Feng Luo Jian Zhang Lei Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Institute of Modern Optics College of Electronic Information and Optical EngineeringNankai UniversityTianjin 300350China School of Materials Science and Engineering&Smart Sensing Interdisciplinary Science Center Nankai UniversityTianjin 300350China College of Chemistry and Materials Science Fujian Normal UniversityFuzhouFujian 350007China

Both the cluster chemistry of tin and lanthanides have attracted extensive research interest,showing wide applications in catalysis,magnetism,luminescence,and ***,their fusion into heterometallic Sn-Ln oxo clusters is still to be *** this study,through the stabilization of alkenyl-type cis-5-norbornene-endo-2,3-dicarboxylic acid(H_(2)NE)ligands,a series of atomically precise Sn-Ln oxo nanoclusters have been successfully constructed from the assembly of heterometallic tetranuclear Sn_(x)Ln((4-x))building ***,Sn_(12)Eu_(8) and Sn_(13)Er_(6) with the highest nuclearities are built from multiple assembly of 8{Sn_(2)Eu_(2)}units and 6{Sn_(3)Er}and{Sn_(2)Er_(2)}units,***-MS analysis indicates that Sn_(13)Er_(6) has high solution stability,allowing their packing into thin films for lithography *** a result of electron beam lithography(EBL)studies,the condensation of Sn_(13)Er_(6) can be triggered by low energy radiation of 10μC/cm^(2),and 50 nm lines have been fabricated at expose energy of 50μC/cm^(2),confirming the satisfying sensitivity and resolution of Sn_(13)Er_(6).Hence,the success of this study develops the chemistry of heterometallic tin-lanthanide clusters that can be applied as novel negative photoresist materials.

关键词： cluster compounds tin lanthanides nanolithography photoresists

Ionothermal Synthesis and Photoactivity of Ti_(17) and Ti_(19)-Oxo clusters Functionalized by Sulfate and 1,10-Phenanthroline Ligands

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Chinese Journal of Chemistry 2023年第24期41卷 3605-3610页

作者： Kalpana Chintakrinda Nagaraju Narayanam Guang-Hui Chen Jian Zhang Lei Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian35002 China University of Chinese Academy of Sciences Beijing100049 China

In this study,we successfully synthesized two titanium-oxo clusters,namely Ti_(19)(μ_(3)-O)_(19)(μ_(2)-O)_(10)(1,10-phn)_(2)(OiPr)_(18)](PTC-178)and(EMIm)_(3)[Ti_(17)(μ_(4)-O)_(4)(μ_(3)-O)_(16)(μ_(2)-O)_(4)(SO_(4))_(3)(μ_(2)-OiPr)_(4)(OiPr)_(13)](PTC-179).These clusters were synthesized using an ionothermal reaction and possess similar nuclearity(Ti19 ***17)***,we observed that these complexes exhibit varying activities for photocatalytic degradation of Methylene Blue(MB)dye and distinct photocurrent responses for photoelectrochemical studies due to their different surface-decorated *** study provides valuable insights into the design of Ti-oxo molecular clusters with similar nuclearity but different surface environments,allowing for the establishment of critical structure-property ***,our research contributes to the exploration of sustainable synthetic methods for high nuclearity TOCs using ionic liquids.

关键词： Ionic liquids Ti-Oxo clusters(TOCs) Photocatalysis Synthesis design cluster compounds

Axially Chiral Dodecanuclear Lanthanide clusters Constructed by“Bottom-Up” Self-assembly for Enantioselective Sensing

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Chinese Journal of Chemistry 2022年第10期40卷 1165-1170页

作者： Honglei Zhao Dongxu Cui Junning Kou Haijuan Gao Guanghui Yu Chunyi Sun Xinlong Wang Zhongmin Su Key Laboratory of Polyoxometalate Science of Ministry of Education Northeast Normal UniversityChangchunJilin 130024China

Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axial chiral lanthanide metal *** the structure,rare four-pointed star coordination mode of oxalic acid is reported by this *** addition,as a fluorescence sensor,the complex 2 exhibits high enantioselectivity for R-/S-BINOL-TF_(2)(EF=2.87)and other chiral binaphthyl derivatives.

关键词： Axial chirality cluster compounds Molecular recognition Self-assembly Host-guest systems

Design and Synthesis of Al_(7)Ni_(2) Heterometallic clusters Based on Metal Substitution and Ligands Protection Strategies

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Chinese Journal of Chemistry 2023年第5期41卷 521-526页

作者： Ya-Jie Liu Li-Min Cui Wei-Hui Fang Jian Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002China University of Chinese Academy of Sciences Beijing 100049China

The synthesis of heterometallic aluminum-based materials is challenging yet attractive,due to their potential applications in optics,catalysis,magnetism and semiconductor *** have now successfully synthesized two Al,Niz heterometallic clusters bearing different peripheral alkoxide ligands through a heterometal substitution strategy.

关键词： cluster compounds Heterometallic complexes Crystal engineering Catalytic properties Aluminum oxo cluster Aluminum

Orientational Isomerism and Its Reactivity of a Main Group Sandwich Anion[Ge_(9)-In-Ge_(9)]^(5-)

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Chinese Journal of Chemistry 2023年第19期41卷 2432-2438页

作者： Hong-Lei Xu Lei Qiao Zhong Ming Sun State Key Laboratory of Elemento-Organic Chemistry Tianjin Key Lab of Rare Earth Materials and ApplicationsSchool of Material Science and EngineeringNankai UniversityTianjin 300350China

Two isomers of a sandwich-type anion [Ge_(9)-In-Ge_(9)]^(5–) were synthesized by controlling the chelating agents (2,2,2-crypt/18-C-6). Further reactions with early/late transition metal complexes, Mo(CO)_(6) and Ni(COD)_(2), respectively, yielded two new types of inorganic sandwich derivatives: a half-sandwich cluster [Ge_(9)-In-Mo(CO)_(5)]^(3–) with a low-valence In(I) center and an unsymmetrical sandwich-type cluster {[(Ni@Ge_(9))In(Ni_(0.648)@Ge_(9))]}^(5–) due to the insertion of Ni atoms, respectively. The isolation of these new derivatives demonstrates the reactivity of sandwich-type [Ge_(9)-In-Ge_(9)]^(5–) acting as the precursor, which provides some enlightenment for constructing new inorganic sandwich compounds.

关键词： Sandwich complex cluster compounds Main group elements Germanium Indium

Synthesis,Structure and Magnetic Behavior of a Novel Series of Trinuclear Windwheel Complexes

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Chinese Journal of Chemistry 2023年第24期41卷 3662-3668页

作者： Rong Luo Chen-Ze Xie Ming-Guang Chen Hai-Yan Shi Xiang-Jian Kong Yu-Hua Fan Feng Shao Key Laboratory of Marine Chemistry Theory and Technology Ministry of EducationCollege of Chemistry and Chemical EngineeringOcean University of ChinaQingdaoShandong266100 China Baotou Research Institute of Rare Earths BaotouInner Mongolia014040 China State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical EngineeringXiamen UniversityXiamenFujian361005 China

A new family of trinuclear windwheel complexes with molecular formula [M^(II)_(3)(tpa)_(3)(μ-ttc)](ClO_(4))_(3)·n(sol) (ttc = 1,3,5-triazine-2,4,6-trithiol;tpa = tris(2-pyridylmethyl)amine;M = Mn,n = 2,sol = CH_(3)CN,1;M = Co,n = 1,sol = CH_(3)CN,2;M = Ni,n = 0,3) were synthesized and ***-crystal X-ray diffraction revealed that three metal centers in 1—3 are connected by ttc bridge,forming a regular triangular MII3 *** metal center is bonded by chelating S,N atoms from ttc and by N atoms from *** studies showed that 1—3 displayed antiferromagnetic behavior and further gave the easy-axis anisotropy (D = −0.77 cm^(−1) for 1 and −8.13 cm^(−1) for 2) and easy-plane anisotropy (D = 5.08 cm^(−1) for 3).Moreover,2 exhibited field-induced slow magnetic relaxation behavior and their effective energy barriers were roughly evaluated Ueff = 6.9 K.

关键词： cluster compounds Crystal growth Magnetic properties Slow magnetic relaxation Magnetic anisotropy

Structural Isomerization in Cu(I)clusters:Tracing the Cu Thermal Migration Paths and Unveiling the Structure-Dependent Photoluminescence

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CCS Chemistry 2023年第2期5卷 350-360页

作者： Xi Fan Furong Yuan Jiaqi Wang Zhibin Cheng Shengchang Xiang Huayan Yang Zhangjing Zhang Fujian Provincial Key Laboratory of Polymer Materials College of Chemistry and Materials ScienceFujian Normal UniversityFuzhouFujian 350007 State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002 Health Science Center School of Biomedical Engineering Shenzhen UniversityShenzhen 518000

Revealing structural isomerization in metal clusters would bridge a huge structural gap between small molecular isomerization and solid–solid phase ***,genuine structural isomerism in metal clusters is still *** this work,we report the first example of structural isomerismin Cu *** utilizing the coordination flexibility of alkyne to enable the migration of partial Cu atoms in Cu metal cores,two Cu_(15)cluster complexes(Cu_(15)-a and Cu_(15)-c)possessing identical composition but different metal core structures have been successfully ***,although the structure of Cu_(15)-a can be retained in CH_(2)C_(l2)solution below 27°C,it will gradually change to give an intermediate state,Cu_(15)-b,as the temperature rises(at about 31°C)before it eventually transforms into Cu_(15)-c(at 40∼65°C).Significantly,atomically precise Cu_(15)-b clearly provides footprints for tracing the thermal migration process of Cu atoms during the thermal transformation from Cu_(15)-a to Cu_(15)-*** addition,Cu_(15)-a and Cu_(15)-c exhibit diverse crystallization-induced emission enhancement *** Cu_(15)-c displays redshifted photoluminescence(820 nm)compared with Cu_(15)-a(726 nm)due to the shorter mean Cu···Cu distance in Cu_(15)-***,crystalline Cu_(15)-a exhibits much more intense photoluminescence at room temperature than that in Cu_(15)-c,which might be attributed to the stronger intermolecular C–H⋯πinteractions in Cu_(15)-*** results indicate that cluster isomerism provides valuable opportunities for insight into the structure–property relationships and understanding the complex evolution of phase transformation in nanometallic solids.

关键词： cluster compounds metal clusters structural isomerism isomeric transformation structure–property relationships

Mesoporous Crystalline Silver-Chalcogenolate cluster-Assembled Material with Tailored Photoluminescence Properties

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CCS Chemistry 2019年第5期1卷 553-560页

作者： Xiao-Hui Wu Zhong Wei Bing-Jie Yan Ren-Wu Huang Yuan-Yuan Liu Kai Li Shuang-Quan Zang Thomas C.W.Mak College of Chemistry and Molecular Engineering Zhengzhou UniversityHenan 450001China Department of Chemistry and Center of Novel Functional Molecules The Chinese University of Hong KongSha TinNew Territories Hong Kong SARChina

Crystalline cluster-assembled materials(CAMs)are emerging as types of exploratory fabrications due to their atomically precise structures and intriguing chemical/physical properties,as well as their lumines-cent funct... 详细信息

关键词： cluster compounds aggregation-induced emission host-guest chemistry circularly pola-rized luminescence white-light-emitting room-temperature phosphorescence

Unraveling the condensation reactions of heterometallic {BiNb_(4)} moieties into hybrid Bi_(x)Nb_(y)-oxo clusters with mass spectrometry

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Science China Chemistry 2021年第3期64卷 413-418页

作者： Lv-Bing Yuan Ya-Yong Sun Jian Zhang Lei Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China University of Chinese Academy of Sciences Beijing 100049China

The most effective methodologies for the construction of polynuclear complexes usually take advantage of preorganized building ***,we successfully developed a new versatile heterometallic{BiNb_(4)}moiety,which can be applied for the assembly of less explored organic-inorganic hybrid *** controlled condensation reactions,three{BiNb_(4)}moieties can be assembled into a pair of isomeric Bi_(3)Nb_(18)clusters at different temperatures;whilst four{BiNb_(4)}moieties can be combined into two unique Bi_(4)Nb_(16)and Bi_(4)Nb_(18)tetramers in different ***,we have used mass spectrometry to probe the above condensation reactions,which clearly confirmed a stepwise bottom-up assembly process by capturing the presence of bismuth subsalicylate precursors,salicylate coordinated intermediates,Nb incorporated{BiNb_(4)}moieties and the final Bi_(x)Nb_(y)-oxo clusters,***,the packing modes of the{BiNb_(4)}units induce different solution behaviors,and the{BiNb_(4)}units in Bi4Nb16can be recombined by post-synthetic recrystallization in acetonitrile to produce a new tetramer Bi_(4)Nb_(18)-***,this work provides not only a useful{BiNb_(4)}building unit but also the mechanism for their condensation,both of which will promote the future development of metal-oxo clusters.

关键词： cluster compounds mass spectrometry heterometallic complexes condensation reactions