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Construction of Naphthalenediimide Lanthanide(Ⅲ)-MOFs and Composites Incorporated Electron-Rich Pyrene Derivative as Multifunctional Fluorescence Sensing for Nitro Aromatic Compounds and Aldehydes

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Chinese Journal of Chemistry 2024年第3期42卷 283-293页

作者： Rong Huo Ting Zhang Guang Zeng Chen Wang Yong Heng Xing Feng Ying Bai College of Chemistry and Chemical Engineering Liaoning Normal UniversityDalianLiaoning116029 China State Key Laboratory of Catalysis Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianLiaoning116023 China

The development of host-guest MOF luminescent composites has attracted considerable attention. However,it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (MOF) and modulate donor-acceptor interaction. Herein,a series of isostructural 3D porous lanthanide MOF [Ln_(2)(BINDI)0.5(NO_(3))(DMA)(H_(2)O)]∙DMA∙2.5H_(2)O (Ln = La (1),Ce (2),Pr (3) and Nd (4);H_(4)BINDI (N,N’-bis(5-isophthalic acid)-1,4,5,8-naphthalenediimide) were synthesized. Considering the electron-deficient performances of Ln-BINDI MOFs,D-A type composites Ln-MOFs (1—4@H_(4)TBAPy) were prepared via the incorporation of electron-rich H_(4)TBAPy (1,3,6,8-tetrakis(p-benzoic acid) pyrene),which more improved the luminescence performance of complexes 1—4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1@H_(4)TBAPy towards pNBA,pNA PNP,DNP,and TNP could be achieved through hydrogen bond interactions between MOF and analytes,as well as the π-π interaction between H_(4)TBAPy and the naphthalene ring of BINDI,thus the fluorescence quenching efficiency of 1@H_(4)TBAPy was better than that of the complex 1. In addition,it is found that 1@H_(4)TBAPy has high selectivity and sensitivity to aromatic aldehyde SA,5-Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln-BINDI MOFs,will open up an avenue to obtain more fluorescent MOFs for sensing.

关键词： Ln-MOF Pyrene molecule NACs Aldehydes Fluorescence sensing carboxylate ligands Charge transfer Donor-acceptor systems

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Water molecules bonded to the carboxylate groups at the inorganic-organic interface of an inorganic nanocrystal coated with alkanoate ligands

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National Science Review 2022年第2期9卷 78-87页

作者： Jiongzhao Li Weicheng Cao Yufei Shu Haibing Zhang Xudong Qian Xueqian Kong Linjun Wang Xiaogang Peng Zhejiang Key Laboratory of Excited-State Materials Department of Chemistry Zhejiang University

High-quality colloidal nanocrystals are commonly synthesized in hydrocarbon solvents with alkanoates as the most common organic ligand.Water molecules with an approximately equal number of surface alkanoate ligands are identified at the inorganic-organic interface for all types of colloidal nanocrystals studied,and investigated quantitatively using CdSe nanocrystals as the model system.carboxylate ligands are coordinated to the surface metal ions and the first monolayer of water molecules is found to bond to the carboxylate groups of alkanoate ligands through hydrogen bonds.Additional monolayer(s) of water molecules can further be adsorbed through hydrogen bonds to the first monolayer of water molecules.The nearly ideal environment for hydrogen bonding at the inorganic-organic interface of alkanoate-coated nanocrystals helps to rapidly and stably enrich the interface-bonded water molecules,most of which are difficult to remove through vacuum treatment,thermal annealing and chemical drying.The water-enriched structure of the inorganic-organic interface of high-quality colloidal nanocrystals must be taken into account in order to understand the synthesis,processing and properties of these novel materials.

关键词： nanocrystals quantum dots water carboxylate ligands interface

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Structural and optical properties of pillared Eu^(3+)-containing layered double hydroxides intercalated by 2-to 12-carbon aliphatic dicarboxylates

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Journal of Rare Earths 2022年第2期40卷 260-267,I0003页

作者： Alexandre Candido Teixeira Ivan Guide Nunes Silva Alysson Ferreira Morais Danilo Mustafa Physics Institute.University of Sao Paulo 05508-090Sao PauloSPBrazil

While the versatile composition of layered double hydroxides(LDHs)allows the introduction of almost any polyvalent cation in their structure,the exchangeable negatively charged ions intercalated between the plates increase their vast range of functionalities.Here we report on the preparation and optical properties of pillared Eu^(3+)-substituted ZnAl LDHs intercalated by aliphatic dicarboxylates:-OOC-(CH_(2))_(n-2)-COO-.The basal distance in these materials is dependent on the size and packing of the intercalated anions.By varying the number(n)of carbon atoms in the aliphatic chain from 2 to 12,the interlayer gallery of these ZnAlEu LDHs is considerably expanded from 0.9 to 2.1 nm.In the interlayer gallery,the aliphatic dicarboxylates form a monolayer,with the aliphatic chain inclined by an angleα≈63°with the hydroxide layers.The carbon atom in the COO-group is 0.43 nm far from the metal plane,showing that these carboxylates are not grafted in the brucite-like layers.These LDHs are thermally stable up to around 150℃,after which dehydroxylation of the hydroxide layers is observed.The Judd-Ofelt intensity parameters were obtained and compared to the Eu^(3+)-containing complexes with the same ligand series indicating a more symmetrical and less polarizable chemical environment around the rare earth ion.

关键词： Europium Layered double hydroxides carboxylate ligands Luminescence Rare earths

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Fe-Based Metal-Organic Frameworks:From Various Synthesis,Diverse Structures to Multifunctional Applications

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Chinese Journal of Chemistry 2023年第24期41卷 3772-3791页

作者： Xiaokang Wang Mingming Xu Weidong Fan Daofeng Sun State Key Laboratory of Heavy Oil Processing School of Materials Science and EngineeringChina University of Petroleum (East China)QingdaoShandong266580 China

Iron-based metal-organic frameworks(Fe-MOFs)have attracted extensive interest from researchers due to their tunability,favorable properties,and chemical versatility.Compared with conventional porous materials,Fe-MOFs exhibit better performance in a wide variety of applications.Herein,the structures of Fe-MOFs are summarized to explore potential structures based on isoreticular chemistry,as well as the recent research progress in their synthesis and multifunctional applications.The rapid development of Fe-MOFs has broadened the application range of Fe-MOFs,and a brief description of Fe-MOF applications in gas storage and separation,catalysis,bioimaging,and magnetism is outlined,with the aim to expand the prospects of Fe-MOFs in more practical applications.

关键词： Fe-based metal-organic frameworks carboxylate ligands Gas storage Gas separation Catalysis Bioimaging Magnesium

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An undecanuclear iron (Ⅲ) oxo-hydroxo aggregate with near nanometer size:Synthesis and crystal structure of[Fe_(11)O_6(OH)_6(O_2CPh)_3(O_2CPhMe-p)_(12)]

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Chinese Journal of Chemistry 1999年第3期17卷 274-283,203页

作者：魏永革章士伟刘业麒邵美成 Department of Chemistry Peking University Beijing 100871 China

The tide compound is formed by controlled hydrolytic polymerization in nonaqueous solution of simple oxo-bridged binuclear ferric salts under the presence of carboxylate ligands. The rhombohedral crystalline form of the cluster with six imidazole molecules, which has crystallographically required C3v symmetry, will be reported. The largest Fe-Fe distance in the undecairon oxo-hydroxo cluster is about 0.68 nm and the cluster has a diameter near 2 nm, which implies that this cluster reaches a nanometer-sized dimension.

关键词： Iron-oxo cluster nanomolecule oxo/hydroxo-bridge carboxylate ligands

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