3-羧基-1,2,4-三氮唑MnⅡ配合物的合成、结构及荧光性质

doi:10.11944/j.issn.1000-0518.2017.03.160210

摘要/Abstract

摘要：

为了探讨3-羧基-1,2,4-三氮唑(MTC)配合物的性质。本文采用水热法合成了一个结构新颖的配合物[Mn(C₃H₂N₃O₂)₂(H₂O)₂]。通过红外光谱(IR)、元素分析、热重分析(TGA)和粉末X射线衍射(PXRD)等技术手段表征了配合物的结构和性能。 X射线单晶衍射分析表明,配合物为一单核结构,属于单斜晶系P21/c空间群.Mn^Ⅱ离子采取六配位,每个Mn离子位于反演中心,分别与两个MTC配体中的1个O和1个N原子螯合配位, 同时还与2个水分子配位,形成一个稍微变形八面体构型结构。同时, 在配合物中存在着丰富的氢键和弱的 π-π作用力,通过分子间氢键和弱π-π相互作用形成一个三维网络结构。固体荧光研究表明,配合物的发射峰为517 nm,较配体发生7 nm蓝移。该研究对新型金属有机配合物荧光材料的开发具有一定的指导和借鉴意义。

关键词: 水热法, 羧基三氮唑, 荧光性质

Abstract:

In order to investigate the properties of 3-carboxyl-1,2,4-triazole complexes, a novel complex, [Mn(C₃H₂N₃O₂)₂(H₂O)₂], was synthesized by the hydrothermal method. The properties of the complex were characterized by Fourier transform infrared spectroscopy(IR), element analysis, thermal gravimetric anlysis(TGA) and powder X-ray diffraction(PXRD). The single crystal X-ray analysis reveals that the complex is a unique single-core structure and belongs to the monoclinic crystal system in space group P21/c. The coordination number of Mn^Ⅱ is six. The Mn^Ⅱ atom is located on an inversion centre. Each Mn^Ⅱ atom is coordinated by two O atoms and two N atoms from two 3-carboxyl-1,2,4-triazole anions and two coordinated water molecules to form a slightly distorted octahedral geometry. The discrete molecules of the complex are furthermore linked, resulting in a three-dimensional network structure through extensive intermolecular hydrogen bonds and π-π interactions. Solid fluorescence of the complex shows an emission peak at 517 nm. Compared with the ligand, there is a 7 nm blue shift. The research provides a reference for exploiting new metal-organic complex fluorescent materials.

Key words: hydrothermal method, carboxyl-triazole, fluorescence properties

谭育慧, 古志峰, 刘艺, 杨昌善, 王宾, 唐云志. 3-羧基-1,2,4-三氮唑Mn^Ⅱ配合物的合成、结构及荧光性质[J]. 应用化学, 2017, 34(3): 354-360.

TAN Yuhui, GU Zhifeng, LIU Yi, YANG Changshan, WANG Bin, TANG Yunzhi. Synthesis, Structure and Fluorescence Properties of Manganese(Ⅱ) Complex Based on 3-Carboxyl-1,2,4-triazole[J]. Chinese Journal of Applied Chemistry, 2017, 34(3): 354-360.

参考文献

[1]	Davidovich R L,Stavila V,Whitmire K H. Stereochemistry of Lead(Ⅱ) Complexes Containing Sulfur and Selenium Donor Atom Ligands[J]. Coord Chem Rev,2010,254(17):2193-2226.
[2]	Kole G K,Cairns A J,Eddaoudi M,et al.Solvent-free Porous Framework Resulted from 3D Entanglement of 1D Zigzag Coordination Polymer[J]. New J Chem,2010,34(11):2392-2395.
[3]	Kole G K,Koh L L,Lee S Y,et al.A New Ligand for Metal-organic Framework and Co-crystal Synthesis:Mechanochemical Route to rctt-1,2,3,4-Tetrakis-(4'-carboxyphenyl)-cyclobutane[J]. Chem Commun,2010,46(21):3660-3662.
[4]	Singh S,Roesky H W. Robust and Efficient Molecular Catalysts with a M-O-M' Framework[J]. Dalton Trans,2007,(14):1360-1370.
[5]	Lan A,Li K,Wu H,et al.A Luminescent Microporous Metal-organic Framework for the Fast and Reversible Detection of High Explosives[J]. Angew Chem Int Ed,2009,48(13):2334-2338.
[6]	XU Qing,GAO Jixing,GU Zhifeng,et al.Syntheses, Structures and Fluorescence Properties of ZnII Complex with 2-(2-Pyridyl)-4-hydroxy Quinazoline[J]. Nonferrous Met Sci Eng,2015,6(6):144-148(in Chinese). 徐庆,高继兴,古志峰,等. 2-(2-吡啶基)-4-羟基喹唑啉锌配合物的合成、结构及荧光性质[J]. 有色金属科学与工程,2015,6(6):144-148.
[7]	GAO Jixing,GU Zhifeng,YANG Changshan,et al.Synthesis, Structures and Properties of FeⅡ,CoⅡ-Imidazolyl Tetrazole Compounds Through in Situ [2+3] Synthesis[J]. Nonferrous Met Sci Eng,2015,6(5):73-79(in Chinese). 高继兴,古志峰,杨昌善,等. 咪唑基四唑FeⅡ、CoⅡ配合物的[2+3]原位合成、结构及性质研究[J]. 有色金属科学与工程,2015,6(5):73-79.
[8]	TANG Yunzhi,WANG Yan,TAN Yuhui,et al.Syntheses, Structures and Properties of CuⅡ Complex with 2,2'-Bipyridine-5,5'-dicarboxylic Acid[J]. Nonferrous Met Sci Eng,2013,4(4):18-21(in Chinese). 唐云志,王艳,谭育慧,等. 2,2'-联吡啶-5,5'-二羧酸CuⅡ配合物的构筑、结构及性质研究[J]. 有色金属科学与工程,2013,4(4):18-21.
[9]	Safarifard V,Morsali A. Solid State Syntheses of Nano Lead(Ⅱ) Iodide Triazole Carboxylate Coordination Polymer from Its Bromide/Thiocyanate/Chloride Analogs via Mechanochemical Cystal to Crystal Transformations[J]. Inorg Chim Acta,2013,405(24):203-208.
[10]	Safarifard V,Morsali A. Reversible Crystal-to-Crystal Transformation of a 3D-3D Coordination Polymer by Solid State Anion-replacement with no Change in Nano-particle Morphology[J]. Cryst Eng Comm,2011,13(15):4817-4819.
[11]	Liu Y Y. Synthesis,Structure and Characterization of Copper(Ⅱ) and Zinc(Ⅱ) Complexes Based on 3-Carboxyl-1,2,4-triazole[J]. J Coord Chem,2007,60(23):2597-2605.
[12]	Ding B,Liu Y Y,Zhao X J,et al.Hydrothermal Synthesis and Characterization of a Novel Luminescent Lead(Ⅱ) Framework Extended by Novel Pb-μ1,1-(N)CS-Pb Bridge[J]. J Mol Struct,2009,920(1):248-251.
[13]	Ding B,Yang E C,Guo J H,et al.A Novel 2D Luminescent Lead(Ⅱ) Framework with 3-Carboxylicacid-4H-1,2,4-triazole Based on Binuclear Pb2Cl2(H2O)2 Building Blocks[J]. Inorg Chem Commun,2008,11(12):1481-1483.
[14]	Sheldrick G M. SHELXS-97,Programs Zur Losung Von Kristallstrukturen[M]. Gottingen:University of Grttingen,1997:509-771.
[15]	Sheldrick G M. SHELXS-97,Program for X-ray Crystal Structure Refinement[M]. Grttingen:University of Grttingen,1997:208-311.
[16]	LI Hongjin,GAO Zhuqing,GU Jinzhong. Znic and Cadmium Coordination Compounds Constructed from 5-Halonicotinic Acid: Synthesis, Crystal Structures, and Luminescent Properties[J]. Chinese J Inorg Chem,2014,30(11):2615-2620(in Chinese). 李红晋,高竹青,顾金忠. 基于5-氯烟酸的锌(Ⅱ)和镉(Ⅱ)配合物的合成、晶体结构及荧光性质[J]. 无机化学学报,2014,30(11):2615-2620.
[17]	MA Kuirong,ZHANG Yu,KAN Yuhe,et al.Syntheses, Structures and Fluorescent Properties of Three Low-dimensional ZnⅡ-Diphosphonate Coordination Polymers[J]. Chinese J Inorg Chem,2014,30(11):2549-2558(in Chinese). 马奎蓉,张宇,阚玉和,等. 三个低维Zn(Ⅱ)-二膦酸配位聚合物的合成、结构及荧光性能研究[J]. 无机化学学报,2014,30(11):2549-2558.
[18]	TAN Yuhui,XIONG Jianbo,HUANG Jun,et al.A Family of Tetrazole Compounds Formed Through in Situ [2+3] Tetrazole Ligand Synthesis, Structures and Fluorescent Properties[J]. Chinese J Inorg Chem,2014,30(7):1621-1628(in Chinese). 谭育慧,熊剑波,黄珺,等. 原位[2+3]环合成法制备四唑化合物、结构及荧光性质[J]. 无机化学学报,2014,30(7):1621-1628.
[19]	Tang Y Z,Zhou M,Huang J,et al.In Situ Synthesis and Ferroelectric, SHG Response, and Luminescent Properties of a Novel 3D Acentric Zinc Coordination Polymer[J]. Inorg Chem,2013,52(4):1679-1681.
[20]	Gao J X,Xiong J B,Xu Q,et al.Supramolecular Interactions Induced Chirality Transmission, Second Harmonic Generation Responses, and Photoluminescent Property of a Pair of Enantiomers from in Situ [2+3] Cycloaddition Synthesis[J]. Cryst Growth Des,2016,16(3):1559-1564.

3-羧基-1,2,4-三氮唑Mn^Ⅱ配合物的合成、结构及荧光性质

Synthesis, Structure and Fluorescence Properties of Manganese(Ⅱ) Complex Based on 3-Carboxyl-1,2,4-triazole

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