Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof
阅读说明：本技术 多孔互穿的锌-有机超分子聚合物及其制备方法与应用 (Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof ) 是由 黄坤林 郭媛媛 陈新 张如意 夏刚 吴越 于 2019-09-06 设计创作，主要内容包括：本发明提供了一种多孔互穿的锌-有机超分子聚合物,其通式为[Zn<Sub>2</Sub>(H<Sub>2</Sub>pbod)<Sub>2</Sub>(bpeb)<Sub>2</Sub>]<Sub>n</Sub>,属于单斜晶系,空间群为P2/c,晶胞参数<Image he="78" wi="380" file="DDA0002193420470000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="47" wi="700" file="DDA0002193420470000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,H<Sub>2</Sub>pbod<Sup>2-</Sup>是半刚性的四元有机羧酸H<Sub>4</Sub>pbod脱去2个质子所得,所述H<Sub>4</Sub>pbod结构如式Ⅰ；共轭联吡啶bpeb结构如式Ⅱ：<Image he="149" wi="700" file="DDA0002193420470000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>采用本发明提供的方法制备的锌-有机超分子聚合物产率可达55％,同时,在甲基丙烯酸甲酯聚合的过程掺杂该有机超分子聚合物,得到了365nm紫外光照射下发射青色(或蓝绿色)荧光的有机玻璃复合材料；该锌-有机超分子聚合物溶液还可作为阴阳离子和溶剂小分子的荧光检测。(The invention provides a porous interpenetrating zinc-organic supramolecular polymer, which has a general formula of [ Zn 2 (H 2 pbod) 2 (bpeb) 2 ] n , belongs to a monoclinic system, has a space group of P2/c, and has unit cell parameters of , wherein H 2 pbod 2- is obtained by removing 2 protons from semi-rigid quaternary organic carboxylic acid H 4 pbod, the structure of H 4 pbod is shown as formula I, the structure of conjugated bipyridine bpeb is shown as formula II, the yield of the zinc-organic supramolecular polymer prepared by the method provided by the invention can reach 55%, and meanwhile, the organic supramolecular polymer is doped in the process of methyl methacrylate polymerization, so that an organic glass composite material emitting cyan (or blue-green) fluorescence under 365nm ultraviolet irradiation is obtained, and the zinc-organic supramolecular polymer solution can also be used for fluorescence detection of anions and solvent micromolecules.)
1.A porous interpenetrating zinc-organic supermolecular polymer with general formula [ Zn ]2(H2pbod)2(bpeb)2]nBelonging to the monoclinic system, space group is P2/c, cell parameter Wherein H2pbod2-Being semi-rigid quaternary organic carboxylic acids H4pbod by stripping off 2 protons, said H4pbod is represented by formula I; the structure of the conjugated bipyridine bpeb is as shown in formula II:
2. The porous interpenetrating zinc-organic supramolecular polymer of claim 1, comprising 2 Zn in crystallographically independent asymmetric structures2+2 of H2pbod2-And 2 coordinated bpeb; 2 of H2pbod2-The coordination mode is shown as formula III, the coordination mode of 2 bpeb is shown as formula IV, and 2 Zn2+Respectively forming tetrahedrons with different O and N atoms of the organic component in coordination, wherein the tetrahedrons are as shown in formulas V and VI; wherein, different atom numbers are used for distinguishing:
3. A process for the preparation of a porous interpenetrating zinc-organic supramolecular polymer according to claim 1 or 2, wherein said porous interpenetrating zinc-organic supramolecular polymer is present as H4pbod, bpeb, zinc salt and HNO3As a raw material, the zinc salt is Zn (NO)3)2·6H2O or ZnSO4·7H2O, with BThe mixed solution of nitrile and water is used as a solvent, and is prepared by a solvothermal synthesis method, which comprises the following steps:
(1) Feeding a raw material H4pbod, bpeb, zinc salt and HNO3Mixing acetonitrile and water as solvents to form a reaction system, and placing the reaction system in a closed container; said H4pbod: bpeb: zinc salt: HNO3The mass ratio of (1): 1: 1-2: 8.4-14, wherein the volume ratio of acetonitrile to water is 3: 7;
(2) Placing the reaction system at room temperature, stirring for 0.5-1.0 h, heating to 120-140 ℃, reacting for 2-4 d, naturally cooling, filtering and drying to obtain blocky crystals, namely [ Zn ]2(H2pbod)2(bpeb)2]n。
4. The method of preparing a porous interpenetrating zinc-organic supramolecular polymer according to claim 3, wherein H is in step (1)4pbod: bpeb: zinc salt: HNO3The mass ratio of (1): 1: 2: 8.4.
5. The method of claim 3, wherein H is in the reaction system4the starting material was at a concentration of pbod or bpeb of 2.5 mmol/L.
6. The method of preparing a porous interpenetrating zinc-organic supramolecular polymer according to claim 3, wherein in step (2) the reaction temperature is 130 ℃ and the reaction time is 3 days; the drying means that the crystal is naturally dried in the air after being washed with distilled water.
7. The application of the porous interpenetrating zinc-organic supramolecular polymer is characterized in that the porous interpenetrating zinc-organic supramolecular polymer prepared by the method of any one of claims 3 to 6 is applied to the preparation of photosensitive composite materials and the optical detection of anions, cations and solvent micromolecules.
Technical Field
The invention belongs to the field of advanced functional materials, and particularly relates to a porous interpenetrating zinc-organic supramolecular polymer, and a preparation method and application thereof.
Background
Ipns (interpenetrating polymer networks), i.e., interpenetrating polymer networks, are two or more polymer networks that are interpenetrating and form a complex network, and materials with interpenetrating structures often have physical properties such as better toughness, mechanical strength, thermal stability, etc. The chemical reaction cross-linking interpenetrating technology has been widely used for improving high polymer materials such as natural rubber, fiber and the like, and the interpenetrating polymer network is prepared by in-situ self-assembly, which is of great interest in the field of new materials.
In recent decades, fluorescent metal-organic supramolecular polymers constructed by organic ligands and metal ions through the supramolecular action such as coordination bonds have become one of the fastest leading directions in the field of luminescent materials due to the advantages of wide raw material sources, accurate, novel and various structures, high purity of crystal samples, mild preparation conditions and the like. Generally, metal-organic supramolecular polymers are mainly prepared by in-situ self-assembly through technologies such as interfacial diffusion, solvent volatilization, hydrothermal or solvothermal technology, and due to the influence of many factors such as temperature, raw material structure, solvent system, pH value and the like, optimizing conditions and obtaining a desired new photopolymer is a very challenging problem. Meanwhile, the kind of metal ions, the structure of organic ligands, the periodic spatial arrangement, etc. are all key factors for controlling performance.
In addition, environmental pollution control is a significant problem in the current human development, and heavy metal ions such as lead, chromium, iron and the like in some industrial wastewater can cause great harm to organisms. Therefore, the novel luminescent material is developed for rapidly detecting certain inorganic ions and organic small molecules, and has positive significance in the fields of environmental monitoring, biomedicine, chemistry and chemical engineering and the like.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a porous interpenetrating zinc-organic supramolecular polymer having the general formula [ Zn ]2(H2pbod)2(bpeb)2]nThe new substance can be used for preparing photosensitive composite materials and detecting the fluorescence of small molecules of ions and solvents.
In order to achieve the purpose, the invention provides the following technical scheme: a porous interpenetrating zinc-organic supermolecular polymer with general formula [ Zn ]2(H2pbod)2(bpeb)2]nBelonging to the monoclinic system, space group is P2/c, cell parameterWherein H2pbod2-Being semi-rigid quaternary organic carboxylic acids H4pbod by stripping off 2 protons, said H4pbod is represented by formula I; the structure of the conjugated bipyridine bpeb is as shown in formula II:
Further, the porous interpenetrating zinc-organic supramolecular polymer comprises 2 Zn in crystallographically independent asymmetric structures2+2 of H2pbod2-And 2 coordinated bpeb; 2 of H2pbod2-The coordination mode is as shown in formula III, 2 bpebThe coordination mode is as in formula IV, 2 Zn2+respectively coordinate with different O and N atoms of the organic component to form tetrahedrons as shown in formulas V and VI, wherein the tetrahedrons are distinguished by different atom numbers:
The porous interpenetrating zinc-organic supramolecular polymer is prepared by the following steps: with H4pbod, bpeb, zinc salt and HNO3As a raw material, the zinc salt is Zn (NO)3)2·6H2O or ZnSO4·7H2The O is prepared by taking a mixed solution of acetonitrile and water as a solvent and adopting a solvothermal synthesis method, and specifically comprises the following steps:
(1) Feeding a raw material H4pbod, bpeb, zinc salt and HNO3Mixing acetonitrile and water as solvents to form a reaction system, and placing the reaction system in a closed container; said H4pbod: bpeb: zinc salt: HNO3The mass ratio of (1): 1: 1-2: 8.4-14, wherein the volume ratio of acetonitrile to water is 3: 7;
(2) placing the reaction system at room temperature, stirring for 0.5-1.0 h, heating to 120-140 ℃, reacting for 2-4 d, naturally cooling, filtering and drying to obtain blocky crystals, namely [ Zn ]2(H2pbod)2(bpeb)2]n。
Further, said H in step (1)4pbod: bpeb: zinc salt: HNO3The mass ratio of (1): 1: 2: 8.4.
Further, H in the reaction system4The starting material was at a concentration of pbod or bpeb of 2.5 mmol/L.
Further, the reaction temperature in the step (2) is 130 ℃, and the reaction time is 3 days; the drying means that the crystal is naturally dried in the air after being washed with distilled water.
The porous interpenetrating zinc-organic supramolecular polymer prepared by the preparation method is used for preparing photosensitive composite materials and is applied to the optical detection of anions and cations and solvent micromolecules.
Compared with the prior art, the invention has the following beneficial effects:
(1) The zinc-organic supermolecular polymer provided by the invention shows Zn in the space structure according to single crystal diffraction2+Metal ion and organic bridging component H2pbod2-And bpeb form a coordination polymerization network with two different nano tunnels, the coordination polymerization network forms a porous three-dimensional supramolecular structure through dual interpenetrating, and the Platon calculated porosity is 28.4%; the interpenetrating of the network reduces the porosity to a certain degree, but is beneficial to the stability of the whole structure; the zinc-organic supermolecule polymer skeleton starts to decompose at about 340 ℃, has higher thermal stability, and stably exists in water, acetonitrile or DMF, DMA and other common solvents; and at room temperature, the crystal material is excited by ultraviolet ray 438nm and emits green fluorescence at 515 nm.
(2) The zinc-organic supramolecular polymer prepared by the method provided by the invention has the yield of 55%, and meanwhile, the organic supramolecular polymer is doped in the polymerization process of methyl methacrylate, so that the organic glass composite material emitting cyan (or blue-green) fluorescence under 365nm ultraviolet irradiation is obtained; the zinc-organic supermolecule polymer solution can also be used for fluorescence detection of anions and cations and solvent micromolecules.
Drawings
FIG. 1 is [ Zn ]2(H2pbod)2(bpeb)2]ncoordination and spatial crystal structure of (a): (a) coordination modes of ligands and metal ions, (b) 4-linked three-dimensional zinc-organic coordination polymeric structures containing two types of nano-tunnels, (c) doubly interpenetrating zinc-organic supramolecular networks (ZnOF);
FIG. 2 is a graph showing X-ray powder diffraction patterns of the zinc-organic supramolecular polymer according to the present invention;
FIG. 3 is a thermogravimetric plot of a zinc-organic supramolecular polymer in accordance with the present invention;
FIG. 4 is an infrared spectrum of a zinc-organic supramolecular polymer of the present invention;
FIG. 5 is a normal temperature solid state fluorescence spectrum of the zinc-organic supramolecular polymer of the invention;
FIG. 6 is a photograph of fluorescent organic glass doped with zinc-organic supramolecular polymer in natural light and 365nm ultraviolet light;
FIG. 7 is a graph showing fluorescence emission spectra of zinc-organic supramolecular polymers of the present invention in several common solvents;
FIG. 8 is a graph showing the emission spectrum of the aqueous solution of zinc-organic supramolecular polymer in accordance with the present invention for the fluorescence detection of anions;
FIG. 9 is the emission spectrum of the zinc-organic supramolecular polymer aqueous solution of the invention for cationic fluorescence detection.
Detailed Description
the process of the present invention will be described in detail with reference to specific examples. The invention provides a zinc-organic supramolecular polymer [ Zn ]2(H2pbod)2(bpeb)2]nThe method can be abbreviated as ZnOF, and the final product is subjected to X-ray single crystal diffraction test and analyzed to obtain an accurate electronic structure; and performing a series of characterizations such as infrared, fluorescence, X-ray powder diffraction, thermogravimetry and the like on the final product to determine that the chemical general formula is [ Zn ]2(H2pbod)2(bpeb)2]n. With O-ligand H4The yield was calculated on the basis of pbod amount, i.e. on the basis of product [ Zn ]2(H2pbod)2(bpeb)2]And n, calculating the mass of the zinc-organic supermolecular polymer which is theoretically obtained, wherein the ratio of the actually obtained product mass to the former is the yield. In the invention H4pbod is the abbreviation for the O-ligand 5,5'- (1,4-phenylenebis (oxy)) diisopthalic acid, English name, bpeb is the N-ligand 1,4' -bis [2- (4-pyridol) ethyl]Abbreviation for benzene english name.
firstly, the preparation of the zinc-organic supermolecular polymer of the invention
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