CN105884804A

CN105884804A - Synthesis method of terephthalic acid containing cadmium coordination polymer

Info

Publication number: CN105884804A
Application number: CN201610267619.8A
Authority: CN
Inventors: 汪永涛; 詹世杰; 李树平; 汤桂梅; 万文珠
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2016-04-27
Filing date: 2016-04-27
Publication date: 2016-08-24

Abstract

The invention discloses a terephthalic acid containing metal cadmium coordination polymer and a synthesis method thereof. A crystal structure of the polymer is determined by single crystal X-rays. A chemical formula of the polymer is C32H24CdN6O5, the structure is a triclinic crystal system, crystal cell parameters of a P-1 space group are as follows: a = 10.6844(12) angstroms, b = 10.9086(12) angstroms, c = 13.3974(16) angstroms, alpha = 74.525(2) DEG, beta = 76.719(2) DEG, gamma = 65.261(2) DEG, and V = 1394.3(3) angstroms<3>. The invention provides a method of a nitronic acid containing metal coordination polymer. The method comprises the following steps that terephthalic acid, cadmium salt and a functional ligand are put in a reaction kettle in proportion under the solvent heating condition, and the novel metal coordination polymer is obtained after heating, cooling and filtration are performed. The method is simple and easy to operate.

Description

A kind of synthetic method containing p-phthalic acid cadmium coordination polymer

Technical field

The invention belongs to inorganic chemistry, organic chemistry and the field of chemical synthesis, relate to the metal of nitrogen heterocyclic ring and carboxylic acid The preparation method of coordination polymer, belongs to field of functional materials.

Background technology

Metal coordinating polymer is a class independently filled by metal center ion and organic ligand and having of being formed is wide should With the novel solid functional material of prospect.This material has the structure of novelty and unique character, such as, inhale at catalysis, gas Receive or the aspect such as storage, fluorescence, sensing and medicament transport suffer from potential using value (S. Rojas, et al, CrystEngComm 2013, 15 , 9364).For the synthesis of metal coordinating polymer, conventional method has conventional soln anti- Ying Fa, hydro-thermal method and solvent-thermal method etc., therefore, it is possible to select simple effective method to synthesize have special construction and character Metal coordinating polymer is the most still being faced with the biggest challenge.

Take (2-(4 '-pyridine radicals) benzimidazole) to participate in synthesis as functional ligand, be because (2-(4 '-pyridine Base) benzimidazole) it is that one has extraordinary function ligand, have an advantage in that (1) has three aromatic rings (phenyl ring, pyridines Ring, imidazole ring), easily form conjugated system, can beneficially strengthen the stability of total；(2) molecule exists three Nitrogen-atoms, one is easily coordinated with cadmium ion, and other nitrogen-atoms easily forms hydrogen bond, can extend further expand to 2d, 3d structure.(Y. Yang, M. H. Zeng, L. J. Zhang, H. Liang. J. Coord. Chem., 2009, 62, 886)。

Therefore (2-(4 '-pyridine radicals) benzimidazole) and p-phthalic acid and metal ion synthesis metal-complexing is used to gather Compound, the metal coordinating polymer having synthesized a kind of new function easy, easy-operating.

Summary of the invention

The present invention provides the synthetic method of a kind of nitrogen heterocyclic ring carboxylic acids coordination polymer, combine containing N heterocyclic ligand and Advantage containing O Carboxylic acid ligand.This kind of part has donor atom N and O of difference in functionality due to it, so having abundanter Coordination mode and stronger coordination ability, the conjugated structure simultaneously produced is that the photoluminescent property of coordination polymer provides bar Part, invention achieves simplification laboratory operating procedures, reaches the purpose of one-step synthesis.

To achieve these goals, p-phthalic acid, alkali, cadmium salt and 2-(4 '-pyridine radicals) benzimidazoles are dissolved in water and In the mixed solution of organic solvent.Then transfer the solution in reactor after being heated to uniform temperature reaction certain time, often Hour fall 5 degree to room temperature, filters precipitation and obtains the coordination polymer 1 of yellow crystals.By the product 1 of gained through monocrystalline X-ray Diffraction analysis determines its molecular structure, sees Fig. 1.

Accompanying drawing explanation

Fig. 1, the molecular structure of coordination polymer 1.

Fig. 2, the one-dimensional chain figure of coordination polymer 1.

Fig. 3, the two-dimensional layer figure of coordination polymer 1.

Fig. 4, the accumulation graph of coordination polymer 1.

Fig. 5, the fluorogram of coordination polymer 1.

Detailed description of the invention

Fig. 1 is to be obtained coordination polymer 1 structure by single crystal diffraction method.The X ray diffraction data of this coordination polymer It is to visit on diffractometer in Bruker smart Apex CCD face, radiates (λ=0.71073) with MoK α, scan with w Lp factor correction is collected and carried out to mode, and absorption correction uses SADABS to be program.Use direct method solution structure, then Obtain whole non-hydrogen atom coordinate by difference Fourier method, and obtain hydrogen atom position with theoretical hydrogenation.With method of least square pair Structure is modified, and evaluation work completes with SHELXTL program bag on PC machine.The crystallographic parameter of coordination polymer is shown in Table 1

The crystallographic parameter of table 1. part

In the coordination structure of coordination compound 1, containing a Cd²⁺Atom, two 4PBI(2-(4 '-pyridine radicals) benzo miaows Azoles) part, two TPA(p-phthalic acids) part and a water part.Wherein, cadmium atom connects the atom N of two 4PBI (N1, N4), the O atom (O1, O2, O3) of two carboxylic acids and a hydrone (O1W).

The formation of one-dimensional chain shown in Fig. 2.Multiple coordination polymers 1 by the carboxyl of carboxylic acid molecules connect two adjacent Cd atom is constantly extended to one-dimensional chain.

The formation of the two-dimensional layer shown in Fig. 3.One-dimensional chain is by the oxygen atom in water of coordination molecule and hydrogen atom and to benzene two Oxygen atom in formic acid carboxyl forms O H O hydrogen bond, intermolecular replacing and stacked arrangement one two dimension of formation by this hydrogen bond Oversubscription sublayer.

Fig. 4 is the packing of molecules figure of coordination compound 1.Intermolecular also have three kinds of π π phase interactions except interaction of hydrogen bond Firmly.One occurs between two different imidazole rings (3.585), and one occurs between pyridine ring and phenyl (3.684 ), another also occurs in (3.592) between pyridine ring and phenyl ring.Two-dimensional layer is expanded in these Hyarogen-bondings and sedimentation One Magnetic Properties of Three-Dimensional Supramolecular Complex system of generated.

Fig. 5 is the room temperature solid fluorescence spectrum figure of coordination compound 1.Just as it is shown in figure 5, be 272nm in excitation wavelength Time, coordination compound 1 occurs in that maximum emission peak in 434nm position, and this can belong ton-π* caused by electron transfer. Compared with the maximum peak of organic ligand, there is obvious Red Shift Phenomena in coordination compound 1, and this is likely due to the phase between molecule Sedimentation mutually.Therefore, coordination compound 1 has the using value that this is potential on luminescent material.

Claims

1. nitrogen heterocyclic ring, carboxylic acid Liang Zhong functional group and metal Cd ion while that a cadmium coordination polymer Han p-phthalic acid being Coordination polymer；Its chemical formula is C₃₂H₂₄CdN₆O₅, the structure of described coordination polymer is anorthic system,P-1 space group, brilliant Born of the same parents' parameter is a=10.6844 (12), b=10.9086 (12), c=13.3974 (16), α=74.525 (2) °, β=76.719 ° (2), γ=65.261 (2) °, V=1394.3 (3)³；Synthetic method is as follows:

A certain proportion of p-phthalic acid, alkali, (2-(4 '-pyridine radicals) benzimidazole) and cadmium salt are dissolved in a certain proportion of water With in organic solvent；Then transfer to reaction mixture reactor heats, at a certain temperature, react certain time After, it is slowly dropped to room temperature, filters, stand, separate out the target product 1 of yellow and determine its crystal structure figure.

2. according to the synthesis of the coordination compound 1 described in claims 1, it is characterised in that the cadmium salt used is cadmium acetate, fluorine In cadmium, Caddy (Cleary), cadmium bromide, cadmium iodide, cadmium nitrate, cadmium sulfate any one.

3. according to the synthesis of the coordination compound 1 described in claims 1, it is characterised in that the alkali used is alkali metal hydrogen-oxygen In compound, alkali metal oxide, alkaline earth metal hydroxide, alkaline earth metal hydroxide any one.

4. according to the synthesis of the coordination compound 1 described in claims 1, it is characterised in that the p-phthalic acid that used, alkali, (2-(4 '-pyridine radicals) benzimidazole) and the ratio of cadmium salt are 0.1 ~ 3.5: 0.1 ~ 3.5: 0.1 ~ 3.5: 0.1 ~ 3.5.

5. according to the synthetic method of the coordination compound 1 described in claims 1, it is characterised in that selected temperature range is from room Temperature is to 200 degrees Celsius.

6. according to the synthetic method of the coordination compound 1 described in claims 1, it is characterised in that required response time model Enclose from 0.4 hour to 168 hour.

7. according to the synthetic method of the coordination compound 1 described in claims 1, it is characterised in that selected organic solvent is for containing Carbon number is the single methanol of 1-10, double alcohol, triol, tetrol or polyhydroxy-alcohol, acetone, ethyl acetate, dimethyl sulfoxide, N, N- Dimethylformamide, dichloromethane, chloroform, carbon tetrachloride, nitromethane, oxolane, N-methyl pyrrolidone, Petroleum ether, benzene, the single solvent of toluene or mixed solvent.