CN101857604B - Three-dimensional hypoxanthine tetraphthalic acid mixed ligand copper coordination polymer and its preparation method - Google Patents

Abstract

The invention relates to a three-dimensional copper coordination polymer containing a hypoxanthine base and pyromellitic benzoic acid mixed ligand, and a preparation method and application thereof. The chemical formula of the three-dimensional coordination polymer is Cu₂(hypH)_0.5(H₂O)_0.5(btec)]·1.5H₂O, wherein hypH is hypoxanthine base and btec is the quaternary anion of pyromellitic benzoic acid. The complex is prepared by a hydrothermal method, and has high yield and good reproducibility. The complex is a first three-dimensional copper coordination polymer containing hypoxanthine base and has ferromagnetic characteristics,can be used for developing materials such as magnetic ink, information recording, magnetic induction, aerospace, microwave and the like.

Description

Three-dimensional hypoxanthine tetraphthalic acid mixed ligand copper coordination polymer and its preparation method

technical field

The invention relates to the field of metal-organic coordination polymers and molecular-based magnets, especially the preparation method and application of high-dimensional magnetic materials containing hypoxanthine bases. The coordination polymer is the first one containing hypoxanthine Three-dimensional copper coordination polymers of bases and pyrene ligands whose magnetic properties enable their use as molecular-based magnets.

Background technique

Coord.Chem.Rev.2001，219-221，379-414；X.-Y.Wang，Z.-M.Wang，S.Gao，Chem.Commun.2008，281-294)。In recent years, the design and synthesis of molecular-based materials with high-dimensional ordered spatial structure and excellent physical and chemical properties have attracted great interest (You Xiaozeng, Molecular Materials-Photoelectric Functional Compounds, Shanghai Science and Technology Press, 2001; Zhu Daoben , Advances in Chemistry of Functional Materials, Chemical Industry Press, 2005; Hong Maochun, Chen Rong, Liang Wenping, Inorganic Chemistry in the 21st Century, Science Press, 2005; Larsson, K. Molecule-Based Materials: The Structural Network Approach, Elsevier BV; Amsterdam, 2005). Compared with traditional inorganic materials, when organic ligands and inorganic cations are aggregated into a solid, the arrangement of atoms and the way of connection have a great impact on the function of the system. As a branch of molecular-based materials, molecular-based magnets involve emerging interdisciplinary research fields in many disciplines such as chemistry, physics, materials, and life sciences. One of its main tasks is to study the interaction and mechanism of spin carriers in molecular systems. , to reveal the intrinsic relationship between molecular magnetism and structure, to discover and screen new functional materials (JSMiller, M.Drillon, Eds.Magnetism: Molecules to Materials (I-IV). Weinheim, Willey-VCH, 2002; E.Coronado , F. Palacio, J. Veciana, Angew. Chem. Int. Ed., 2003, 42, 2570-2572; O. Kahn, Molecular Magnetism, VCH, Weinheim, Germany, 1993; M. Sakamoto, K. Manseki, H .

Coord. Chem. Rev. 2001, 219-221, 379-414; X.-Y. Wang, Z.-M. Wang, S. Gao, Chem. Commun. 2008, 281-294).

H.W.Schmalle，Acta Crystallogr.1987，C43，1872-1875；E.Dubler，G.

H.W.Schmalle，Inorg.Chem.1990，29，2518-2523；G.H.W.Schmalle，E.Dubler，Acta Crystallogr.1992，C48，1008-1012；P.Annen，S.Schildberg，W.S.Sheldrick，Inorg.Chim.Acta 2000，307，115-124；M.A.Salam，K.Aoki，Inorg.Chim.Acta 2001，314，71-82；D.Badura，H.Vahrenkamp，Inorg.Chem.2002，41，6013-6019；García-Raso，A.；Fiol，J.J.；Tasada，A.；Prieto，M.J.；Moreno，V.；I.Mata，E.Molins，T.

A.

I.Turel，Inorg.Chem.Commun.2005，8，800-804；K.Aoki，M.A.Salam，C.Munakata，I.Fujisawa，Inorg.Chim.Acta 2007，360，3658-3670；M.A.Salam，H.-Q.Yuan，T.Kikuchi，N.A.Prasad，I.Fujisawa，K.Aoki，Inorg.Chim.Acta 2009，362，1158-1168)。The hypoxanthine nucleic acid base contains multiple N and O donors that can coordinate with paramagnetic metal ions, and can display a variety of different coordination modes, and has become an ideal ligand for the construction of ordered aggregates of different dimensions (E.Sletten, ActaCrystallogr.1970, B26, 1609-1614; MEKastner, KFCoffey, MJClarke, SEEdmonds, K.Eriks, J.Am.Chem.Soc.1981, 103, 5747-5752; E.Dubler, G. W. Bensch, J. Inorg. Biochem. 1987, 29, 269-288; E. Dubler, G.

HWSchmalle, Acta Crystallogr. 1987, C43, 1872-1875; E. Dubler, G.

HWSchmalle, Inorg. Chem. 1990, 29, 2518-2523; G. HWSchmalle, E. Dubler, Acta Crystallogr. 1992, C48, 1008-1012; P. Annen, S. Schildberg, WS Sheldrick, Inorg. Chim. Acta 2000, 307, 115-124; MASalam, K. Aoki, Inorg. Chim. Acta 2001, 314, 71-82; D. Badura, H. Vahrenkamp, Inorg. Chem. 2002, 41, 6013-6019; García-Raso, A.; Fiol, JJ; Tasada, A.; Prieto, MJ; Moreno , V.; I. Mata, E. Molins, T.

a.

I. Turel, Inorg. Chem. Commun. 2005, 8, 800-804; K. Aoki, MASalam, C. Munakata, I. Fujisawa, Inorg. Chim. Acta 2007, 360, 3658-3670; MASalam, H.- Q. Yuan, T. Kikuchi, NAPrasad, I. Fujisawa, K. Aoki, Inorg. Chim. Acta 2009, 362, 1158-1168).

adillas-Delgado，F.S.Delgado，F.Lloret，M.Julve，C.Ruiz-Pérez，Inorg.Chem.2008，47，8053-8061；W.Li，Z.-F.Ju，Q.-X.Yao，J.Zhang，CrystEngComm2008，10，1325-1327；Y.-Z.Zheng，Y.-B.Zhang，M.-L.Tong，W.Xue，X.-M.Chen，Dalton Trans.2009，1396-1406；O.Fabelo，L.adillas-Delgado，J.Pasán，F.S.Delgado，F.Lloret，J.Cano，M.Julve，C.Ruiz-Pérez，Inorg.Chem.2009，48，11342-11351等)。然而，同时含有次黄嘌呤和均四苯甲酸混合配体的铜配位聚合物的磁性材料还未见报道，相关研究为磁性油墨、信息记录、磁感应、航天和微波等材料的开发探索开辟新的道路。On the other hand, polycarboxylic acid ligands with rich coordination modes, especially polycarboxylic ligands containing aromatic rings, can effectively control ferromagnetism and antiferromagnetic properties through the coordination configurations formed by metal ions and carboxyl groups in different conformations. magnetic coupling. In fact, the construction of complexes with ferromagnetic, antiferromagnetic, and field-induced spin transition properties through different aromatic acids has been extensively and extensively studied (Z.-B.Han, J.-W.Ji, H.-Y.An, W. Zhang, G.-X. Han, G.-X. Zhang, L.-G. Yang, Dalton Trans. 2009, 9807-9811; YY Karabach, AM Kirillov, M. Haukka, J .Sanchiz, MNKopylovich, AJL Pombeiro, Cryst.Growth Des.2008, 8, 4100-4108; X.Zhu, J.-W.Zhao, B.-L.Li, Y.Song, Y.-M.Zhang, Y. .Zhang, Inorg.Chem.2010, 49, 1266-1270; H.-P.Jia, W.Li, Z.-F.Ju, J.Zhang, Dalton Trans.2007, 3699-3704; O.Fabelo, J. Pasán, L.

adillas-Delgado, FSDelgado, F.Lloret, M.Julve, C.Ruiz-Pérez, Inorg.Chem.2008, 47, 8053-8061; W.Li, Z.-F.Ju, Q.-X.Yao, J. Zhang, CrystEngComm2008, 10, 1325-1327; Y.-Z. Zheng, Y.-B. Zhang, M.-L. Tong, W. Xue, X.-M. Chen, Dalton Trans. 2009, 1396 -1406; O. Fabelo, L. adillas-Delgado, J. Pasán, FS Delgado, F. Lloret, J. Cano, M. Julve, C. Ruiz-Pérez, Inorg. Chem. 2009, 48, 11342-11351, etc.). However, magnetic materials containing copper coordination polymers containing mixed ligands of hypoxanthine and pyridine have not been reported yet, and related research has opened up new horizons for the development and exploration of materials such as magnetic ink, information recording, magnetic induction, aerospace and microwave. path of.

Contents of the invention

An object of the present invention is to provide a three-dimensional copper coordination polymer of hypoxanthine pyretate, which is the first example of a three-dimensional copper coordination polymer containing hypoxanthine base, and has ferromagnetic properties.

Another object of the present invention is to provide a method for preparing a three-dimensional hypoxanthine copper coordination polymer.

Another object of the present invention is to provide the application of a three-dimensional hypoxanthine copper coordination polymer in the preparation of molecular-based magnets. To achieve the above object, the present invention provides the following technical solutions:

A three-dimensional hypoxanthine copper coordination polymer having the following general chemical formula:

[Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)]·1.5H ₂ O

Among them, hypH is hypoxanthine base, btec is the quaternary anion of pyridine, and its molecular formula is as follows:

Z＝4；次黄嘌呤碱基通过环外羰基氧原子和咪唑环氮原子双齿桥联两个二价铜离子形成一维波浪状的铜-次黄嘌呤带状结构，进而通过均苯四甲酸的羧基与铜离子的配位行为拓展形成三维共价结构。The three-dimensional hypoxanthine pyrene acid mixed ligand copper coordination polymer of the present invention is characterized in that the copper coordination polymer belongs to the orthorhombic crystal system, the space group is Pmn2 ₁ , and the unit cell parameter is a =12.0693(5), b=11.0441(5),

Z=4; the hypoxanthine base bridges two divalent copper ions through the exocyclic carbonyl oxygen atom and the imidazole ring nitrogen atom bidentate to form a one-dimensional wavy copper-hypoxanthine ribbon structure, and then through the pyromellitic The coordination behavior of the carboxyl group of formic acid and copper ions expands to form a three-dimensional covalent structure.

The three-dimensional hypoxanthine copper coordination polymer of the present invention has main infrared absorption peaks of 3437cm ^-1 , 1693cm ^-1 , 1636cm ^-1 , 1566cm ^-1 , 1497cm ^-1 , 1434cm ^-1 , 1398cm ^-1 , 1283cm ^-1 , 1185cm ^-1 , 1138cm ^{-1 ,} 1100cm -1 , 920cm ^-1 , 889cm ^-1 , 848cm ^-1 , 812cm ^-1 , 765cm ^-1 , 689cm ^-1 , 647cm ^-1 , 579cm ^-1 , 516cm ^-1 (see Figure 3); the complex begins to decompose at 340°C.

The preparation method of the three-dimensional hypoxanthine copper coordination polymer of the present invention is characterized in that hypoxanthine, pyrene carboxylic acid and copper nitrate trihydrate or copper chloride dihydrate are hydrothermally reacted in twice distilled water to obtain Blue bulky single crystal, washed with methanol, and dried; the molar ratio of hypoxanthine, pyrene, and copper nitrate trihydrate or copper chloride dihydrate is 1-2:1:2. Wherein, the amount of water used for secondary distillation in the hydrothermal reaction is 8.0 mL to 10.0 mL. The pH range of the hydrothermal reaction is between 5 and 8. The hydrothermal reaction temperature is 120° C. to 140° C. for 3 days and then lowered to room temperature.

The hydrothermal reaction of the present invention refers to that in a special airtight container (generally using a stainless steel reactor lined with polytetrafluoroethylene), with water or other organic solvents as the reaction medium, through external heating (temperature range : 100-300°C) to generate autogenous pressure (1-100Mpa) inside the container, so that the insoluble or insoluble substances are usually dissolved and crystallized.

The structural characterization of the three-dimensional hypoxanthine copper coordination polymer (Example 1-5) prepared by the present invention is as follows:

(1) Determination of crystal structure (Figure 1)

方式收集衍射数据。所有衍射数据通过SADABS软件用multi-scan方法进行半经验吸收校正。晶胞参数用最小二乘法确定。数据还原和结构解析分别使用SAINT和SHELXL程序包完成。所有非氢原子用全矩阵最小二乘法进行各向异性精修。结构见图1。晶体学衍射点数据收集和结构精修的部分参数见表1。Select a single crystal of appropriate size under a microscope, and use graphite monochromatized Mo-Kα rays ( ),by

to collect diffraction data. All diffraction data were semi-empirically corrected by SADABS software using the multi-scan method. The unit cell parameters were determined using the least squares method. Data restoration and structure elucidation were accomplished using the SAINT and SHELXL program packages, respectively. All non-hydrogen atoms were anisotropically refined using full matrix least squares. The structure is shown in Figure 1. Some parameters of crystallographic diffraction point data collection and structure refinement are shown in Table 1.

Table 1. The main crystallographic data and refinement parameters of the three-dimensional hypoxanthine copper coordination polymer

^a R ₁ ＝∑||F _o |-|F _c ||/|F _o |;

^b wR ₂ ＝[∑w(F _o ² -F _c ² ) ² /∑w(F _o ² ) ² ] ^1/2 .

(2) Infrared spectrometry (Fig. 2)

Infrared spectra were measured on a Nicolet IR-200 infrared spectrometer by the potassium bromide tablet method.

(3) thermogravimetric analysis (Fig. 3)

The thermogravimetric analysis experiment was completed on a Shimadzu simultaneous DTG-60A thermogravimetric analyzer. Under the protection of nitrogen, it was heated from room temperature to 800 °C at a rate of 5 °C/min. The results showed that the crystal of the complex decomposed at 340 °C.

(4) Powder diffraction characterization of phase purity (Figure 4)

Powder diffraction data were collected on a Rigaku D/Max-2500 diffractometer. The operating voltage of the instrument is 40kV and the current is 100mA. Cu target X-rays monochromated using graphite. Fixed scanning, the divergence deviation is 1°, the receiving slit width is 0.3mm; the density data collection uses 2θ/θ scanning mode, and the scanning is completed continuously within the range of 3° to 60°, the scanning speed is 8°/s, and the step size is 0.02°. Cerius2 program was used for data fitting, and Mercury 1.4.1 software package was used for simulation transformation of single crystal structure powder diffraction spectrum.

The invention further discloses the application of the copper coordination polymer of the mixed ligand of three-dimensional hypoxanthine pyrene in the preparation of molecular-based magnets. It can be applied to fields such as magnetic ink, information recording, magnetic induction, aerospace and microwave materials.

The molecular-based magnet described in the present invention is a class of compounds constructed by self-assembly and controlled assembly of paramagnetic metal ions and organic bridging ligands by means of supramolecular chemistry, and has spontaneous magnetization behavior below the critical temperature . Molecular-based magnets have the advantages of small size, light weight, high transparency, good solubility, diverse structures, and easy composite processing and molding.

The salient features of the three-dimensional hypoxanthine copper coordination polymer prepared by the present invention are:

(1) The present invention is the first coordination polymer containing a three-dimensional structure of hypoxanthine base.

(2) In the coordination polymer prepared by the present invention, the exocyclic carbonyl oxygen atom of the hypoxanthine base participates in coordination for the first time, and two bivalent copper ions are bidentately bridged with the nitrogen atom of the imidazole ring to expand the structure.

(3) The coordination polymer in the present invention is prepared by hydrothermal synthesis, with high yield, good reproducibility, high thermal stability, and ferromagnetic properties, which can be used as molecular-based magnets for Future magnetic ink, information recording, magnetic induction, aerospace and microwave materials and other fields.

Description of drawings

Figure 1 The three-dimensional structure of [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)]·1.5H ₂ O;

Figure 2 [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)] · 1.5H ₂ O infrared spectrum;

Figure 3 [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)]·1.5H ₂ O thermogravimetric analysis diagram;

Figure 4 [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)] · 1.5H ₂ O powder diffraction pattern;

Fig. 5 Magnetic diagram of [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)]·1.5H ₂ O.

Detailed ways

For the purpose of simplicity and clarity, descriptions of known technologies are appropriately omitted below, so as not to affect the description of the technical solution with unnecessary details. Below in conjunction with the preferred embodiment, the present invention is further described, and it is particularly illustrated that the starting material hypoxanthine for the preparation of the compound of the present invention, pyromellitic acid, copper nitrate trihydrate or copper chloride dihydrate can all be obtained from available in the market.

Example 1

Synthesis of three-dimensional hypoxanthine copper coordination polymer A:

The organic ligands, hypoxanthine (0.1 mmol, 13.6 mg), pyromellitic acid (0.05 mmol, 12.7 mg) and copper nitrate trihydrate (0.1 mmol, 24.2 mg) were dissolved in double distilled water (10.0 mL), adjust the pH to 8 with triethylamine, stir for a few minutes and seal it into a hydrothermal kettle. After incubating at 120° C. for 3 days, the temperature was programmed to cool down to room temperature to obtain a blue bulk single crystal, which was then washed with methanol and dried.

Example 2

Synthesis of three-dimensional hypoxanthine copper coordination polymer B:

The organic ligands, hypoxanthine (0.05 mmol, 6.8 mg), pyromellitic acid (0.05 mmol, 12.7 mg) and copper nitrate trihydrate (0.1 mmol, 24.2 mg) were dissolved in double distilled water (8.0 mL), adjust the pH to 5 with triethylamine, stir for a few minutes and seal it into a hydrothermal kettle. After incubating at 140° C. for 3 days, the temperature was programmed to cool down to room temperature to obtain a blue bulk single crystal, which was then washed with methanol and dried.

Example 3

Synthesis of three-dimensional hypoxanthine copper coordination polymer C:

The organic ligands, hypoxanthine (0.1 mmol, 13.6 mg), pyrene (0.05 mmol, 12.7 mg) and copper chloride dihydrate (0.1 mmol, 17.5 mg) were dissolved in double distilled water ( 10.0mL), adjust the pH to 8 with triethylamine, stir for a few minutes and seal it into a hydrothermal kettle. After incubating at 120° C. for 3 days, the temperature was programmed to cool down to room temperature to obtain a blue bulk single crystal, which was then washed with methanol and dried.

Example 4

Synthesis of three-dimensional hypoxanthine copper coordination polymer D:

The organic ligands, hypoxanthine (0.05 mmol, 6.8 mg), pyrene (0.05 mmol, 12.7 mg) and copper chloride dihydrate (0.1 mmol, 17.5 mg) were dissolved in double distilled water ( 8.0mL), adjust the pH to 6 with triethylamine, stir for a few minutes and seal it into a hydrothermal kettle. After incubating at 140° C. for 3 days, the temperature was programmed to cool down to room temperature to obtain a blue bulk single crystal, which was then washed with methanol and dried.

Example 5

Ferromagnetic properties of three-dimensional hypoxanthine copper coordination polymer:

The magnetic properties were measured by Quantum Design MPMS-XL-7 SQUID magnetometer, and the temperature-varying magnetic susceptibility curve of the complex single crystal was measured at 2-300K using a 2000 Gauss DC field. The magnetic measurement data of the crystalline sample shows that the coordination polymer is a three-dimensional magnetically ordered ferromagnet, which can be used as a molecular-based magnet in the fields of magnetic ink, information recording, magnetic induction, aerospace and microwave materials, as shown in Figure 5. For example, the complex has ferromagnetism similar to iron oxide black or iron oxide brown and is easier to pulverize and disperse, so it can be used as the basic component of magnetic ink, that is, magnetic pigment. Compared with traditional pigments (iron oxide black or iron oxide brown), the magnetic pigments containing this complex have better heat resistance and acid and alkali resistance.

After the preferred embodiment described in detail, those skilled in the art can clearly understand that various changes and modifications can be carried out without departing from the scope and spirit of the above-mentioned patent application. Any simple modifications, equivalent changes and modifications all belong to the scope of the technical solution of the present invention. And the present invention is not limited by the example implementations in the specification.

Claims (7)

1. A three-dimensional hypoxanthine pyrene-tetraphthalic acid mixed ligand copper coordination polymer having the following general chemical formula: [Cu ₂ (hypH) _0.5 (H ₂ O) _0.5 (btec)]·1.5H ₂ O; Among them, hypH is hypoxanthine base, btec is the quaternary anion of pyridine, and its molecular formula is as follows:

The coordinated copper coordination polymer belongs to the orthorhombic crystal system, the space group is Pmn2 ₁ , and the unit cell parameter is

Z=4; the hypoxanthine base bridges two divalent copper ions through the exocyclic carbonyl oxygen atom and the imidazole ring nitrogen atom bidentate to form a one-dimensional wavy copper-hypoxanthine ribbon structure, and then through the pyromellitic The coordination behavior of the carboxyl group of formic acid and copper ions expands to form a three-dimensional covalent structure. 2. The three-dimensional hypoxanthine copper coordination polymer according to claim 1, its main infrared absorption peaks are 3437cm ^-1 , 1693cm ^-1 , 1636cm ^-1 , 1566cm ^-1 , 1497cm ^-1 , 1434cm ^-1 , 1398cm ^{-1 1} , 1283cm ^-1 , 1185cm -1 ^, 1138cm ^-1 , 1100cm ^-1 , 920cm ^-1 , 889cm ^-1 , 848cm ^-1 , 812cm ^-1 , 765cm ^-1 , 689cm ^-1 , 647cm ^-1 , 579cm ^-1 , 516cm ^-1 ; the complex decomposes at 340°C. 3. the preparation method of the three-dimensional hypoxanthine copper coordination polymer described in claim 1 is characterized in that hypoxanthine, pyrene carboxylic acid and copper nitrate trihydrate or copper chloride dihydrate are passed through water in twice distilled water Heat reaction to obtain blue blocky single crystal, then wash with methanol, and dry; the molar ratio of hypoxanthine, pyrene carboxylic acid and copper nitrate trihydrate or copper chloride dihydrate is 1-2:1:2. 4. The preparation method according to claim 3, characterized in that the amount of double distilled water in the hydrothermal reaction is 8.0mL-10.0mL. 5. The preparation method according to claim 3, wherein the pH range of the hydrothermal reaction is between 5-8. 6. The preparation method of the coordination polymer according to claim 3, characterized in that the hydrothermal reaction temperature is 120°C-140°C for 3 days and then dropped to room temperature. 7. The application of the three-dimensional hypoxanthine copper coordination polymer according to claim 1 in the preparation of molecular-based magnets.

Images