CN103087111B - Tetrazolyl cobalt (II) complex magnetic material and preparation method and application thereof - Google Patents

Tetrazolyl cobalt (II) complex magnetic material and preparation method and application thereof Download PDF

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CN103087111B
CN103087111B CN201210524298.7A CN201210524298A CN103087111B CN 103087111 B CN103087111 B CN 103087111B CN 201210524298 A CN201210524298 A CN 201210524298A CN 103087111 B CN103087111 B CN 103087111B
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tetrazole
cobalt
ligand
isophthalic acid
magnetic material
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CN103087111A (en
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赵小军
杨恩翠
刘忠义
刘婧
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Tianjin Normal University
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Abstract

The invention relates to a 5-methyl-1H-tetrazole and isophthalic acid mixed ligand cobalt (II) coordination polymer magnetic material, and a preparation method and application thereof. The chemical formula of the coordination polymer magnetic material provided by the invention is {[Co7(H2O)2(mu3-OH)4(mtz)2(ip)4].13/4H2O}, wherein mtz is the 5-methyl tetrazole anion with valence of -1, and ip is the isophthalic acid anion with valence of -2. The coordination polymer magnetic material is prepared by solvothermal synthesis, and is high in productivity and good in reproducibility. The coordination polymer magnetic material is the three-dimensional cobalt (II) compound simultaneously including 5-methyl-1H-tetrazole and isophthalic acid mixed ligand, presents continuous two-step field-induced metamagnetic transition and spin-flop transition, which are from antiferromagnetic order to week spontaneous magnetization, in different external magnetic fields, and can be used as molecular-based magnetic material to have great application value in the field of material science.

Description

Tetrazyl cobalt (II) coordination compound magnetic material and preparation method thereof and application
Present patent application obtains Tianjin Natural Science Fund In The Light (subsidy number: 10JCZDJC21600 and 10JCYBJC04800) and state natural sciences fund (subsidy number: subsidy 20973125,21171129 and 21173157).
Technical field
The present invention relates to metal-organic coordination polymer and molecule based magnetic materials technical field thereof, particularly contain preparation method and the application thereof of three-dimensional cobalt (II) coordination polymer magnetic material of mixed ligand of 5-methyl isophthalic acid H-tetrazole part, described compound is cobalt (II) ligand polymer that simultaneously contains 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand, and its magnetic property makes it can be used as molecule based magnetic materials to be applied at material science.
Background technology
In recent years, design and the synthetic molecular based functional materials with higher-dimension ordered space structure and good physicochemical property caused the great interest of people (trip effect once, molecular material-photoelectric functional compound, Shanghai science tech publishing house, 2001; Primary track basis, functional materials chemical progress, Chemical Industry Press, 2005; Larsson, K. Molecule-Based Materials:The Structural Network Approach, Elsevier B. V.; Amsterdam, 2005).Compare with traditional inorganic materials, when one or more organic bridge ligands form crystalline state solid material with the paramagnetic transition metal ion self-assembly with different electronic structures and spin-orbit coupling, the arrangement mode of metal ion and the coordination mode of organic bridge ligand have important effect to the structure and function of assembly.Yi Ge branch as molecular based functional materials, the design and researchp of molecular based magnet relates to many cross disciplines such as chemistry, physics, material and life science, one of its main task is magnetic interaction and the mechanism thereof between the spin plasmid being connected by bridge ligand in research molecular system, disclose the magnetic performance of molecule macroscopic view and the internal relation between microtexture, screen and find new magnetic functional material (J. S. Miller, M. Drillon, Eds. magnetism:Molecules to Materials(I-IV). Weinheim, Willey-VCH, 2002; O. Kahn, molecular Magnetism, VCH, Weinheim, Germany, 1993; M. Sakamoto, K. Manseki, H. kawa, coord. Chem. Rev. 2001, 219– 221, 379 – 414; Kurmoo, M. chem. Soc. Rev. 2009, 38, 1353 – 1379).
The tetrazole part of rigidity is common penta azacyclo organic molecule, N atom on its heterocycle contains the lone-pair electron that cloud density is larger, can form metal-organic coordination polymer with the coordination of paramagnetic transition metal ion, and its four continuous nitrogen-atoms can make it show the multiple variable coordination mode that enriches.Their structural singularity makes these transition metal complexes that contain tetrazolium class part possess potential peculiar property, at absorption, catalysis, magnetic, nonlinear optics, many Material Fields such as luminous and field of medicaments, all there is potential using value (Y.-L. Yao, L. Xue, Y.-X. Che, J.-M. Zheng cryst. Growth Des. 2009, 9,606. Y.-C. Qiu, H. Deng, J.-X. Mou, S.-H. Yang, M. Zeller, S. R. Batten, H.-H. Wu, J. Li, chemComm. 2009, 5415. W.-C. Song, J.-R. Li, P.-C. Song, Y.Tao, Q.Yu, X.-L. Tong, X.-H. Bu, inorg. Chem. 2009, 48,3792. Z. Li, M. Li, X.-P. Zhou, T. Wu, D. Li, S. W. Ng, cryst. Growth Des. 2007, 7,1992.).
Yet up to now, the research of the paramagnetic metal ligand polymer that 5-methyl isophthalic acid H-tetrazole and m-phthalic acid be mixed ligand of take is also very limited.Correlative study is expected to open up new road for the development and application of novel molecule based magnetic materials.
Summary of the invention
The preparation method and the application thereof that provide one to contain 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer and this ligand polymer are provided the object of the invention simultaneously.This ligand polymer is three-dimensional cobalt (II) compound that simultaneously contains 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand, shows change magnetic transition and the spin(-)flop transition behavior to weak spontaneous magnetization state by antiferromagnetic order of two continuous step field inductions under different externally-applied magnetic fields.
For achieving the above object, the invention provides following technology contents:
5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer with following chemical general formula: { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2o}, wherein mtz is the negative univalent anion of 5-methyl tetrazole, the negative dianion of ip m-phthalic acid, its molecular formula is as follows:
。
The preparation method of mixed ligand cobalt of the present invention (II) ligand polymer, it is characterized in that 5-methyl isophthalic acid H-tetrazole, m-phthalic acid and Cobaltous nitrate hexahydrate via solvent thermal reaction, to obtain red bulk crystals in redistilled water and ethanol, wherein the mol ratio of 5-methyl isophthalic acid H-tetrazole, m-phthalic acid and Cobaltous nitrate hexahydrate is 3:2:3 ~ 3.5; The volume of redistilled water is 7.0 mL, and the volume of ethanol is 3.0 mL; The pH value scope of controlling is 4 ~ 5; After being incubated three days at 180 ~ 190 ℃, drop to room temperature, then washing, dry; Obtain red bulk crystals.
Solvent thermal reaction of the present invention refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, take redistilled water and organic solvent as reaction medium, by temperature control oven, heat (heated perimeter: 100 ~ 300 ℃) and make internal tank produce spontaneous pressure (1 ~ 100 Mpa), make indissoluble or insoluble substance dissolves crystallization under normal conditions.The following examples 1-4 all adopts this method, and spy is illustrated.
Mixed ligand cobalt of the present invention (II) ligand polymer, is characterized in that this complex crystal is in oblique system p2 1 / cspacer, unit cell parameters is a=8.7597 (4), b=18.6069 (8), c=14.5879 (6), b=97.7600 (10) o, v=2355.92 (18) 3, z=2; Its structure is shown in Fig. 1.
Cobalt (II) ion that contains 3.5 positive divalence in the unsymmetrical structure unit of this ligand polymer, a coordinated water molecule, 5-methyl tetrazole negative univalent anion, the m-phthalic acid negatively charged ion of two negative divalence and 1.625 dissociating water molecules.As shown in Figure 1a, three crystallography is cobalt (II) ion independently, all be in the octahedral coordination environment of distortion, its ligating atom comes from respectively the nitrogen-atoms of tetrazyl, the carboxyl oxygen atom of the phthalic acid of two deprotonations, the hydroxyl oxygen atom of tridentate ligand or the water molecules of end group coordination.By comparison, cobalt (II) ion of another one in symmetry centre is in octahedral coordination environment of axial compression, and by two centrosymmetric tetrazyl nitrogen-atoms, the hydroxyl oxygen atom of carboxyl oxygen atom and tridentate ligand surrounds respectively.As shown in Figure 1 b.Two right titles μ 3-OH -connect different cobalt (II) ions and form the alternately one dimension cummerbund structure of the unlimited extension of appearance of He Gong limit, common summit trilateral, and pass through μ 4– atz –coordination mode make the structure in one dimension broadband more firm.The adjacent one dimension wideband structural further carboxyl of the m-phthalic acid by two deprotonations is expanded and is formed three-dimensional title complex skeleton (seeing Fig. 1 c).
And then He Gong limit, summit trilateral is alternately connected to form a unlimited one dimension cummerbund structure (seeing Fig. 1 b) of extending altogether, and pass through μ 4– atz –coordination mode make the structure in one dimension broadband more firm.The adjacent one dimension wideband structural further carboxyl of the m-phthalic acid by two deprotonations is expanded and is formed three-dimensional title complex skeleton (seeing Fig. 1 c).
The main infrared absorption peak of this ligand polymer is 3461 cm -1, 1603 cm -1, 1558 cm -1, 1543 cm -1, 1524 cm -1, 1482 cm -1, 1457 cm -1, 1356 cm -1, 1267 cm -1, 1159 cm -1, 1083 cm -1, 751 cm -1, 707 cm -1, 666 cm -1, 419 cm -1(see figure 2); The two-dimensional framework of title complex decomposes (see figure 3) between 352 to 405 ℃.
This ligand polymer has reliable phase purity (Fig. 4).Along with the enhancing of externally-applied magnetic field, this ligand polymer is transformed into the change magnetic behavior with weak spontaneous magnetization state by the magnetic behavior of antiferromagnetic order.Continuing increases foreign field, and this ligand polymer presents again spin(-)flop transition behavior (Fig. 5).Two continuous steps become critical magnetic field corresponding to magnetic transition behavior and are respectively 2.0 and 20.0 kOe.This magnetic response ability that this coordination polymer magnetic material shows at different externally-applied magnetic fields makes it can be used as magneticsensor use, is expected to be applied on the information storing materials such as low density hard disc of computer.
The distinguishing feature that contains 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer prepared by the present invention is:
(1) the present invention is three-dimensional cobalt (II) metal-organic coordination polymer that simultaneously contains 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand.
(2) magneticsubstance in the present invention adopts solvent thermal process preparation, productive rate is higher, favorable reproducibility, there is higher thermostability, under different externally-applied magnetic fields, present the magnetic transformation behavior of two continuous step field inductions, can be used as magneticsensor, be expected to be applied on the information storing materials such as low density hard disc of computer.
Accompanying drawing explanation
Fig. 1 title complex { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2the tomograph of O} (Fig. 1 a-c);
Fig. 2 title complex { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2the infrared spectrogram of O};
Fig. 3 title complex { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2the thermogravimetric analysis figure of O};
Fig. 4 title complex { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2the powder diagram of O};
Fig. 5 title complex { [Co 7(H 2o) 2( μ 3-OH) 4(mtz) 2(ip) 4] 13/4H 2the magnetic chart of O} (Fig. 5 a-b).
Embodiment
For simple and object clearly, below appropriate omission the description of known technology, in order to avoid those unnecessary details impact descriptions to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, is illustrated especially, prepares initial substance 5-methyl isophthalic acid H-tetrazole, m-phthalic acid and the Cobaltous nitrate hexahydrate of the compounds of this invention and all can buy from the market.
embodiment 1
5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer A's is synthetic:
By 5-methyl isophthalic acid H-tetrazole (0.3 mmole, 25.2 milligrams), m-phthalic acid (0.2 mmole, 33.2 milligrams) and Cobaltous nitrate hexahydrate (0.3 mmole, 87.3 milligrams) be dissolved in redistilled water (7.0 mL) and ethanol (3.0 mL), with triethylamine, regulating pH is 4, after stirred for several minute, encloses in water heating kettle.At 180 ℃, be incubated after three days, programmed cooling obtains red bulk-shaped monocrystal body to room temperature, then uses washing with alcohol, air drying.See the crystalline structure figure of Fig. 1.
embodiment 2
5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer B's is synthetic:
By 5-methyl isophthalic acid H-tetrazole (0.3 mmole, 25.2 milligrams), m-phthalic acid (0.2 mmole, 33.2 milligrams) and Cobaltous nitrate hexahydrate (0.3 mmole, 87.3 milligrams) be dissolved in redistilled water (7.0 mL) and ethanol (3.0 mL), with triethylamine, regulating pH is 4, after stirred for several minute, encloses in water heating kettle.At 190 ℃, be incubated after three days, programmed cooling obtains red bulk-shaped monocrystal body to room temperature, then uses washing with alcohol, air drying.See the crystalline structure figure of Fig. 1.
embodiment 3
5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer C's is synthetic:
By 5-methyl isophthalic acid H-tetrazole (0.3 mmole, 25.2 milligrams), m-phthalic acid (0.2 mmole, 33.2 milligrams) and Cobaltous nitrate hexahydrate (0.35 mmole, 101.9 milligrams) be dissolved in redistilled water (7.0 mL) and ethanol (3.0 mL), with triethylamine, regulating pH is 5, after stirred for several minute, encloses in water heating kettle.At 180 ℃, be incubated after three days, programmed cooling obtains red bulk-shaped monocrystal body to room temperature, then uses washing with alcohol, air drying.See the crystalline structure figure of Fig. 1.
embodiment 4
5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer D's is synthetic:
By 5-methyl isophthalic acid H-tetrazole (0.3 mmole, 25.2 milligrams), m-phthalic acid (0.2 mmole, 33.2 milligrams) and Cobaltous nitrate hexahydrate (0.3 mmole, 87.3 milligrams) be dissolved in redistilled water (7.0 mL) and ethanol (3.0 mL), with triethylamine, regulating pH is 5, after stirred for several minute, encloses in water heating kettle.At 190 ℃, be incubated after three days, programmed cooling obtains red bulk-shaped monocrystal body to room temperature, then uses washing with alcohol, air drying.See the crystalline structure figure of Fig. 1.
The mixed ligand cobalt (II) of (embodiment 1-4) prepared by the present invention (II) structural characterization of ligand polymer is as follows:
(1) crystal structure determination (Fig. 1)
Choose under the microscope the monocrystalline of the suitable size of size, under low temperature 173 K, on Bruker APEX II CCD diffractometer, use through the Mo-K of graphite monochromatization alpha-ray (λ=0.71073), with j- ωmode is collected diffraction data.All diffraction datas carry out semiempirical absorption correction by SADABS software by multi-scan method.Unit cell parameters is determined by method of least squares.Reduction of data and structure elucidation are used respectively SAINT and SHELXL routine package to complete.All non-hydrogen atoms carry out anisotropy refine by complete matrix method of least squares.Structure is shown in Fig. 1.The partial parameters of the data gathering of crystallography point diffraction and structure refinement is in Table 1.
Table 1. 5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer
Main crystallographic data and refine parameter
(2) infrared measurement (Fig. 2)
Infrared spectra adopts pellet technique to measure on the infrared spectrometer of Nicolet FT – IR – 200.
(3) (Fig. 3) measured in thermogravimetric analysis
Thermogravimetric analysis experiment is to complete on the thermogravimetric analyzer of Shimadzu simultaneous DTG – 60A, and the speed with 5 ℃/min under nitrogen protection is heated to 900 ℃ of mensuration from room temperature.Water molecules in result demonstration coordination compound magnetic material is 352 obefore C, slowly lose, the three-dimensional framework of title complex starts to decompose afterwards, and 405 oafter C, remaining residue is cobalt oxide.
(4) powdery diffractometry characterizes phase purity (Fig. 4)
Powder diffraction data is collected on Bruker D8 ADVANCE diffractometer and measures.Instrumentation voltage is 40 kV, and electric current is 40 mA.Use the Cu target X ray of graphite monochromatization.Divergent slit width is 0.6 mm, and anti-scatter slit width is 3 mm, and Soller slit is 4 o; Data gathering is used 2 q/ qscan pattern, 5 oto 50 oin scope, continuous sweep completes, and sweep velocity is 0.1 o/ second, step-length is 0.01 o.Single crystal structure powdery diffractometry Spectrum simulation transforms and uses Mercury 1.4.1 software package.
embodiment 5(measurement result of the magnetic property of embodiment 1-4 compound)
The magnetic performance research of (embodiment 1-4, A-D) coordination polymer magnetic material prepared by the present invention is as follows:
The MPMS-XL-7 superconducting quantum interference device (SQUID) magnetometer that the magnetic performance test of crystalline state title complex is used U.S. Airoam to produce completes, and wherein the alternating temperature susceptibility within the scope of 2 ~ 300 K is measured under additional 2 kOe direct magnetic fields.Variable field specific magnetising moment during 2 K is measured under additional DC fields 0 ~ 70 kOe.All magnetic datas are all used pascal's constant to carry out diamagnetic correction, test the background datas such as sample hose used and sample thin film and are deducted.
Magnetic Measurement result shows: when externally-applied magnetic field intensity is 2.0 kOe, and each Co in mixed ligand cobalt (II) ligand polymer iI 7the molar susceptibility of unit and the product of temperature ( χ m t) value is 22.1 cm when 300 K 3mol – 1k(Fig. 5 a), far above seven not coupling high-spins octahedra cobalt (II) ion ( s=3/2, g=2.0) pure spin value (13.1 cm 3mol – 1k), its reason is the Spin-orbital coupling effect due to cobalt (II) ion.Along with the continuous reduction of temperature, the molar susceptibility of mixed ligand cobalt (II) ligand polymer and the product of temperature ( χ m t) constantly decline of value.When 2.0 K, the product of molar susceptibility and temperature ( χ m t) drop to minimumly, be 1.99 cm 3mol – 1k.At 40.0 K, in the temperature range of 300 K, this ligand polymer meets Ju Li – weiss law, its Curie constant c=24.6 cm 3mol – 1k, weiss temperature θ=– 36.2 K.Weiss temperature is less than zero and shows to exist obvious antiferromagnetic coupling effect between neighbour's cobalt ion.It is pointed out that this coordination polymer magnetic material χ mright tthere is a spike in curve, show that this coordination polymer magnetic material presents antiferromagnetic order behavior at low temperatures when 2.5 K, ac magnetization rate curve further confirm its Ne&1&el temperature ( t n) be 2.5 K.Ironically, when externally-applied magnetic field intensity is greater than 2.0 kOe, this coordination polymer magnetic material χ mright tspike in curve under low temperature disappears, and coordination polymer magnetic material shows strong field dependence (Fig. 5 a).
When 2.0 K, the variable field specific magnetising moment of this mixed ligand cobalt (II) coordination polymer magnetic material is along with the increase of externally-applied magnetic field presents two obvious magnetic transition behaviors (Fig. 5 b).When externally-applied magnetic field intensity is strengthened to 1.2 kOe from 0, the specific magnetising moment of mixed ligand cobalt (II) coordination polymer magnetic material also presents the linear trend increasing, and from 0, is increased to 0.17 n β, this is consistent with antiferromagnetic order.When externally-applied magnetic field intensity is increased to 2.5 kOe by 1.2, the specific magnetising moment of mixed ligand cobalt (II) coordination polymer magnetic material is promptly by 0.17 n βbe increased to 0.47 n β, show weak spontaneous magnetization effect.Show that mixed ligand cobalt (II) coordination polymer magnetic material exists a metamagnetic transformation process from antiferromagnetic order to weak spontaneous magnetic state.When externally-applied magnetic field intensity continues to be strengthened to 15 kOe, the specific magnetising moment of mixed ligand cobalt (II) coordination polymer magnetic material is by 0.47 n βlinearity is increased to 3.2 n β.When the magneticstrength of externally-applied magnetic field reaches 15.0 kOe when above, the specific magnetising moment of mixed ligand cobalt (II) coordination polymer magnetic material increases suddenly again.When magneticstrength is 40.0 kOe, the specific magnetising moment of magneticsubstance is 9.16 n β, show that the spin(-)flop transition of secondary induction appears in this magneticsubstance.When the magneticstrength of externally-applied magnetic field is 50.0 kOe, the specific magnetising moment of magneticsubstance is 9.81 n β.By the specific magnetising moment to additional magneticstrength differentiate ( d m/ d h) can show that two transition magnetic field are greatly about 2.0 and 22.5 kOe (Fig. 5 b).This two steps magnetic changes mutually and can further pass through under different externally-applied magnetic fields χ mright tfigure is proven.
Method: mixed ligand cobalt (II) coordination polymer magnetic material is ground to form to uniform powder, obtain certain thickness solid thin layer with mixed with resin extrusion forming.This solid thin layer can respond foreign field fast, delicately to be changed, and records the magnetic signal of different magnetic field.Compare with traditional hard disc of computer information storing material, it is little that the disc material that contains this mixed ligand cobalt (II) ligand polymer composition has volume, relative density is light, good dispersity, the advantages such as easy machine-shaping, can be used as magneticsensor and use, be expected to be applied on the information storage materials such as low density hard disc of computer.
Conclusion: as can be seen here, this coordination polymer magnetic material can record the magnetic signal of different magnetic field, can be used as magneticsensor and uses, and is expected to be applied on the information storage materials such as low density hard disc of computer.

Claims (4)

1. cobalt (II) ligand polymer with 5-methyl isophthalic acid H-tetrazole and the m-phthalic acid mixed ligand of following chemical general formula:
{[Co 7(H 2O) 2( μ 3-OH) 4(mtz) 2(ip) 4]·13/4H 2O}；
Wherein: the structural formula of mtz, ip is as follows:
Mtz is the negative univalent anion of 5-methyl tetrazole, and ip is the negative dianion of m-phthalic acid; Its monocrystalline crystallization is in oblique system p2 1 / cspacer, unit cell parameters is a=8.7597 (4), b=18.6069 (8), c=14.5879 (6), β =97.7600 (10) o, v=2355.92 (18) 3, z=2, there is structure as shown in Figure 1; The main infrared absorption peak of this ligand polymer is 3461 cm- 1, 1603 cm -1, 1558 cm -1, 1543 cm -1, 1524 cm -1, 1482 cm -1, 1457 cm -1, 1356 cm -1, 1267 cm -1, 1159 cm -1, 1083 cm -1, 751 cm -1, 707 cm -1, 666 cm -1, 419 cm -1; There is infrared spectrogram as shown in Figure 2; The three-dimensional framework of ligand polymer decomposes between 352 to 405 ℃, and residual residue is cobalt oxide, has thermogravimetric analysis figure as shown in Figure 3.
2. the preparation method of mixed ligand cobalt (II) ligand polymer described in a claim 1, it is characterized in that: 5-methyl isophthalic acid H-tetrazole, m-phthalic acid and Cobaltous nitrate hexahydrate are obtained to red bulk crystals via solvent thermal reaction in redistilled water and ethanol, and wherein the mol ratio of 5-methyl isophthalic acid H-tetrazole, m-phthalic acid and Cobaltous nitrate hexahydrate is 3:2:3 ~ 3.5; The volume of redistilled water is 7.0 mL, and the volume of ethanol is 3.0 mL; The pH value scope of controlling is 4 ~ 5; After being incubated three days at 180 ~ 190 ℃, drop to room temperature, then washing, dry; Obtain red bulk crystals.
3. preparation method claimed in claim 2, wherein said solvent thermal reaction refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, take redistilled water and ethanol as reaction medium, by temperature control oven, heat 180 ~ 190 ℃ and make internal tank produce spontaneous 1-100 Mpa pressure, make indissoluble or insoluble substance dissolves crystallization under normal conditions.
4. described in claim 1,5-methyl isophthalic acid H-tetrazole and m-phthalic acid mixed ligand cobalt (II) ligand polymer are being applied at material science as molecule based magnetic materials.
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