CN104341460B - Dy (III) Mn (II) mixed metal magnetic complex and preparation method and application - Google Patents
Dy (III) Mn (II) mixed metal magnetic complex and preparation method and application Download PDFInfo
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Abstract
Dy (III) Mn (II) mixed metal magnetic complex constructed the present invention relates to mixed ligand and preparation method and application.The chemical formula of complex of the present invention is [Dy2Mn3(L1)2(L2)12], wherein L1It is Phen or 2,2 '-bipyridyl, L2It is the univalent anion of m-methyl benzoic acid or benzoic acid.Complex is prepared using solvent thermal process, and yield is higher, favorable reproducibility.The coordination compound magnetic material is Dy (III) Mn (II) mixed metal complex containing phenyl aromatic carboxylic acid and azacyclo- neutral ligand, the imaginary signals of its ac magnetic susceptibility have obvious frequency to rely on phenomenon under externally-applied magnetic field, with the behavior similar to single molecular magnetses, there can be huge application value in material science as molecule based magnetic materials.
Description
Statement on subsidizing research or development
The present patent application obtains state natural sciences fund (fund number：21173157) and Tianjin is high etc. 21171129 and
School's science and technology development fund planning item (fund number：Subsidy 2012ZD01).
Technical field
The present invention relates to metal-organic coordination compounds and its molecule based magnetic materials technical field, particularly by fragrance
Organic acid and azacyclo- neutral ligand construct 3d-4fMixed metal magnetic complex and preparation method and application.The cooperation
Thing is Dy (III)-Mn (II) mixed metal complex simultaneously containing phenyl aromatic monoacid and azacyclo- neutral ligand, and its is only
Special magnetic property makes it to be applied in material science as molecule based magnetic materials.
Background technology
3d-fDifferent metal cluster compound is numerous ambits such as contemporary inorganic chemistry, Coordinative Chemistry and material science
One of study hotspot, where the research interest as numerous scientific research personnel, particularly this kind of compound can be used as molecular-based magnets
With molecule magnetic refrigerants the fields such as high density information storage, super low temperature refrigeration have wide tempting application prospect (
X.-J. Kong, Y.-P. Ren, L.-S. Long, Z.-P. Zheng, R.-B. Huang, L.-S.
Zheng, J. Am. Chem. Soc., 2007, 129, 7016 ~ 7017; V. M. Mereacre, A. M. Ako,
R. Clérac, W. Wernsdorfer, G. Filoti, J. Bartolomé, C. E. Anson, A. K.
Powell, J. Am. Chem. Soc., 2007, 129, 9248 ~ 9249).Realize single molecular magnetses in high density information
The practical application of the aspects such as storage, quantum calculation needs to improve their blocking temperature.The raising of blocking temperature then needs increase
The energy barrier of molecular magnetic moment reversion, that is, require that molecule has spin ground states and bigger magnetic anisotropy higher.In transition
Introducing rare earth ion constructs mixed metal magnetic complex in metal complex following advantage：(1) existed in rare earth ion big
That measures is not pairedfElectronics, with ligancy and changeable coordination geometric configuration very high, advantageously forms many of various structures
Core metal cluster compound；(2) many rare earth ions have obvious magnetic anisotropic and big spin ground states in itself.Rare earth and transition
Often it is ferromagnetic coupling between metal ion so as to produce spin ground states high, promotes the formation of single molecular magnetses；(3) transition gold
Category single molecular magnetses are generally required containing more metal ion, and check figure is generally higher than 4, and 3d-4fDifferent metal cluster compound molecule
In containing less metal ion when be likely to turn into single molecular magnetses.In view of above advantage, at the beginning of 2004, Matsumoto etc.
Report the four core [Cu that the copper ion and terbium ion of first ring-type are alternately arranged2Tb2] single molecular magnetses (S. Osa, T.
Kido, N. Matsumoto, N. Re, A. Pochaba, J. Mrozinski, J. Am. Chem. Soc.2004,126, 420 ~ 421).The Magnetic Measurement of the complex shows Cu2+-Tb2+Between be ferromagnetic coupling, the relaxation time is 2.7
x10-8Second, effective energy barrier is 21 K.Hereafter, 3d-4fThe preparation and magnetic property research of mixed metal magnetic complex have obtained wide
General concern.Up to the present, substantial amounts of 3d-4fSingle molecular magnetses, such as Cu (II)-Ln (III), Fe (III)-Ln (III), Co
(II)-Ln (III), Ni (II)-Ln (III), Zn (II)-Ln (III) and Mn (II)-Ln (III) etc. successively reported, wherein
Ln (III) can be rare earth ion (the X.-J. Feng, W.-Z. such as Tb (III), Dy (III), Er (III), Ho (III)
Zhou, Y.-G. Li, H.-S. Ke, J.-K. Tang, R. Clérac, Y.-H. Wang, Z.-M. Su, E.-B.
Wang, Inorg. Chem., 2012, 51, 2722 ~ 2724; C. E. Burrow, T. J. Burchell, P.- H. Lin, F. Habib, W. Wernsdorfer, R. Clérac, M. Murugesu, Inorg. Chem., 2009,48, 8051 ~ 8053; T. Shiga, T. Onuki, T. Matsumoto, H. Nojiri, G. N. Newton,
N. Hoshino, H. Oshio, Chem. Commun., 2009, 3568 ~ 3570; P. Díaz-Gallifa, O.
Fabelo, J. Pasán, L. Cañadillas-Delgado, F. Lloret, M. Julve, C. Ruiz-Pérez,Inorg. Chem.,2014, 53, 6299 ~ 6308; I. A. Kühne, N. Magnani, V. Mereacre, W.
Wernsdorfer, C. E. Anson, A. K. Powell, Chem. Commun., 2014, 50, 1882 ~ 1885;
J.-B. Peng, Q.-C. Zhang, X.-J. Kong, Y.-Z. Zheng, Y.-P. Ren, L.-S. Long, R.-
B. Huang, L.-S. Zheng, Z.-P. Zheng, J. Am. Chem. Soc., 2012, 134, 3314 ~
3317)。
In addition to the species and magnetic attribute that change spin plasmid, the selection of bridging ligand is also influence 3d-4fMagnetic is matched somebody with somebody
One of key factor of compound performance.Up to now, constructed by mixed ligand of phenyl aromatic acid and azacyclo- neutral molecule
The magnetic partner of rare earth-transition metal is also than relatively limited (E. Colacio, J. Ruiz, A. J. Mota, M. A.
Palacios, E. Cremades, E. Ruiz, F. J. White, E. K. Brechin, Inorg. Chem., 2012, 51, 5857 ~ 5868；Y. Zhu, F. Luo, X.-F. Feng, Z.-W. Liao, Y.-M. Song, H.-
X. Huang, X.-Z. Tian, G.-M. Sun, M.-B. Luo, Aust. J. Chem.,2013, 66 ,75 ~ 83;
V. Chandrasekhar, T. Senapati, A. Dey, S. Das, M. Kalisz, R. Clérac, Inorg. Chem., 2012, 51, 2031 ~ 2038;A. Baniodeh, V. Mereacre, N. Magnani, Y.-H. Lan,
J. A. Wolny, V. Schünemann, C. E. Anson, A. K. Powell, Chem. Commun.,2013,49, 9666 ~ 9668).Correlative study contributes to the announcement of the structure-activity relationship for promoting molecule based magnetic materials, and for it is developed
New road is opened up with application.
The content of the invention
Present invention aim at the Dy that one class of offer is constructed by phenyl aromatic monocarboxylic acid and azacyclo- neutral ligand
(III) preparation method of the mixed metal magnetic complexs of-Mn (II) and such complex and application.Such complex is by phenyl
Dy (III)-Mn (II) mixed metal magnetic complex that the n-heterocyclic ligand of fragrant monocarboxylic acid and neutrality is constructed jointly, its exchange
The imaginary signals of magnetic susceptibility have obvious frequency to rely on phenomenon under additional alternating-current field, with the row similar to single molecular magnetses
For that can be used widely in material science as molecule based magnetic materials.
To achieve the above object, the present invention provides following technology contents：
The Dy (III) constructed by the n-heterocyclic ligand of phenyl aromatic monocarboxylic acid and neutrality with following chemical general formulas-
The mixed metal magnetic complexs of Mn (II)：[Dy2Mn3(L1)2(L2)12], wherein L1For neutral Phen (phen) or 2,2 '-
Bipyridyl (bpy)；L2It is the univalent anion of m-methyl benzoic acid (mnb) or benzoic acid (nb).Neutral Phen, 2,
The molecular formula of the univalent anion of 2 '-bipyridyl molecule and phenyl aromatic monoacid (the preferred methyl of substituent R or hydrogen atom) according to
It is secondary to be：
Dy (III)-Mn (II) mixed gold constructed by fragrant organic acid and azacyclo- neutral ligand of the present invention
Belong to the preparation method of magnetic partner, it is characterised in that：By azacyclo- neutral ligand, phenyl aromatic monoacid, nitric hydrate dysprosium
With four nitric hydrate manganese yellow bulk crystals, wherein azepine are obtained in redistilled water and organic solvent via solvent thermal reaction
The mol ratio of ring neutral ligand, phenyl aromatic acid, hydrated rare-earth dysprosium nitrate and four nitric hydrate manganese is 1：5 - 10：1 - 2：
1.5；Redistilled water：The volume ratio of organic solvent is 3：2；The pH value range of reaction system is 5-6；Protected at 160-170 DEG C
Room temperature is dropped to after Wen Sitian, is washed out, dried, obtain yellow bulk crystals.
Solvent thermal reaction of the present invention refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, with second distillation
Water and organic solvent are reaction medium, are heated by temperature control oven（Heated perimeter：100 - 300℃）Make to be produced from inside container
Raw pressure（1 - 100 Mpa）So that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
Dy (III)-Mn (II) mixed metal that phenyl aromatic monoacid of the present invention and azacyclo- neutral ligand are constructed
The monocrystal of magnetic partner, it is characterised in that the complex crystal is in anorthic system space group, cell parametera =
11.4189(5) - 13.696(2) Å, b = 13.999(3) - 15.2503(9) Å, c = 15.904(3) -
17.2802(9) Å, V = 2420.94(19) - 2741.1(3) Å3, Z= 1 - 2；See Fig. 1.Of the present invention
The basic structure of Dy (III)-Mn (II) mixed metal magnetic complex is a centrosymmetric five core restrained molecular, is in symmetrical
Transient metal Mn (II) ion at center connects a pair centrosymmetric rare earth β-diketone complex (III) by three pairs of six carboxyls of aromatic acid
Ion, and then by three pairs of the six of aromatic acid carboxyls two other centrosymmetric transient metal Mn (II) ion is connected again,
Wherein azacyclo- neutral molecule participates in building the coordination polyhedrom of outermost Mn (II) ion as capping ligand.Such mixed gold
Belong to magnetic partner infrared signature absorption peak be
(see Fig. 2)；Complex has heat endurance higher, and its molecular skeleton is 230 oCDecompose (see Fig. 3) afterwards；
The complex has reliable phase purity (see Fig. 4).
The preparation method of the mixed metal magnetic complex monocrystal body of Dy (III)-Mn (II) of the present invention is as follows：
By azacyclo- neutral ligand, phenyl aromatic monoacid, hydrated rare-earth dysprosium nitrate and four nitric hydrate manganese are in secondary steaming
Obtain yellow bulk crystals via solvent thermal reaction in distilled water and organic solvent, wherein azacyclo- neutral ligand, phenyl aromatic acid,
The mol ratio of hydrated rare-earth dysprosium nitrate and four nitric hydrate manganese is 1：5 - 10：1 - 2：1.5；Redistilled water and organic solvent
Volume ratio be 3：2；The pH value range for controlling reaction system is 5 ~ 6；Room temperature is dropped to after being incubated four days at 160-170 DEG C, so
After wash, dry；Obtain yellow bulk crystals.The following examples 1 (A) -4 (D) use the method, and spy is illustrated.
The present invention further discloses Dy (the III)-Mn constructed by phenyl aromatic monocarboxylic acid and azacyclo- neutral ligand
(II) application of the metal cluster magnetic partner in terms of molecule based magnetic materials are prepared is mixed.Molecule based magnetic materials therein are tools
There is the molecule sill of magnetics physical features, with small volume, relative density light, structure diversification, be easy to Compound Machining shaping
The advantages of, can be as high density data storage materials'use.
Dy (III)-Mn (II) mixed metal constructed by phenyl monocarboxylic acid and azacyclo- neutral ligand prepared by the present invention
The distinguishing feature of magnetic partner is：
(1) the compounds of this invention is that Dy (III)-Mn (II) simultaneously containing phenyl monocarboxylic acid and n-heterocyclic ligand is mixed
Metal magnetic complex.
(2) the mixed metal magnetic complex in the present invention is prepared using solvent thermal process, and yield is higher, favorable reproducibility, tool
There is heat endurance and phase purity higher, can be applied in material science as magnetic material.
Brief description of the drawings
Fig. 1 complexs [Dy2Mn3(L1)2(L2)12] crystal structure figure；
Fig. 2 complexs [Dy2Mn3(L1)2(L2)12] infrared spectrogram；
Fig. 3 complexs [Dy2Mn3(L1)2(L2)12] thermogravimetric analysis figure；
Fig. 4 complexs [Dy2Mn3(L1)2(L2)12] powder diagram；
Fig. 5 complexs [Dy2Mn3(L1)2(L2)12] ac magnetic susceptibility curve.
Specific embodiment
For purposes of simplicity and clarity, the hereafter appropriate description for eliminating known technology, in case those are unnecessary
Details influences the description to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, is especially subject to
Illustrate, prepare the initial substance of complex of the present invention, such as phenyl monocarboxylic acid, azacyclo- neutral ligand, four nitric hydrates
Manganese and Dysprosium nitrate hexahydrate can be commercially.
Embodiment 1
Phen is the synthesis of Dy (III)-Mn (II) magnetic partners A of mixed ligand with m-methyl benzoic acid：
By Phen (0.1 mM, 19.8 milligrams), m-methyl benzoic acid (1.0 mMs, 136.0 milligrams), four
Nitric hydrate manganese (0.15 mM, 37.7 milligrams) and Dysprosium nitrate hexahydrate (0.2 mM, 91.3 milligrams) are dissolved in two
Secondary distilled water (6.0 mL) and ethanol (4.0 mL), it is 5 to adjust pH with solid NaOH, and solvent heat kettle is enclosed after stirring several minutes
In.After being incubated four days at 160 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature after obtain yellow bulk crystals, then
Use second distillation water washing, air drying.
Embodiment 2
Phen is the synthesis of Dy (III)-Mn (II) magnetic partners B of mixed ligand with benzoic acid：
By Phen (0.1 mM, 19.8 milligrams), benzoic acid (0.5 mM, 61.0 milligrams), four hydration nitre
Sour manganese (0.15 mM, 37.7 milligrams) and Dysprosium nitrate hexahydrate (0.2 mM, 91.3 milligrams) are dissolved in second distillation
Water (6.0 mL) and ethanol (4.0 mL), it is 5 to adjust pH with solid NaOH, is enclosed in solvent heat kettle after stirring several minutes.170
After being incubated four days at DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature after obtain yellow bulk crystals, then use secondary steaming
Distilled water is washed, air drying.
Embodiment 3
2,2 '-bipyridyl is the synthesis of Dy (III)-Mn (II) magnetic partners C of mixed ligand with m-methyl benzoic acid：
By 2,2 '-bipyridyl (0.1 mM, 15.6 milligrams), m-methyl benzoic acid (0.5 mM, 68.0 milligrams),
Four nitric hydrate manganese (0.15 mM, 37.7 milligrams) and Dysprosium nitrate hexahydrate (0.2 mM, 91.3 milligrams) are dissolved in
Redistilled water (6.0 mL) and ethanol (4.0 mL), it is 6 to adjust pH with solid NaOH, and solvent heat kettle is enclosed after stirring several minutes
In.After being incubated four days at 170 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature after obtain yellow bulk crystals, then
Use second distillation water washing, air drying.
Embodiment 4
2,2 '-bipyridyl is the synthesis of Dy (III)-Mn (II) magnetic partners D of mixed ligand with benzoic acid：
By 2,2 '-bipyridyl (0.1 mM, 15.6 milligrams), benzoic acid (0.5 mM, 61.0 milligrams), four hydrations
Manganese nitrate (0.15 mM, 37.7 milligrams) and Dysprosium nitrate hexahydrate (0.1 mM, 45.7 milligrams) are dissolved in secondary steaming
Distilled water (6.0 mL) and ethanol (4.0 mL), it is 6 to adjust pH with solid NaOH, is enclosed in solvent heat kettle after stirring several minutes.
After being incubated four days at 170 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature after obtain yellow bulk crystals, then with two
Secondary distillation water washing, air drying.
Prepared by the present invention（Embodiment 1-4, A-D）The Dy constructed by phenyl aromatic monocarboxylic acid and n-heterocyclic ligand
(III) structural characterization of-Mn (II) magnetic partner is as follows：
(1) crystal structure determination (Fig. 1)
The monocrystalline of the suitable size of size is chosen under the microscope, in Bruker APEX II CCD diffractometers under 296 K
On, with through graphite monochromatised Mo-K alpha rays (λ=0.71073), withMode collects diffraction data.All diffraction
Data carry out semiempirical absorption correction by SADABS softwares with multi-scan methods.Cell parameter is true with least square method
It is fixed.Data convert and structure elucidation are completed using SAINT and SHELXL program bags respectively.All non-hydrogen atoms are minimum with complete matrix
Square law carries out anisotropy refine.The partial parameters of crystallography point diffraction Data Collection and structure refinement are shown in Table 1, crystal structure
See Fig. 1.
The predominant crystal data and refined parameters of the mixed metal magnetic complex of table 1. Dy (III)-Mn (II)
(2) infrared spectrum measurement (Fig. 2)
The infrared spectrum of mixed metal magnetic complex uses pellet technique in the infrared light of Nicolet FT-IR -200
Determined on spectrometer.
(3) thermogravimetric analysis determines (Fig. 3)
The thermogravimetric analysis experiment of mixed metal magnetic complex is the thermogravimetric in Shimadzu simultaneous DTG -60A
Completed on analyzer, under nitrogen protection with 5 oThe speed of C/min is heated to 800 DEG C of measure from room temperature.Test result shows matches somebody with somebody
The skeleton of compound being capable of stable existence before 230 DEG C.After temperature continues to raise, the skeleton of complex starts to decompose, remaining
Residue is the mixture of rare earth oxide and transition metal oxide.
(4) powder diffraction characterizes phase purity (Fig. 4)
The powder diffraction data of mixed metal magnetic complex is collected and determined on Bruker D8 ADVANCE diffractometers.Instrument
Device operating voltage is 40 kV, and electric current is 40 mA.Use graphite monochromatised Cu target X-rays.Divergent slit width is 0.6 mm,
Antiscatter slits width is 3 mm, and Soller slits are 4 o；Data Collection uses 2θ/θScan pattern, 5 oTo 50 oIn the range of
Continuous scanning is completed, and sweep speed is 0.1 o/ second, step-length is 0.01 o.The simulation conversion of mono-crystalline structures powder diffractogram is used
Mercury 1.4.1 software kits.The powder diffraction result (Fig. 4) of rare earth compounding A-D shows that it has reliable phase purity, is
It provides as the application of molecule based magnetic materials and ensures.
Embodiment 5
The alternating temperature magnetic of Dy (III)-Mn (II) mixed metal magnetic complex (embodiment 1-4, A-D) prepared by the present invention
Rate test result shows, is zero or during 3 kOe when externally-applied magnetic field, and the real part and imaginary part of such complex ac magnetic susceptibility are equal
There is obvious frequency dependent behavior (see Fig. 5).Also, with the continuous reduction of temperature, the imaginary part of ac magnetic susceptibility is in low temperature
4.0 K appear below obvious peak value, show that such complex has slow intensity of magnetization relaxation behavior in low temperature, can dive
Used as molecule based magnetic materials on ground.
Hybrid metal magnetic partner proposed by the present invention be it is a kind of in normal conditions can be with the magnetic material of stable existence
Material, has the advantages that small volume, relative density light, structure diversification, is easy to Compound Machining and is molded, and can be used to make high density
Information storing material and magnetic pipe recording material（Such as CD, floppy disc, hard disc and tape etc.）, it is expected in molecule-based magnetic
It is applied in Material Field.
Claims (3)
1. Dy (III)-Mn (II) mixed metal magnetic complex that the mixed ligand with following chemical general formulas is constructed：
Wherein L1It is Phen phen or 2,2 '-bipyridyl bpy, its chemical structural formula is respectivelyWith；L2It is the univalent anion of m-methyl benzoic acid or benzoic acid, its chemical structural formula isWherein replace
Base R is methyl or hydrogen atom；
The main infrared absorption peak of such complex be 3060 ± 5 cm-1, 2923 ± 5 cmˉ1, 1596 ± 5 cm
ˉ1, 1543 ±5 cmˉ1, 1401 ± 4cmˉ1, 1075 ± 8 cmˉ1, 757 ± 7 cmˉ1, 680 ± 5 cmˉ1,
552 ± 8 cmˉ1, the skeleton of complex being capable of stable existence before 230 DEG C；
The complex crystal is in anorthic system, space groupCell parameter isa = 11.4189(5) - 13.696(2)
Å, b = 13.999(3) - 15.2503(9) Å, c = 15.904(3) - 17.2802(9) Å, V = 2420.94
(19) - 2741.1(3) Å3, Z= 1 - 2；Five symmetrical core molecules, are in the mistake of symmetrical centre centered on basic structure
Cross metal Mn (II) ion by six carboxyls of the three pairs of aromatic acids connect a pair centrosymmetric rare earth metal Dy (III) from
Son, and then by three pairs of the six of aromatic acid carboxyls two other centrosymmetric transient metal Mn (II) ion is connected again, its
Middle azacyclo- neutral molecule participates in building the coordination polyhedrom of outermost Mn (II) ion as capping ligand.
2. mixed ligand described in claim 1 mixes the preparation method of metal magnetic complex, it is characterised in that：Azacyclo- is neutral
Part, phenyl aromatic monoacid, hydrated rare-earth dysprosium nitrate and manganese nitrate are in redistilled water and organic solvent via solvent heat
Reaction obtains yellow bulk crystals, wherein azacyclo- neutral ligand, phenyl aromatic monoacid, and nitric hydrate dysprosium and manganese nitrate rub
You are than being 1：5 - 10：1 - 2：1.5；Redistilled water is 3 with the volume ratio of organic solvent：2；The pH value range of reaction system
It is 5-6；Room temperature is dropped to after being incubated four days at 160-170 DEG C, is washed out, dried, obtain yellow bulk crystals.
3. Dy (III)-Mn (II) that is constructed by phenyl aromatic monoacid and azacyclo- neutral ligand described in claim 1 mixes gold
Application of the category magnetic partner in terms of molecule based magnetic materials are prepared；Molecule based magnetic materials therein are with magnetics physics
The molecule sill of feature can be used as high density data storage materials'use.
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