CN101857604B - Three-dimensional copper coordination polymer with hypoxanthine and pyromellitic benzoic acid mixed ligand and preparation method thereof - Google Patents
Three-dimensional copper coordination polymer with hypoxanthine and pyromellitic benzoic acid mixed ligand and preparation method thereof Download PDFInfo
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- CN101857604B CN101857604B CN2010101730855A CN201010173085A CN101857604B CN 101857604 B CN101857604 B CN 101857604B CN 2010101730855 A CN2010101730855 A CN 2010101730855A CN 201010173085 A CN201010173085 A CN 201010173085A CN 101857604 B CN101857604 B CN 101857604B
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Abstract
The invention relates to a three-dimensional copper coordination polymer with a hypoxanthine base and pyromellitic benzoic acid mixed ligand, a preparation method and application thereof. The chemical formula of the three-dimensional copper coordination polymer provided by the invention is Cu2 (hypH)0.5(H2O)0.5(btec)] . 1. 5H2O, wherein, hypH is the hypoxanthine base and btec is quadrivalent anion of pyromellitic benzoic acid. The coordination polymer is prepared by a hydrothermal method and has higher production rate and good repeatability. The coordination polymer is the first three-dimensional copper coordination polymer with the hypoxanthine base and has ferromagnetic features; and the polymer can be applied to development of materials such as magnetic printing ink, information record, magnetic induction, aerospace, microwave and the like.
Description
Technical field
The present invention relates to metal-organic coordination polymer and molecular based field of magnets; Particularly contain the preparation method and the application thereof of the higher-dimension magneticsubstance of xanthoglobulin base; Said ligand polymer is first three-dimensional copper coordination polymer that contains xanthoglobulin base and equal four phenylformic acid parts, and its magnetic property makes it can be used as the molecular based magnet.
Background technology
In recent years, molecular based material with the orderly space structure of higher-dimension and good physicochemical property of design and synthetic has caused the great interest of people (trip had been imitated once, molecular material-photoelectric functional compound, Shanghai science tech publishing house, 2001; The primary track basis, functional materials chemical progress, Chemical Industry Press, 2005; Hong Maochun, Chen Rong, Liang Wenping, the inorganic chemistry of 21 century, Science Press, 2005; Larsson, K.Molecule-Based Materials:TheStructural Network Approach, Elsevier B.V.; Amsterdam, 2005).Compare with traditional inorganic materials, when organic part and inorganic cation were gathered into solid, the ordering of atom and mode of connection had great influence to the function of system.A branch as the molecular based material; The molecular based magnet relates to the emerging crossing research field of many subjects such as chemistry, physics, material and life science; One of its main task is interaction and the mechanism thereof between the spin plasmid in the research molecular system, discloses the internal relation between molecular magnetism and the structure, finds and screen new functional materials (J.S.Miller; 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).
The xanthoglobulin nucleic acid base contains a plurality ofly can give body with paramagnetic metal ion coordinate N and O; And can demonstrate multiple different coordination mode, become desirable part (E.Sletten, the ActaCrystallogr.1970 of the ordered aggregation of constructing different dimensions; B26,1609-1614; M.E.Kastner, K.F.Coffey, M.J.Clarke, S.E.Edmonds, 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.
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; Garc í a-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).
On the other hand, have the polycarboxylic acid class part that enriches coordination mode, the many carboxyls part that particularly contains aromatic nucleus can be regulated and control ferromagnetic and the antiferromagnetic coupling effect through the metals ion and the coordination configuration of the not carboxyl formation of isomorphic map effectively.In fact, through different aromatic acids construct have ferromagnetic, antiferromagnetic; And a title complex of inducing the spinning change nature is by the extensive and a large amount of research of people (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; Y.Y.Karabach, A.M.Kirillov, M.Haukka, J.Sanchiz, M.N.Kopylovich, A.J.L.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.Pas á n, L.
adillas-Delgado; F.S.Delgado, F.Lloret, M.Julve; C.Ruiz-P é rez; 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.Pas á n; F.S.Delgado, F.Lloret, J.Cano; M.Julve, C.Ruiz-P é rez, Inorg.Chem.2009; 48,11342-11351 etc.).Yet the magneticsubstance that contains the copper coordination polymer of xanthoglobulin and equal four benzoic acid mixed ligands does not simultaneously also appear in the newspapers, and correlative study is that new road is opened up in the exploitation exploration of materials such as magnetic ink, information record, magneticinduction, space flight and microwave.
Summary of the invention
One object of the present invention is to provide a kind of three-dimensional hypoxanthine and pyromellitic benzoic acid copper coordination polymer, and this title complex is the three-dimensional copper coordination polymer that first example contains the xanthoglobulin base, has ferromagnetic character.
Another object of the present invention is to provide a kind of preparation method of three-dimensional xanthoglobulin copper coordination polymer.
A further object of the present invention be to provide a kind of three-dimensional xanthoglobulin copper coordination polymer in preparation as the application aspect the molecular based magnet.For realizing above-mentioned purpose, the present invention provides following technical scheme:
Three-dimensional xanthoglobulin copper coordination polymer with following chemical general formula:
[Cu
2(hypH)
0.5(H
2O)
0.5(btec)]·1.5H
2O
Wherein hypH is the xanthoglobulin base, and btec is equal four benzoic quadrivalent anions, and its molecular formula is following:
Three-dimensional hypoxanthine and pyromellitic benzoic acid mixed ligand copper coordination polymer according to the invention is characterized in that said coordination copper coordination polymer belongs to rhombic system, and spacer is Pmn2
1, unit cell parameters is a=12.0693 (5), b=11.0441 (5),
Z=4; The xanthoglobulin base forms the wavy copper of one dimension-xanthoglobulin zonal structure through the outer carbonylic oxygen atom of ring and two bivalent cupric ions of imidazole ring nitrogen-atoms bidentate bridging, and then forms three-dimensional covalent structure through the carboxyl of Pyromellitic Acid and the coordination behavior expansion of cupric ion.
Three-dimensional xanthoglobulin copper coordination polymer according to the invention, its main infrared absorption peak is 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); Title complex begin to decompose at 340 ℃.
The preparation method of three-dimensional xanthoglobulin copper coordination polymer according to the invention; It is characterized in that xanthoglobulin, equal four phenylformic acid and Gerhardite or Copper dichloride dihydrate are obtained blue bulk-shaped monocrystal body via hydro-thermal reaction in redistilled water; Use methanol wash then, drying; Wherein the mol ratio of xanthoglobulin, equal four phenylformic acid and Gerhardite or Copper dichloride dihydrate is 1～2: 1: 2.Wherein the consumption of the water of hydro-thermal reaction second distillation is 8.0mL～10.0mL.The pH value scope of described hydro-thermal reaction is between 5～8.Said hydrothermal temperature is that 120 ℃～140 ℃ insulations dropped to room temperature after 3 days.
Hydro-thermal reaction of the present invention refers to finger in special encloses container (generally using the stainless steel cauldron of inner liner polytetrafluoroethylene); With water or other organic solvents is reaction medium; Heating (TR: 100-300 ℃) through the external world makes internal tank produce spontaneous pressure (1-100Mpa), and feasible indissoluble under normal conditions or insoluble substance dissolves and crystallization are separated out.
The structural characterization of (embodiment 1-5) three-dimensional xanthoglobulin copper coordination polymer of the present invention's preparation is following:
(1) crystal structure determination (Fig. 1)
Choose the monocrystalline of suitable size at microscopically; Under the room temperature on Bruker APEX II CCD diffractometer; Use through the Mo-K of graphite monochromatization alpha-ray (
), collect diffraction data with
mode.All diffraction datas carry out the semiempirical absorption correction through SADABS software with the multi-scan method.Unit cell parameters is confirmed with method of least squares.Reduction of data and structure elucidation use SAINT and SHELXL routine package to accomplish respectively.All non-hydrogen atoms carry out the anisotropy refine with the complete matrix method of least squares.Structure is seen Fig. 1.The partial parameters of data gathering of crystallography point diffraction and structure refinement is seen table 1.
The main crystallographic data of the three-dimensional xanthoglobulin copper coordination polymer of table 1. and refine parameter
aR
1＝∑||F
o|-|F
c||/|F
o|；
bwR
2＝[∑w(F
o 2-F
c 2)
2/∑w(F
o 2)
2]
1/2.
(2) infrared measurement (Fig. 2)
It is to measure on the IR of Nicolet IR-200 in model that ir spectra adopts pellet technique.
(3) (Fig. 3) measured in thermogravimetric analysis
The thermogravimetric analysis experiment is on the thermogravimetric analyzer of Shimadzu simultaneous DTG-60A, to accomplish, and the speed with 5 ℃/min under nitrogen protection is heated to 800 ℃ of mensuration from room temperature, and the result shows that complex crystal decomposes at 340 ℃.
(4) powdery diffractometry characterizes phase purity (Fig. 4)
Powder diffraction data is collected on the Rigaku D/Max-2500 diffractometer and measures.Instrumentation voltage is 40kV, and electric current is 100mA.Use the Cu target X ray of graphite monochromatization.Scanning constant disperses that to depart from be 1 °, and the reception slit width is 0.3mm; Density data is collected and is used 2 θ/θ scan pattern, and continuous sweep is accomplished in 3 ° to 60 ° scopes, and sweep velocity is 8 °/second, and step-length is 0.02 °.Data fitting is used the Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury 1.4.1 software package.
The present invention further discloses the application of copper coordination polymer aspect preparation molecular based magnet of three-dimensional hypoxanthine and pyromellitic benzoic acid mixed ligand.Can be applicable to fields such as magnetic ink, information record, magneticinduction, space flight and microwave material.
Molecular based magnet of the present invention is a method of utilizing supramolecular chemistry, and paramagnetic metal ion and organic bridge ligand with the mode constructed compounds of self-assembly with the control assembling, are had the spontaneous magnetization behavior below critical temperature.The molecular based magnet has that volume is little, in light weight, transparency is high, solvability good, structure is diversified and be easy to advantages such as Compound Machining moulding.
The distinguishing feature of the three-dimensional xanthoglobulin copper coordination polymer of the present invention's preparation is:
(1) the present invention is the first ligand polymer that contains the three-dimensional structure of xanthoglobulin base.
(2) the outer carbonylic oxygen atom of ring of xanthoglobulin alkali is participated in coordination first in the ligand polymer of the present invention's preparation, and expands structure with two bivalent cupric ions of imidazole ring nitrogen-atoms bidentate bridging.
(3) ligand polymer among the present invention adopts the hydrothermal synthesis method preparation, and productive rate is higher, favorable reproducibility; Has higher thermostability; And have ferro-magnetic character, can be used as the molecular based magnet, be applied to following fields such as magnetic ink, information record, magneticinduction, space flight and microwave material.
Description of drawings
Fig. 1 [Cu
2(hypH)
0.5(H
2O)
0.5(btec)] 1.5H
2The tomograph of O;
Fig. 2 [Cu
2(hypH)
0.5(H
2O)
0.5(btec)] 1.5H
2The infrared spectrogram of O;
Fig. 3 [Cu
2(hypH)
0.5(H
2O)
0.5(btec)] 1.5H
2The thermogravimetric analysis figure of O;
Fig. 4 [Cu
2(hypH)
0.5(H
2O)
0.5(btec)] 1.5H
2The powder diagram of O;
Fig. 5 [Cu
2(hypH)
0.5(H
2O)
0.5(btec)] 1.5H
2The magnetic chart of O.
Embodiment
For simple and purpose clearly, the omission that hereinafter is appropriate the description of known technology, in order to avoid those unnecessary details influences are to the description of present technique scheme.Below in conjunction with preferred embodiment, the present invention is done further description, what explain especially is, prepares the starting substance xanthoglobulin of The compounds of this invention, Pyromellitic Acid, Gerhardite or Copper dichloride dihydrate all can have been bought from market.
Three-dimensional xanthoglobulin copper coordination polymer A's is synthetic:
With organic ligand, xanthoglobulin (0.1 mmole, 13.6 milligrams), Pyromellitic Acid (0.05 mmole; 12.7 milligram) with Gerhardite (0.1 mmole; 24.2 milligram) be dissolved in (10.0mL) in the redistilled water, using triethylamine to regulate pH is 8, encloses in the water heating kettle after the stirred for several minute.Obtain blue bulk-shaped monocrystal in insulation under 120 ℃ after programmed cooling to the room temperature after 3 days, use methanol wash then, drying.
Embodiment 2
Three-dimensional xanthoglobulin copper coordination polymer B's is synthetic:
With organic ligand, xanthoglobulin (0.05 mmole, 6.8 milligrams), Pyromellitic Acid (0.05 mmole; 12.7 milligram) with Gerhardite (0.1 mmole; 24.2 milligram) be dissolved in (8.0mL) in the redistilled water, using triethylamine to regulate pH is 5, encloses in the water heating kettle after the stirred for several minute.Obtain blue bulk-shaped monocrystal in insulation under 140 ℃ after programmed cooling to the room temperature after 3 days, use methanol wash then, drying.
Three-dimensional xanthoglobulin copper coordination polymer C's is synthetic:
With organic ligand, xanthoglobulin (0.1 mmole, 13.6 milligrams), equal four phenylformic acid (0.05 mmole; 12.7 milligram) with Copper dichloride dihydrate (0.1 mmole; 17.5 milligram) be dissolved in (10.0mL) in the redistilled water, using triethylamine to regulate pH is 8, encloses in the water heating kettle after the stirred for several minute.Obtain blue bulk-shaped monocrystal in insulation under 120 ℃ after programmed cooling to the room temperature after 3 days, use methanol wash then, drying.
Embodiment 4
Three-dimensional xanthoglobulin copper coordination polymer D's is synthetic:
With organic ligand, xanthoglobulin (0.05 mmole, 6.8 milligrams), equal four phenylformic acid (0.05 mmole; 12.7 milligram) with Copper dichloride dihydrate (0.1 mmole; 17.5 milligram) be dissolved in (8.0mL) in the redistilled water, using triethylamine to regulate pH is 6, encloses in the water heating kettle after the stirred for several minute.Obtain blue bulk-shaped monocrystal in insulation under 140 ℃ after programmed cooling to the room temperature after 3 days, use methanol wash then, drying.
Ferromagnetic property research to three-dimensional xanthoglobulin copper coordination polymer:
Magnetic performance adopts Quantum Design MPMS-XL-7 SQUID magnetometer mensuration to select for use 2000 Gauss's dc fields to measure the alternating temperature susceptibility curve of complex monocrystal at 2-300K.The Magnetic Measurement data of crystalline state sample show that this ligand polymer is the ferro-magnetic of a three-dimensional magnetic order, can be applicable to fields such as magnetic ink, information record, magneticinduction, space flight and microwave material as the molecular based magnet, see Fig. 5.For example this title complex has the ferromegnetism similar with iron oxide black or iron oxide brown and is easier to grinding dispersion, thereby the basal component that can be used as magnetic ink is that magnetic paint uses.Compare with traditional pigment (iron oxide black or iron oxide brown), the magnetic paint that contains this title complex has better resistance toheat and resistance to acids and bases.
After the preferred embodiment that specifies; Being familiar with this technological personage can be well understood to; Do not break away from above-mentioned claim with spirit under can carry out various variations and modification; All foundations technical spirit of the present invention all belongs to the scope of technical scheme of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the present invention does not also receive the restriction of the embodiment that gives an actual example in the specification sheets.
Claims (7)
1. the three-dimensional hypoxanthine and pyromellitic benzoic acid mixed ligand copper coordination polymer that has following chemical general formula:
[Cu
2(hypH)
0.5(H
2O)
0.5(btec)]·1.5H
2O；
Wherein hypH is the xanthoglobulin base, and btec is equal four benzoic quadrivalent anions, and its molecular formula is following:
Said coordination copper coordination polymer belongs to rhombic system, and spacer is Pmn2
1, unit cell parameters does
Z=4; The xanthoglobulin base forms the wavy copper of one dimension-xanthoglobulin zonal structure through the outer carbonylic oxygen atom of ring and two bivalent cupric ions of imidazole ring nitrogen-atoms bidentate bridging, and then forms three-dimensional covalent structure through the carboxyl of Pyromellitic Acid and the coordination behavior expansion of cupric ion.
2. the said three-dimensional xanthoglobulin copper coordination polymer of claim 1, its main infrared absorption peak is 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
-1Title complex is 340 ℃ of decomposition.
3. the preparation method of the said three-dimensional xanthoglobulin copper coordination polymer of claim 1; It is characterized in that xanthoglobulin, equal four phenylformic acid and Gerhardite or Copper dichloride dihydrate are obtained blue bulk-shaped monocrystal body via hydro-thermal reaction in redistilled water; Use methanol wash then, drying; Wherein the mol ratio of xanthoglobulin, equal four phenylformic acid and Gerhardite or Copper dichloride dihydrate is 1-2: 1: 2.
4. the described preparation method of claim 3, the consumption that it is characterized in that the redistilled water of said hydro-thermal reaction is 8.0mL-10.0mL.
5. the described preparation method of claim 3, the pH value scope of wherein said hydro-thermal reaction is between the 5-8.
6. the preparation method of the said ligand polymer of claim 3 is characterized in that said hydrothermal temperature is that 120 ℃-140 ℃ insulations dropped to room temperature after 3 days.
7. the application of the said three-dimensional xanthoglobulin copper coordination polymer of claim 1 aspect preparation molecular based magnet.
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