CN101787043B - Novel light-emitting transition metal organic framework structured compound and preparation method thereof - Google Patents

Novel light-emitting transition metal organic framework structured compound and preparation method thereof Download PDF

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CN101787043B
CN101787043B CN2010101077604A CN201010107760A CN101787043B CN 101787043 B CN101787043 B CN 101787043B CN 2010101077604 A CN2010101077604 A CN 2010101077604A CN 201010107760 A CN201010107760 A CN 201010107760A CN 101787043 B CN101787043 B CN 101787043B
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任铁真
郑冉
肖鹏艳
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Hebei University of Technology
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Abstract

The invention belongs to the technical field of chemical compound preparation and in particular provides a novel metal organic framework structured compound and a preparation method thereof. The structural formula of the compound is [Zn4(mu4-O)(BTC)2(phen)2].4H2O, wherein mu4 is oxo-bridged; BTC is 1,3,5-trimesic acid (C9H6O6); phen is 1,10-o-phenanthroline (C12H8N2); the molecular formula of the compound is C42H30N4O17Zn4 and the molecular weight is 1124.18; the compound belongs to the monoclinic system and C2/c space group; the cell parameter beta is 92.353(3) degrees; the cell volume is shown in the specification, Z is 4 and Dc is 1.806g/cm3. In the method, the cheap and nontoxic zinc acetate or zinc chloride is used as the reactant and the organics trimesic acid and o-phenanthroline are used as the ligands to obtain the Zn-MOFs material. The compound has simple preparation process and equipment and high heat stability at the temperature of more than 450 DEG C and can be widely applied to fluorescent organism markers.

Description

Light-emitting transition metal organic framework structured compound and preparation method thereof
Technical field
The invention belongs to technical field of chemical compound preparation, be specially a kind of novel metal organic framework structured compound and preparation method thereof.
Background technology
Metallic organic framework (MOFs) is the method synthetic Web materials that is passed through the molecule self-assembly by organic ligand that contains oxygen or nitrogen and transition metal, is one of current hot research field.It has the soda acid amphoteric properties, removes the Lewis base position, and the Lewis acid position also is provided.Metal ion has played two effects in skeleton, one is the maincenter that skeleton is provided as node, and another is to form branch in maincenter, strengthens the physical properties (as porousness and chirality) of MOFs.MOFs can still keep the integrity of structure behind the solvent molecule in removing the duct, specific surface area is much larger than the molecular sieve in similar duct, so the MOFs material has many potential properties, in new functional materials such as gas storage, fractionation by adsorption, selectivity catalysis, molecular recognition, reversibility Subjective and Objective molecule (ion) exchange, ultra-high purity is separated, biological conductive material, photoelectric material, shown tempting application prospect [Ling-Guang Qiu in the exploitation of novel material such as magneticsubstance and chip, Li-Na Gu, Solid State Chem., 2009,182.].In recent years, the research by nitrogen heterocyclic ring and aromatic carboxylic acid class part synthesizing new metallic organic framework was the emphasis in this field.
Metal-organic emission type comprises: 1, luminous based on part, i.e. L *→ L type luminous [Christina A.Bauer, J.AM.CHEM.SOC., 2007,129.], when this class ion cooperates with organic ligand, can be that original non-rigid plane configuration changes the inflexible plane configuration into, make originally the organic ligand of do not fluoresce (or hypofluorescence) change a hyperfluorescence person into; 2, luminous based on metal ion, i.e. m *→ m type is luminous, this class luminous normally with rare earth ion as central ion; 3, with transition metal ion as central ion, i.e. π *→ d type and d *→ d type, how fluorescence and phosphorescence do not take place in they and the formed title complex of organic ligand, 4, the charge transfer from the part to the metal ion (LMCT) luminous or from the metal ion to the part (MLCT) [Bai Z S, Liu G X, Lu Y, et al.Inorg.Chem.Commun., 2008,11:513-517] form, the luminous form of this class mainly exists in the metallic organic framework structured material of transition metal and organic ligand formation.
Yet rare earth-organic frame thing has the high problem of cost as molecule and ion fluorescence probe.Compare with transition metal ion, the higher ligancy of rare earth ion often causes the number of the connection mode in the organic frame significantly to increase, and then network interpenetrating takes place, and changes original duct, open metal position and skeleton construction.At present the rare earth that the is used for fluorescence detection-organic frame thing of report mostly is to be media with the organic solvent, and is unstable in the aqueous solution, thereby limited its practical ranges.In addition, luminous intensity is greatly to hinder an important factor of its application inadequately.
Therefore, the transition metal ion of research with fluorescent effect has important practical significance with the title complex of organic ligand formation.
Summary of the invention
Purpose of the present invention is for providing a kind of novel three-dimensional metallic organic framework structural compounds with luminescent properties and preparation method thereof.This luminescent material has the three-dimensional micropore pore passage structure that the metal organic coordination forms, and has that skeletal density is low, adsorptivity strong and advantage such as fluorescence radiation characteristic, and preparation technology and equipment are simple, the crystal phase structure of controlled Zn-MOFs, the thermostability height of material.
The technical solution used in the present invention is:
A kind of novel light-emitting transition metal organic framework structured compound, its structural formula: [Zn 4(μ 4-O) (BTC) 2(phen) 2] 4H 2O, wherein μ 4Be the oxo bridge connection; BTC is: 1,3, and 5-trimesic acid (C 9H 6O 6); Phen is 1,10-phenanthroline (C 12H 8N 2).
Novel light-emitting transition metal organic framework structured compound recited above belongs to oblique system, and its molecular formula is C 42H 30N 4O 17Zn 4, molecular weight is 1124.18, belongs to oblique system, C2/c spacer, unit cell parameters
Figure GSA00000029123200021
β=92.353 (3) °, unit cell volume is
Figure GSA00000029123200024
Z=4, Dc=1.806g/cm 3
Above the preparation method of described light-emitting transition metal organic framework structured compound, may further comprise the steps:
1) under agitation condition, trimesic acid is joined in the sodium hydroxide solution, its mol ratio is a trimesic acid: sodium hydroxide=1: 5-5.2;
2) treating that top mixed solution becomes colorless behind the transparent solution, is that the phenanthroline ethanolic soln of 0.4M～0.8M adds in the above-mentioned solution with volumetric molar concentration, and the same trimesic acid of mole number that phenanthroline adds stirs 30min then;
3) zinc solution is added dropwise in the above-mentioned solution, add-on is the mol ratio zinc salt: trimesic acid: phenanthroline=2: 1: 1, stir reaction 40min down;
4) solution is transferred in the closed reactor and under 180 ℃ of autogenous pressures, reacts 120h, naturally cooling at room temperature after reaction finishes, washing is filtered, and sends into baking oven in 45～55 ℃ of dryings, has obtained having the metallic organic framework structural compounds of luminosity.
Above described zinc salt be zinc acetate or zinc chloride.
The concentration of sodium hydroxide solution recited above is 2M.
Beneficial effect of the present invention is:
1. adopting cheap, nontoxic zinc acetate or zinc chloride is reactant, uses organism trimesic acid and phenanthroline to be part, and acquisition has the organic framework structured Zn-MOFs material of 3-dimensional metal.
2. preparation technology and equipment are simple, the crystal phase structure of controlled Zn-MOFs, and the thermostability height of material can reach more than 450 ℃.
3. Zhi Bei material has good purple-blue-fluorescence spectral response curve, can be widely used in the organism fluorescent marker.Simple on preparation method and the means, workable, be easy to promote.
Description of drawings
The Zn1 of the light-emitting transition metal organic framework structured material that Fig. 1 makes for embodiment 1, Zn2 clustering architecture synoptic diagram;
Duct structural representation in the light-emitting transition metal organic framework structured material that Fig. 2 makes for embodiment 1 (along the c direction of principal axis);
The structure iron of the light-emitting transition metal organic framework structured material that Fig. 3 makes for embodiment 1 (along [101] direction of principal axis);
X-ray diffraction pattern in the light-emitting transition metal organic framework structured material that Fig. 4 makes for embodiment 1;
Thermogravimetric analysis spectrogram in the light-emitting transition metal organic framework structured material that Fig. 5 makes for embodiment 1;
The emmission spectrum of the light-emitting transition metal organic framework structured material that Fig. 6 makes for embodiment 1 (λ ex=330nm).
Embodiment
Embodiment 1
Under agitation condition, the 4mmol trimesic acid is joined in the 10ml sodium hydroxide solution that concentration is 2mol/L, generate water white solution; The 4mmol phenanthroline is dissolved in 10ml ethanol, adds in the above-mentioned solution, form clarifying ligand solution, stir 30min; The aqueous solution that 19ml is contained the 8mmol zinc chloride is added dropwise in the ligand solution, obtains milky white solution, continues to stir 40min; Solution is transferred to 40ml to be had and carries out hydro-thermal reaction 120h under 180 ℃ of autogenous pressures in the teflon-lined stainless steel closed reactor.Naturally cooling at room temperature after reaction finishes, washing is filtered, and sends into baking oven in 45～55 ℃ of dryings, has obtained having the about 0.47g of metallic organic framework structural material of luminosity.With the trimesic acid is reference, the productive rate of HUT-76 about 58%.
By thermogravimetric analysis in conjunction with single crystal diffraction (Bruker SamrtAPEXII X ray single crystal diffractometer) to product, physico-chemical property and structural analysis:
Its molecular formula is C 42H 30N 4O 17Zn 4, molecular weight is 1120, belongs to oblique system, C2/c spacer, unit cell parameters
Figure GSA00000029123200031
β=92.353 (3) °, unit cell volume is
Figure GSA00000029123200034
Z=4, Dc=1.806g/cm 3
As can be seen, an outstanding feature is on this complex structure from accompanying drawing 2 and 3: along the c direction of principal axis one-dimensional channels is arranged, the cross section, duct is
Figure GSA00000029123200035
Parallelogram (accompanying drawing 2); And pore structure is cut off by the little parallelogram that is surrounded by four phenanthroline molecules on [101] direction, makes the duct become bilayer structure, and the axial aperture of b has been divided into trisection (accompanying drawing 3).
Powder X-ray RD x ray diffraction analysis x (accompanying drawing 4) finds out that the synthetic material is mutually attached with the single crystal diffraction fitting data, does not have other impurity.Thermogravimetric analysis shows (accompanying drawing 5), near 500 ℃ of the roastings obvious weightlessness is arranged in air, and 72% weight loss is oxycarbide and oxynitride part as calculated, and remaining be that zinc oxide in the skeleton is about 28%, conforms to the molecular formula of single crystal diffraction calculating.In conjunction with the single crystal diffraction analysis, determine that its structural formula is [Zn by thermogravimetric analysis 4(μ 4-O) (BTC) 2(phen) 2] 4H 2O, its space structure formula is seen Fig. 2 and Fig. 3.
(accompanying drawing 5) determined in thermogravimetric analysis, and it is stable that the skeleton structure of this structure can keep before 450 ℃.Like this, this material can be applied to fields such as catalysis, high temperature absorption.Fluorescence spectrum shows that (accompanying drawing 6) this material has absorption at 400nm, shows as good purple-blue-fluorescence spectral response curve, can be widely used in the organism fluorescent marker.
Its structured data is as follows:
Table 1. crystallographic structural analysis data
Figure GSA00000029123200036
Data gathering scope indication range diffraction collect/is independently finished the final R index of degree of conforming to (I＞2sigma (I)) R index (all data) highest peak value and the hole of angle=26.02 analytic methods data/qualification/parameter F ^2 3.86?to?26.02(°)-18＜＝h＜＝19，-19＜＝k＜＝11，-20＜＝1＜＝2012997/4041[R(int)＝0.0774]99.0％Full-matrix?least-squares?on?F^24041/0/3080.940R1＝0.0485，wR2＝0.0571R1＝0.1133，wR2＝0.06320.947?and?-0.583?e.A^-3
Table 2. atomic coordinate (x 10^4) and effective homogeneity displacement parameter U (eq)
Figure GSA00000029123200041
Figure GSA00000029123200051
Embodiment 2
Other step is with embodiment 1, and difference is that zinc chloride changes zinc acetate into, and the 4mmol phenanthroline is dissolved in 5ml ethanol, obtains having the metallic organic framework structural material 0.465g of luminosity at last
Embodiment 3
Other step is with embodiment 1, and difference is that the mol ratio of trimesic acid and alkali lye is 1: 5.2, obtains having the metallic organic framework structural material 0.479g of luminosity at last.

Claims (4)

1. light-emitting transition metal organic framework structured compound, it is characterized by it is the compound of following chemical formula: [Zn 4(μ 4-O) (BTC) 2(phen) 2] 4H 2O, wherein μ 4Be the oxo bridge connection; BTC is: 1,3, and the 5-trimesic acid; Phen is 1, the 10-o-phenanthroline;
Its structural unit belongs to oblique system, and C2/c spacer, its molecular formula are C 42H 30N 4O 17Zn 4, molecular weight is 1124.18, unit cell parameters
Figure FSB00000648536600011
Figure FSB00000648536600012
Figure FSB00000648536600013
β=92.353 (3) °, unit cell volume is
Figure FSB00000648536600014
Z=4, Dc=1.806g/cm 3
2. the preparation method of the light-emitting transition metal organic framework structured compound in the claim 1 is characterized by and may further comprise the steps:
1) under agitation condition, trimesic acid is joined in the sodium hydroxide solution, its mol ratio is a trimesic acid: sodium hydroxide=1: 5-5.2;
2) treating that top mixed solution becomes colorless behind the transparent solution, is that the o-phenanthroline ethanolic soln of 0.4M～0.8M adds in the above-mentioned solution with volumetric molar concentration, and the same trimesic acid of mole number that o-phenanthroline adds stirs 30min then;
3) zinc solution is added dropwise in the above-mentioned solution, add-on is the mol ratio zinc salt: trimesic acid: o-phenanthroline=2: 1: 1, stir reaction 40min down;
4) solution is transferred in the closed reactor and under 180 ℃ of autogenous pressures, reacts 120h, naturally cooling at room temperature after reaction finishes, washing is filtered, and sends into baking oven in 45～55 ℃ of dryings, has obtained having the metallic organic framework structural compounds of luminosity.
3. as the preparation method of claim 2 light-emitting transition metal organic framework structured compound, it is characterized by described zinc salt is zinc acetate or zinc chloride.
4. as the preparation method of claim 2 light-emitting transition metal organic framework structured compound, the concentration that it is characterized by described sodium hydroxide solution is 2M.
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CN103524539B (en) * 2013-10-08 2015-09-30 重庆师范大学 Luminescent material Zn (phen) (HL) 2and preparation method thereof
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