CN105001247B - 4 bromine M-phthalic acids and 1,4 2 (methylene of imidazoles 1) benzene mixture cadmium complexes and preparation method - Google Patents
4 bromine M-phthalic acids and 1,4 2 (methylene of imidazoles 1) benzene mixture cadmium complexes and preparation method Download PDFInfo
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- CN105001247B CN105001247B CN201510413672.XA CN201510413672A CN105001247B CN 105001247 B CN105001247 B CN 105001247B CN 201510413672 A CN201510413672 A CN 201510413672A CN 105001247 B CN105001247 B CN 105001247B
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- imidazoles
- methylene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 150000001661 cadmium Chemical class 0.000 title claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title abstract 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title abstract 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 26
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000011835 investigation Methods 0.000 abstract description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
A kind of 4 bromine M-phthalic acids and Isosorbide-5-Nitrae two (methylene of imidazoles 1) benzene mixture cadmium complex, chemical formula are：{[Cd(4‑Br‑ip) (bix)]·H2O}∞, 4 described bromine M-phthalic acids and Isosorbide-5-Nitrae two (methylene of imidazoles 1) benzene mixed cadmium complex crystal belong to monoclinic system；Preparation method is, by 4 bromine M-phthalic acids, alkali, 1,4 two (methylene of imidazoles 1) benzene and metal cadmium salt are soluble in water, enclose in reactor, 120 ~ 160 DEG C are heated to 10 DEG C per hour of heating rate, maintains this temperature 3 days, the colourless bulk crystals being collected into, successively by washing, drying process, complex is obtained；The complex has certain heat endurance, and the fluorometric investigation result of crystal prototype shows and can be developed and applied as fluorescent material in materials science field.
Description
Technical field
The present invention relates to a kind of complex, specifically 4- bromines M-phthalic acid and Isosorbide-5-Nitrae-two (imidazoles -1- methylene)
Benzene mixture cadmium complex and preparation method thereof.
Background technology
At present, the various metals formed by organic ligand and metallic ion coordination self assembly or controllable self assembly-organic
The research of complex material is very active, this be due to complex not only have interesting and various molecular structure and
Topological structure, it is often more important that it shows tempting application prospect in field of new materials such as fluorescence, absorption, catalysis, magnetic.One
Since straight cadmium basigamy compound due to abundant structure and various potential applications and as Coordinative Chemistry study hotspot it
One.Phenyl polycarboxylic acid part has abundant coordination mode, is paid close attention to by chemist.M-phthalic acid and its derivative are one
The important organic ligand of class, and show excellent Potential performance.
The content of the invention
The present invention provide a kind of 4- bromines M-phthalic acid and (imidazoles -1- methylene) the benzene mixture cadmium complexes of 1,4- bis- and its
Preparation method.
4- bromines M-phthalic acid and Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene mixture cadmium complex, chemical formula are：{[Cd(4-
Br-ip) (bix)]·H2O}∞；
Described 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixed cadmium complex crystal belong to monocline
Crystallographic system, space group areP2(1)/n, cell parameter isa=7.4410 (13),b=14.676 (3),c = 21.473(4)
,α=90 °,β=107.362 (6) °,γ=90 °,V = 2238.1(7) Å3；
The complex basic structure is a three-dimensional net structure, and basic structural unit contains a CdIIIon, Cd1
Octahedral coordination, Cd1 six coordination atoms be respectively two Isosorbide-5-Nitraes-two (imidazoles -1- methylene) benzene two nitrogen-atoms and
Four carboxyl oxygen atoms of two 4- bromine M-phthalic acid ions.4- bromine M-phthalic acids ion connects adjacent Cd ions difference
Formed it is one-dimensional withbAxle is the left hand helix chain and right-handed helix chain of symmetry axis.Adjacent one dimensional helical chain passes through the (miaows of 1,4- bis-
Azoles -1- methylene) benzene N atoms and Cd ions between Cd-N key connections formed three-dimensional structure.Three independent three-dimensional structures
The interspersed triple interspersed structures for forming 3D → 3D mutually.From the point of view of topological structure, the three-dimensional structure of complex can be reduced to
The cds- (6 of 4- connections5.8 it is) topological.
Wherein 4-Br-H2Ip is 4- bromine M-phthalic acids, and structure is as follows：
；
Wherein bix is Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene, and structure is as follows：
。
The preparation method of 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex：In hydro-thermal
Under conditions of, by 4-Br-H2Ip, alkali, bix and metal cadmium salt are soluble in water, enclose in reactor, with 10 DEG C per hour of liter
Warm speed is heated to 120 ~ 160 DEG C, maintains this temperature 3 days, and then natural conditions drop to room temperature, you can obtain colourless bulk
Crystal, then, by the colourless bulk crystals being collected into successively by washing, drying process, 4- bromines M-phthalic acid and 1 are obtained,
4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；
The 4- bromines M-phthalic acid, the addition of 1,4- bis- (imidazoles -1- methylene) benzene, cadmium salt and inorganic base are respectively
Every 1 L water adds 0.005 ~ 0.015 mol 4- bromines M-phthalic acid, (imidazoles -1- is sub- by 0.005 ~ 0.015 mol 1,4- bis-
Methyl) benzene, 0.005 ~ 0.015 mol cadmium salt and 0.005 ~ 0.015 mol alkali.
Described alkali is inorganic base, is preferably potassium hydroxide or sodium hydroxide；Described cadmium salt is three acetate hydrate cadmiums
Or four nitric hydrate cadmium.
Beneficial effect is：
The complex that synthetic method provided by the invention obtains, have stability good, synthesis is simple, easy to operate, yield
The advantages that high and reproducibility is good.The fluorometric investigation result of crystal prototype, provided for further exploitation fluorescent functional molecular material
Theoretical foundation, can be developed and applied as fluorescent material in materials science field.The thermogravimetric analysis of complex characterizes aobvious
Show that its skeleton can be stabilized below 120 DEG C, there is certain heat endurance, be that it should as the further exploitation of material
Ensured with providing.
Brief description of the drawings
Fig. 1 is Cd coordination environments in 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex
Figure；
Fig. 2 is the three-dimensional network figure of 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；
Fig. 3 is the topological network of 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；
4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex prepared by Fig. 4 embodiments 1
Infared spectrum；
Fig. 5 is the powder diagram of 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；
Fig. 6 is 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex thermogravimetric curve figure；
Fig. 7 is 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixed cadmium complex fluorescent collection of illustrative plates.
Embodiment
As illustrated, 4- bromines M-phthalic acid and Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene mixture cadmium complex, chemical formula
For：{[Cd(4-Br-ip) (bix)]·H2O}∞；Described 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene
Mixed cadmium complex crystal belongs to monoclinic system, and space group isP2(1)/n, cell parameter isa=7.4410 (13),b =
14.676 (3),c=21.473 (4),α=90 °,β=107.362 (6) °,γ=90 °,V = 2238.1(7)
Å3；
The complex basic structure is a three-dimensional net structure, and basic structural unit contains a CdIIIon, Cd1
Octahedral coordination, Cd1 six coordination atoms be respectively two Isosorbide-5-Nitraes-two (imidazoles -1- methylene) benzene two nitrogen-atoms and
Four carboxyl oxygen atoms of two 4- bromine M-phthalic acid ions.4- bromine M-phthalic acids ion connects adjacent Cd ions difference
Formed it is one-dimensional withbAxle is the left hand helix chain and right-handed helix chain of symmetry axis.Adjacent one dimensional helical chain passes through the (miaows of 1,4- bis-
Azoles -1- methylene) benzene N atoms and Cd ions between Cd-N key connections formed three-dimensional structure.Three independent three-dimensional structures
The interspersed triple interspersed structures for forming 3D → 3D mutually.From the point of view of topological structure, the three-dimensional structure of complex can be reduced to
The cds- (6 of 4- connections5.8 it is) topological.
Wherein 4-Br-H2Ip is 4- bromine M-phthalic acids, and structure is as follows：
；
Wherein bix is Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene, and structure is as follows：
。
The preparation method of 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex：In hydro-thermal
Under conditions of, by 4-Br-H2Ip, alkali, bix and metal cadmium salt are soluble in water, enclose in reactor, with 10 DEG C per hour of liter
Warm speed is heated to 120 ~ 160 DEG C, maintains this temperature 3 days, and then natural conditions drop to room temperature, you can obtain colourless bulk
Crystal, then, by the colourless bulk crystals being collected into successively by washing, drying process, 4- bromines M-phthalic acid and 1 are obtained,
4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；
The 4- bromines M-phthalic acid, the addition of 1,4- bis- (imidazoles -1- methylene) benzene, cadmium salt and inorganic base are respectively
Every 1 L water adds 0.005 ~ 0.015 mol 4- bromines M-phthalic acid, (imidazoles -1- is sub- by 0.005 ~ 0.015 mol 1,4- bis-
Methyl) benzene, 0.005 ~ 0.015 mol cadmium salt and 0.005 ~ 0.015 mol alkali.
Described alkali is inorganic base, is preferably potassium hydroxide or sodium hydroxide；Described cadmium salt is three acetate hydrate cadmiums
Or four nitric hydrate cadmium.
With reference to embodiment, the present invention is further elaborated.
Embodiment one
By 4- bromines M-phthalic acid (0.1 mmol), 1,4- bis- (imidazoles -1- methylene) benzene (0.1 mmol), NaOH
(0.1 mmol) is dissolved in water with three acetate hydrate cadmiums (0.1 mmol)（12 mL）In, enclose in 25 mL reactor, with per small
When 10 DEG C of speed be heated to 130 DEG C, maintain this temperature 3 days, be then naturally cooling to room temperature, you can obtain colourless block brilliant
Body, the crystal is separated, successively by washing, drying process, obtain target product, yield about 58%.Main infrared suction
Receiving peak is：3410 w, 3118 w, 2940 w, 1613 s, 1569 s, 1517 s, 1463 s, 1437 s, 1352
s, 1322 s, 1297 s, 1263 s, 1247 m, 931 s, 882 s, 778 s。
By the 4- bromines M-phthalic acid prepared by embodiment one and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex
Further characterization is as follows：
（1）The crystal structure determination of complex
The monocrystalline for choosing suitable size carries out X-ray diffraction experiment at room temperature.In Bruker Apex II X-rays
Single crystal diffractometer collects diffraction data, with the Mo of graphite monochromator monochromatizationKαRay (λ=0.71073), withφ – ω
Mode collects diffraction data.Total data passes throughLpThe factor and empirical absorption correction, crystal structure use SHELXS -97 programs
Solved by direct method, hydrogen atom synthesizes and is fixed on calculated optimum position by difference Fourier and determines.With SHELX-
97 programs, whole non-hydrogen atoms and its anisotropy thermal parameter are based onF 2Complete matrix least square method amendment.In detail
Thin axonometry data are shown in Table 1；Important bond distance and bond angle data is shown in Table 2.Crystal structure is shown in Fig. 1 to Fig. 3.
（2）The IR Characterization of complex
The infared spectrum of complex is shown in Fig. 4.（INSTRUMENT MODEL：The infrared spectrometers of NICOLET 6700）.
（3）The powder x-ray diffraction phase purity of complex characterizes
The powder x-ray diffraction collection of illustrative plates of complex and the diffracting spectrum of test simulation coincide, and illustrate that it has reliable phase
Purity, guarantee is provided as the application of fluorescent material for it, sees Fig. 5.（INSTRUMENT MODEL：Bruker/D8 Advance）.
The predominant crystal data of the complex of table 1
The important bond distance's () of table 2 and bond angle (°)
Symmetric code: #1 -x + 3, y - 1/2, -z + 3/2
（4）The heat endurance of complex characterizes
The thermogravimetric analysis of complex, which characterizes, shows that its skeleton remains to be stabilized at 120 DEG C or so, has certain heat steady
It is qualitative, provide heat endurance as the further development and application of material for it and ensure.It is finally organic to match somebody with somebody with the rise of temperature
Body all loses.See Fig. 6.（INSTRUMENT MODEL：SII EXStar6000 TG/DTA6300）.
（5）The solid fluorescence performance study of complex
Complex crystal sample after enrichment processing carries out the test of solid fluorescence：Complex obtains one at 402 nm
Emission peak, see Fig. 7.（INSTRUMENT MODEL：HITACHI/F-4500）.
It can see by above-mentioned characterization result, complex complex crystal of the present invention belongs to monoclinic system, space group
ForP2(1)/n, cell parameter isa=7.4410 (13),b=14.676 (3),c=21.473 (4),α=90 °,β=107.362 (6) °,γ=90 °,V = 2238.1(7) Å3.It is a three-dimensional net structure, and basic structural unit contains
There is a CdIIIon, Cd1 are octahedral coordinations, and Cd1 six coordination atoms are respectively two Isosorbide-5-Nitraes-two (imidazoles -1- methylenes
Base) two nitrogen-atoms of benzene and four carboxyl oxygen atoms of two 4- bromine M-phthalic acid ions.4- bromine M-phthalic acid ions
Connect adjacent Cd ions formed respectively it is one-dimensional withbAxle is the left hand helix chain and right-handed helix chain of symmetry axis.Adjacent is one-dimensional
Cd-N key connections between N atoms and Cd ions that coiled strand passes through 1,4- bis- (imidazoles -1- methylene) benzene form three-dimensional structure.
Three independent three-dimensional structures intert mutually the triple interspersed structures for forming 3D → 3D.From the point of view of topological structure, complex
Three-dimensional structure can be reduced to the cds- (6 of 4- connections5.8 it is) topological.
Embodiment two
By 4- bromines M-phthalic acid (0.06 mmol), 1,4- bis- (imidazoles -1- methylene) benzene (0.06 mmol), KOH
(0.06 mmol) is dissolved in water with three hydration cadmium acetates (0.18 mmol)（12 mL）In, enclose in 25mL reactor, with per small
When 10 DEG C of speed be heated to 160 DEG C, maintain this temperature 3 days, be then naturally cooling to room temperature, you can obtain colourless block brilliant
Body, the crystal is separated, successively by washing, drying process, obtain target product, yield about 53%.
Embodiment three
By 4- bromines M-phthalic acid (0.18 mmol), 1,4- bis- (imidazoles -1- methylene) benzene (0.18 mmol), NaOH
(0.18 mmol) is dissolved in water with four nitric hydrate cadmiums (0.06 mmol)（12 mL）In, enclose in 25mL reactor, with every
The speed of 10 DEG C of hour is heated to 130 DEG C, maintains this temperature 3 days, is then naturally cooling to room temperature, you can obtain colourless bulk
Crystal, the crystal is separated, successively by washing, drying process, obtain target product, yield about 45%.
Example IV
By 4- bromines M-phthalic acid (0.12 mmol), 1,4- bis- (imidazoles -1- methylene) benzene (0.12 mmol), KOH
(0.1 mmol) is dissolved in water with three hydration cadmium acetates (0.12 mmol)（12 mL）In, enclose in 25 mL reactor, with per small
When 10 DEG C of speed be heated to 120 DEG C, maintain this temperature 3 days, be then naturally cooling to room temperature, you can obtain colourless block brilliant
Body, the crystal is separated, successively by washing, drying process, obtain target product, yield about 46%.
Above example is merely to illustrate present disclosure, and in addition, the present invention also has other embodiment.But
It is that all technical schemes formed using equivalent substitution or equivalent deformation mode are all fallen within protection scope of the present invention.The present invention
Described in 4- bromines M-phthalic acid, 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex, potassium hydroxide, sodium hydroxide；
The chemical reagent such as three acetate hydrate cadmiums and four nitric hydrate cadmiums can be commercially available by market.
Claims (2)
- The preparation method of 1.4- bromines M-phthalic acid and Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene mixture cadmium complex, it is special Sign is:Chemical formula is:{[Cd(4-Br-ip) (bix)]·H2O}∞, described 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixed cadmium complex crystal belongs to monoclinic system, and space group is P 2 (1)/n, cell parameter Fora =7.4410 (13),b=14.676 (3),c =21.473 (4),α=90 °,β=107.362 (6) °,γ= 90 °,V= 2238.1(7) Å 3；The ip of 4-Br-H 2 are 4- bromine M-phthalic acids, and structure is as follows：；The bix is Isosorbide-5-Nitrae-two (imidazoles -1- methylene) benzene, and structure is as follows：；The complex basic structure is three-dimensional net structure, and basic structural unit contains a Cd II ion, and Cd1 is octahedral Body is coordinated, and Cd1 six coordination atoms are respectively two nitrogen-atoms and two of two Isosorbide-5-Nitraes-two (imidazoles -1- methylene) benzene Four carboxyl oxygen atoms of individual 4- bromines M-phthalic acid ion；4- bromine M-phthalic acids ion connects adjacent Cd ions difference Form one-dimensional left hand helix chain and right-handed helix chain using b axles as symmetry axis；Adjacent one dimensional helical chain passes through the (miaows of 1,4- bis- Azoles -1- methylene) benzene N atoms and Cd ions between Cd-N key connections formed three-dimensional structure；Three independent three-dimensionals Structure interts mutually the triple interspersed structures for forming 3D → 3D；4- bromines M-phthalic acid, inorganic base, (imidazoles -1- methylene) benzene of Isosorbide-5-Nitrae-two and metal cadmium salt is soluble in water, enclose anti- Answer in kettle, be heated to 120 ~ 160 DEG C with 10 DEG C per hour of heating rate, maintain this temperature 3 days, then under natural conditions It is down to room temperature, you can colourless bulk crystals are obtained, the colourless bulk crystals of collection are then passed through into washing, drying process successively, Obtain 4- bromines M-phthalic acid and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex；The 4- bromines M-phthalic acid, the addition of 1,4- bis- (imidazoles -1- methylene) benzene, cadmium salt and inorganic base are respectively every 1 L water adds 0.005 ~ 0.015 mol 4- bromines M-phthalic acid, (imidazoles -1- is sub- by 0.005 ~ 0.015 mol 1,4- bis- Methyl) benzene, 0.005 ~ 0.015 mol cadmium salt and 0.005 ~ 0.015 mol inorganic base；Described cadmium salt is three hydrations Cadmium acetate or four nitric hydrate cadmiums.
- 2. the system of 4- bromines M-phthalic acid as claimed in claim 1 and 1,4- bis- (imidazoles -1- methylene) benzene mixture cadmium complex Preparation Method, it is characterised in that：Described inorganic base is potassium hydroxide or sodium hydroxide.
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