CN102584867B - 6-thionicotinic acid cadmium coordination complex and preparation method thereof - Google Patents
6-thionicotinic acid cadmium coordination complex and preparation method thereof Download PDFInfo
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- CN102584867B CN102584867B CN201210015631.1A CN201210015631A CN102584867B CN 102584867 B CN102584867 B CN 102584867B CN 201210015631 A CN201210015631 A CN 201210015631A CN 102584867 B CN102584867 B CN 102584867B
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Abstract
The invention relates to a 6-thionicotinic acid cadmium coordination complex and a preparation method thereof. The coordination complex has the following chemical formula: {[Cd2L2(SO4)].DMF.2NH2(CH3)2}infinity, wherein L is equal to a 6-thionicotinic acid carboxylic anion ligand; and DMF is equal to N,N-dimethylformamide. The synthesis method of the coordination complex is characterized by dissolving a 6,6'-dithiodinicotinic acid ligand and cadmium sulfate into N,N-dimethylformamide under the solvothermal condition to prepare solution, sealing the solution into a 25mL reaction kettle, heating the solution to a certain temperature at a rate of 10 DEG C per hour, maintaining the temperature for three days and then naturally reducing the temperature to the room temperature, thus obtaining the coordination complex. The coordination complex has the advantages of good stability, simpleness in synthesis, convenience in operation, high yield, good reproducibility and the like. The obtained crystalline material is expected to be further researched, developed and applied in the field of fluorescent materials.
Description
Technical field
The present invention is specifically related to d
10a kind of 6-sulphur nicotinic acid cadmium complex and the preparation method of metal complex fluorescent material and gas adsorbing domain.Described title complex has the three-dimensional { 48 of three nodes (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2topology network architecture.
Background technology
Using experience and the method appropriate design of crystal engineering is one of study hotspot of current coordination chemistry, supramolecular chemistry, materials chemistry and association area with the ligand polymer that preparation has particular network structure and physicochemical property.As a class novel molecular base crystalline material, ligand polymer all demonstrates potential application prospect in all many-sides such as object exchange and separated, gas storage, chiral separation, medicament slow release, electroluminescent, selective catalysis, molecular recognition and micropore devices.International and domestic research institution is all synthetic in the orientation of making great efforts to be devoted to function ligand polymer, has obtained in this respect a lot of great successes.Yet because constructing of ligand polymer is subject to the impact of several factors, structure is wayward, and the formation mechanism of title complex is not also had enough knowledge.So up to the present, realize needed ligand polymer or the no small difficult problem with specific function of NW-TFT regulation and control.
Particularly by flexible ligand assemble ligand polymer network more wayward and prediction.Flexible ligand is because its special configuration feature makes distance between hapto, joins angle between tooth and the shape of coordination group is all easy to change, and this makes us be difficult to control reaction conditions to reach target ligand polymer., not only easily there is in configuration framework deformation in the flexible ligand that wherein contains cystine linkage, and at some reaction conditionss unstablely very easily there is the formation that reaction in－situ causes new part.6,6 '-bis-sulphur nicotinic acid are the flexible ligands that typically contain cystine linkage.And the organic ligand of sulfur-bearing has good biological activity, and because the yielding ability of structure can the place of constructing has the ligand polymer of special topological framework.For example the Wang Yao space teach problem of Northwest University selects this part under different reaction conditionss, to carry out the self-assembly of title complex from transition metal, rare earth metal salt respectively, introduce simultaneously and severally there is the nitrogenous bridgingligand of different flexible neutrality and carry out the regulation and control of complex structure, a series of Zn/Cd/Cu/Ln (Ln=Gd have been synthesized, Tb, Er) etc. 18 title complexs that structure is various.(as: Zhang Y.N.; Wang Y.Y.; Shi Q.Z. et al. Cryst. Growth Des.
2011, 1531 – 1541; CrystEngComm,
2010, 3840 – 3851; Inorg. Chem. Acta.
2010, 3413 – 3419; Zhang Yanan, based on flexible ligand 6, the ligand polymer that 6'-bis-sulphur two nicotinic acid are constructed synthetic, the research of structure and character, Ph D dissertation, 2011).But under the condition of solvent thermal, there is reaction in－situ, by 6,6'-, bis-sulphur two nicotinic acid, obtain 6-sulphur nicotinic acid cadmium complex { [Cd
2 l 2(SO
4)] DMF2NH
2(CH
3)
2)
∞, and this title complex has the three-dimensional { 48 of three nodes (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2so far also nobody topology network architecture report for work.The advantages such as the invention discloses a kind of 6-sulphur nicotinic acid cadmium complex, its synthetic method is simple, easy to operate, and has good stability, and productive rate height and reproducibility are good.
Summary of the invention
The object of the invention is to disclose a kind of synthetic method and application of 6-sulphur nicotinic acid cadmium complex.
For achieving the above object, the technical solution used in the present invention is as follows:
6-sulphur nicotinic acid cadmium complex of the present invention, described title complex has following chemical formula, that is: { [Cd
2 l 2(SO
4)] DMF2NH
2(CH
3)
2)
∞, wherein
l=6-sulphur nicotinic acid carboxyl anion part, DMF=DMF;
lskeleton symbol is as follows:
And described complex crystal belongs to triclinic(crystalline)system, spacer is
p-1, unit cell parameters is a=7.8398 (3), b=14.4250 (10), c=14.4884 (10), α=90.760 (6)
o, β=97.907 (5)
o, γ=105.506 (5)
o, V=1561.68 (16)
3.
Described complex crystal has three-dimensional coordinated network structure, wherein, has two kinds of different Cd
iIcoordination environment, the tetrahedral coordination environment that Cd1 is distortion, and the pentagonal bipyramid that the sterie configuration of Cd2 is distortion.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: SO
4 2 –ion connects two Cd2 metal centers, can be simplified to connective bar; Cd1 respectively with four
lpart is connected, and Cd2 respectively with two
lpart is connected with another Cd2, and Cd1 and Cd2 can be simplified to respectively 4 connections and 3 connected nodes; Part
lrespectively with two Cd1 and a Cd2 totally three metal centers be connected, so can be simplified to 3 connected nodes.Thus, the three-dimensional net structure of this title complex can be simplified as { 48 of three nodes (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2topological network.
The preparation method of 6-sulphur nicotinic acid cadmium complex of the present invention, be under the condition of solvent thermal, 6,6'-, bis-sulphur two nicotinic acid parts and sulfuric acid cadmium salt are dissolved in to N, in dinethylformamide, making solution encloses in the reactor of 25 mL, with the speed of 10 ℃ per hour, be heated to certain temperature, maintain this temperature 3 days, be then naturally down to room temperature, can obtain colourless rhabdolith, this monocrystalline is separated, through washing, drying treatment, obtained target product successively.
Described 6,6'-bis-sulphur two nicotinic acid parts are dissolved in that in DMF, to make strength of solution be 0.005 ~ 0.01 mol L
– 1.
Described sulfuric acid cadmium salt is dissolved in that in DMF, to make strength of solution be 0.01 ~ 0.02 mol L-1.
6,6'-, bis-sulphur two nicotinic acid parts and sulfuric acid cadmium salt are dissolved in to be made solution and encloses in the reactor of 25 mL and be heated to 120 ~ 140 ℃ with 10 ℃ per hour in DMF.
The advantages such as synthetic method provided by the invention obtains title complex, has good stability, synthetic simple, easy to operate, and productive rate height and reproducibility are good.The fluorescence data of crystal prototype shows that this type of title complex has stable fluorescence property, can be used as fluorescent material and is applied at material science.The thermogravimetric analysis of title complex characterize show its skeleton approach 120 ℃ of left and right still can stable existence, there is certain thermostability, for its further Application and Development as fluorescent material provides assurance.
Accompanying drawing explanation
Fig. 1 contains Cd in 6-sulphur nicotinic acid cadmium complex
iIcoordination environment figure;
The tomograph that Fig. 2 contains 6-sulphur nicotinic acid cadmium complex;
{ 48 of three nodes that Fig. 3 contains 6-sulphur nicotinic acid cadmium complex (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2topological network;
The solid state fluorescence spectrogram that Fig. 4 contains 6-sulphur nicotinic acid cadmium complex;
The test of the powdery diffractometry (XPRD) that Fig. 5 contains 6-sulphur nicotinic acid cadmium complex and theoretical contrast figure;
The thermogravimetric curve figure that Fig. 6 contains 6-sulphur nicotinic acid cadmium complex.
Embodiment
Complex crystal of the present invention is characterized in that described complex crystal belongs to triclinic(crystalline)system, and spacer is
p-1, unit cell parameters is
a=7.8398 (3),
b=14.4250 (10),
c=14.4884 (10), α=90.760 (6)
o,
β=97.907 (5)
o, γ=105.506 (5)
o,
v=1561.68 (16)
3.Basic structure is a novel three-dimensional net structure, has two kinds of different Cd
iIcoordination environment, the tetrahedral coordination environment that Cd1 is distortion, Cd2 is the octahedral coordination environment of distortion.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: SO
4 2 –ion connects two Cd2 metal centers, can be simplified to connective bar; Cd1 is connected with four parts, and Cd2 is connected with another Cd2 with two parts, and Cd1 and Cd2 can be simplified to respectively 4 connections and 3 connected nodes; Part is connected with three metal centers respectively, so can be simplified to 3 connected nodes.Thus, the three-dimensional net structure of this title complex can be simplified as { 48 of three nodes (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2topological network.
In the preparation method of title complex of the present invention, 6,6'-, bis-sulphur two nicotinic acid parts are dissolved in that in DMF, to make strength of solution be 0.005 ~ 0.01 mol L
– 1, sulfuric acid cadmium salt is dissolved in that in DMF, to make strength of solution be 0.01 ~ 0.02 mol L
-1; Reaction conditions is that constant temperature drops to room temperature for three days afterwards naturally under 120 ~ 140 ° of C.
Embodiment 1
6,6'-, bis-sulphur two nicotinic acid (0.05 mmol, 15.4 mg) and Cadmium Sulphate (0.1 mmol, 20.8 mg) are dissolved in to stirring in DMF (10 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 120 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 45%.Main infrared absorption peak is: 3438m, 3055m, 2798m, 2462w, 1674m, 1592s, 1530w, 1467w, 1395vs, 1347m, 1257w, 1129m, 1102m, 1024w, 858w, 782w, 748w, 661w, 620w, 547w.
Embodiment 2
6,6'-, bis-sulphur two nicotinic acid (0.05 mmol, 15.4 mg) and Cadmium Sulphate (0.1 mmol, 20.8 mg) are dissolved in to stirring in DMF (8 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 130 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 55%.Main infrared absorption peak is: 3438m, 3055m, 2798m, 2462w, 1674m, 1592s, 1530w, 1467w, 1395vs, 1347m, 1257w, 1129m, 1102m, 1024w, 858w, 782w, 748w, 661w, 620w, 547w.
Embodiment 3
6,6'-, bis-sulphur two nicotinic acid (0.1 mmol, 15.4 mg) and Cadmium Sulphate (0.2 mmol, 20.8 mg) are dissolved in to stirring in DMF (15 mg) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 120 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 65%.Main infrared absorption peak is: 3438m, 3055m, 2798m, 2462w, 1674m, 1592s, 1530w, 1467w, 1395vs, 1347m, 1257w, 1129m, 1102m, 1024w, 858w, 782w, 748w, 661w, 620w, 547w.
Embodiment 4
6,6'-, bis-sulphur two nicotinic acid (0.1 mmol, 15.4 mg) and Cadmium Sulphate (0.2 mmol, 20.8 mg) are dissolved in to stirring in DMF (15 mg) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 140 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 60%.Main infrared absorption peak is: 3438m, 3055m, 2798m, 2462w, 1674m, 1592s, 1530w, 1467w, 1395vs, 1347m, 1257w, 1129m, 1102m, 1024w, 858w, 782w, 748w, 661w, 620w, 547w.
Get gained 6-sulphur nicotinic acid cadmium complex in embodiment 1 and further characterize, its process is as follows:
(1) crystal structure determination of title complex
The monocrystalline of choosing under the microscope suitable size at room temperature carries out the experiment of X – ray diffraction.At Xcalibur, Eos, on Gemini diffractometer, uses the K through the Mo of graphite monochromator monochromatization –
aray (
l=0.71073), Yi φ – ω mode is collected diffraction data.With CrysAlisPro, Agilent Technologies, Version 1.171.35.15 program is carried out reduction of data.The diffraction data of part-structure carries out absorption correction by SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out complete matrix least-squares refinement, and hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and methyl alcohol is processed by the method for difference Fourier peak-seeking.Detailed axonometry data are in Table 1; Important bond distance and bond angle data are in Table 2.Crystalline structure is shown in Fig. 1 and Fig. 2, and Fig. 3 is shown in by the topological network of title complex.
(2) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment is processed, through further milled processed, carries out the test of solid fluorescence: title complex excites at 358 nm places, at 487,545 and 574 nm places, obtains three emission peaks, sees Fig. 4.(instrument model: HITACHI/F – 7000).
(3) the XPRD phase purity of title complex characterizes
The XPRD of title complex characterizes and shows that it has reliable phase purity, for its application as fluorescent material provides assurance, sees Fig. 5.(instrument model: Bruker/D8 Advance).
(4) thermal stability of title complex characterizes
The thermogravimetric analysis of title complex characterize show its skeleton approach 120 ℃ of left and right still can stable existence, there is certain thermostability, for its further Application and Development as fluorescent material provides assurance, see Fig. 6.(instrument model: Perkin – Elmin Diamond TG/DTA).
By above-mentioned characterization result, can be seen, complex crystal of the present invention is characterized in that described complex crystal belongs to triclinic(crystalline)system, and spacer is
p-1, unit cell parameters is
a=7.8398 (3),
b=14.4250 (10),
c=14.4884 (10), α=90.760 (6)
o,
β=97.907 (5)
o, γ=105.506 (5)
o,
v=1561.68 (16)
3.Basic structure is a novel three-dimensional net structure, has two kinds of different Cd
iIcoordination environment, the tetrahedral coordination environment that Cd1 is distortion, Cd2 is the octahedral coordination environment of distortion.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: SO
4 2 –ion connects two Cd2 metal centers, can be simplified to connective bar; Cd1 is connected with four parts, and Cd2 is connected with another Cd2 with two parts, and Cd1 and Cd2 can be simplified to respectively 4 connections and 3 connected nodes; Part is connected with three metal centers respectively, so can be simplified to 3 connected nodes.Thus, the three-dimensional net structure of this title complex can be simplified as { 48 of three nodes (3,3,4)-connection
2}
2{ 4
28
210
2{ 810
2topological network.
Above embodiment is only for illustrating content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replaces or technical scheme that equivalent deformation mode forms all drops in protection scope of the present invention.
table 1the main crystallographic data of title complex
Empirical formula C
19H
29Cd
2N
5O
9S
3
Formula weight 792.45
Crystal system Triclinic
Space group P
–1
Unit cell dimensions ( ,
o)
a 7.8398(3)
b 14.4250(10)
c 14.4884(10)
α 90.760(6)
b 97.907(5)
γ 105.506(5)
Volume (
3) 1561.68(16)
Z 2
D calcd (g/cm
3) 1.685
m (mm
–1) 1.611
Crystal size (mm) 0.24 × 0.22 × 0.18
F (000) 788
Range of
h,
k,
l –9/9, –15/17, –17/17
Reflections collected/unique 11610 / 5515
Max. & min. transmission 0.7602 & 0.6984
Data/restraints/parameters 5515/0/349
R(int) 0.0311
T(K) 293(2)
Goodness–of–fit on
F 2 1.007
R 1 a &
wR 2 b [
I >2
σ(
I)] 0.0326 & 0.0761
R 1 a &
wR 2 b (All data) 0.0429 & 0.0810
Largest diff. peak & hole (e
. 3) 0.611 & –0.508
a R 1 = S(||
F o|
-|
F c||)/S|
F o|;
b wR 2 = [S
w(|
F o|
2 -|
F c|
2)
2/S
w(
F o 2)
2]
1/2
Claims (6)
1. a 6-sulphur nicotinic acid cadmium complex crystal, is characterized in that: described title complex has following chemical formula, that is: { [Cd
2 l 2(SO
4)] DMF2NH
2(CH
3)
2)
∞, wherein
l=6-sulphur nicotinic acid carboxyl anion part, DMF=DMF;
lskeleton symbol is as follows:
And described complex crystal belongs to triclinic(crystalline)system, spacer is
p-1, unit cell parameters is a=7.8398 (3), b=14.4250 (10), c=14.4884 (10), α=90.760 (6)
o, β=97.907 (5)
o, γ=105.506 (5)
o, V=1561.68 (16)
3.
2. 6-sulphur nicotinic acid cadmium complex crystal as claimed in claim 1, is characterized in that: described complex crystal has three-dimensional coordinated network structure, wherein, has two kinds of different Cd
iIcoordination environment, the tetrahedral coordination environment that Cd1 is distortion, and the pentagonal bipyramid that the sterie configuration of Cd2 is distortion.
3. the preparation method of 6-sulphur nicotinic acid cadmium complex crystal as claimed in claim 1, it is characterized in that: be under the condition of solvent thermal, by 6,6'-bis-sulphur two nicotinic acid parts and sulfuric acid cadmium salt are dissolved in N, in dinethylformamide, making solution encloses in the reactor of 25 mL, with the speed of 10 ℃ per hour, be heated to certain temperature, maintain this temperature 3 days, then be naturally down to room temperature, can obtain colourless rhabdolith, this monocrystalline is separated, through washing, drying treatment, obtained target product successively.
4. the preparation method of 6-sulphur nicotinic acid cadmium complex crystal as claimed in claim 3, is characterized in that: described 6,6'-bis-sulphur two nicotinic acid parts are dissolved in that in DMF, to make strength of solution be 0.005 ~ 0.01 mol L
– 1.
5. the preparation method of 6-sulphur nicotinic acid cadmium complex crystal as claimed in claim 3, is characterized in that: described sulfuric acid cadmium salt is dissolved in that in DMF, to make strength of solution be 0.01 ~ 0.02 mol L
-1.
6. the preparation method of 6-sulphur nicotinic acid cadmium complex crystal as claimed in claim 3, it is characterized in that: by 6,6'-bis-sulphur two nicotinic acid parts and sulfuric acid cadmium salt are dissolved in to be made solution and encloses in the reactor of 25 mL and be heated to 120 ~ 140 ℃ with 10 ℃ per hour in DMF.
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Non-Patent Citations (2)
| Title |
|---|
| Syntheses and Crystal Structures of a Series of Zn(II)/Cd(II) Coordination Polymers Constructed from a Flexible 6,6"-Dithiodinicotinic Acid;Ya-Nan Zhang, et al.;《Cryst. Growth Des.》;20110404;第11卷;1531-1541 * |
| Ya-NanZhang et al..Syntheses and Crystal Structures of a Series of Zn(II)/Cd(II) Coordination Polymers Constructed from a Flexible 6 |
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