CN104892684A - Heterometal-organic coordination polymer containing trinuclear copper cluster, and preparation method and application thereof - Google Patents
Heterometal-organic coordination polymer containing trinuclear copper cluster, and preparation method and application thereof Download PDFInfo
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- CN104892684A CN104892684A CN201510153496.0A CN201510153496A CN104892684A CN 104892684 A CN104892684 A CN 104892684A CN 201510153496 A CN201510153496 A CN 201510153496A CN 104892684 A CN104892684 A CN 104892684A
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Abstract
The invention discloses a heterometal-organic coordination polymer containing a trinuclear copper cluster, and a preparation method and application thereof, belonging to the technical field of metal organic chemistry. The general chemical formula of the polymer is [Ag3(H2O)2(NO3)6{Cu3(OH)(pz)3(Hpz)1.5(H2O)0.5}2]n(NO3)n.1.5nH2O, wherein Hpz represents pyrazole. The preparation method for the polymer comprises a step of subjecting a copper salt, a silver salt, pyrazole and inorganic base or organic base to a reaction in a mixed phase of a water phase and an organic phase under a heating condition. According to the invention, cheap and easily available pyrazole ligand and metal salts are used to construct a metal magnetic material; the preparation method is simple and is easy to operate; the prepared polymer is precipitated in the form of a crystal and has high purity and yield; and the polymer has good dissolvability in a common solvent and, as a novel magnetic material, has latent application prospects in the field of information storage.
Description
Technical field
The present invention relates to Organometallic Chemistry technical field, particularly relate to and a kind ofly contain assorted metal organic coordination polymer of three core copper bunch and its preparation method and application; More specifically, relating to one utilizes Ag-π effect by three core copper bunch (Cu
3o) preparation method of two-dimensional metallic organic coordination polymer and the utilization in magnetic fields thereof is connected into.
Background technology
The material with metal organic frame (MOFs) is commonly employed in catalysis, host-guest chemistry, light and magnetic fields.Nearly ten years, MOF chemistry obtains and develops rapidly, many metallo organic materials with novel structure are synthesized out, these materials are combined with motive power by intramolecular secondary structure unit (SBUs), and these reactive forces comprise hydrogen bond, pi-pi accumulation, coordinate bond effect between metal and part.Although a large amount of MOFs of bibliographical information is rare by the metal organic polymer material constructed by the π key effect between metal and part.
Multi-nuclear metal duster compound to have become in current chemical research one of the most active study hotspot, not only because they have the molecular structure of nano-scale, but also shows interesting optical, electrical, magnetic and catalytic property.
Pyrazoles and derivative thereof are classes good 1, the bridging junctor of 2, and in the basic conditions, they can connect Cu (II) and form [the Cu containing three cores
iI 3(μ
3-OH) (μ-pz)
3]
2+the duster compound of structure.Three core copper bunch as duster compound, have excellent magnetic performance.[Cu
iI 3(μ
3-OH) (μ-pz)
3]
2+unit can as an interesting secondary structure unit (SBUs), and be also the supplier with delocalizedπelectron.Although there are many title complexs containing three core copper bunch unit to be in the news at present, but using this three core copper bunch as secondary structure unit (SBUs), and utilize the metal π effect of delocalization that these copper bunch are connected into high-dimensional metal organic coordination polymer, not yet have report at present.
Summary of the invention
The present invention, in order to solve the problem, provide and a kind ofly contains assorted metal organic coordination polymer of three core copper bunch and its preparation method and application.
For achieving the above object, the present invention by the following technical solutions:
Contain an assorted metal organic coordination polymer for three core copper bunch, this polymkeric substance is the handkerchief polymer that Cu-Ag mixes metal, and its chemical general formula is as follows:
[Ag
3(H
2O)
2(NO
3)
6{Cu
3(OH)(pz)
3(Hpz)
1.5(H
2O)
0.5}
2]
n(NO
3)
n·1.5nH
2O；
Wherein, Hpz represents pyrazoles.
Above-mentioned Cu-Ag mixes the elementary cell of nine nuclear polymers, by 2 [Cu
iI 3(μ
3-OH) (μ-pz)
3] unit and 3 [Ag (H
2o)
x(NO
3)
y] unit composition, both are linked together by Ag-π effect.Two pz in each copper bunch unit
-take part in Ag-π coordination.The Ag2 atom at center is by Ag-η
1-pz bridging two copper bunch unit, only have a pz
-group is with η
2pattern and Ag1 or Ag3 Atomic coordinate.Ag
3cu
6cu-O (the NO of duster compound by elongating
3 -) act on the assorted metal organic layer with micropore being interconnected into a two dimension (6,3).The layer of these two dimensions is piled up along a direction of principal axis and is defined the three-dimensional micropore supramolecular structure that has 1D passage, and what fill in passage is crystalline water molecules and the free nitrate anion not having coordination.
Preferably, described polymer crystals belongs to oblique system, and spacer is P2
1/c, unit cell parameters is:
α=90.00 °, β=100.735 (3) °, γ=90.00 °.
Preferably, there is anti-ferromagnetic coupling interaction in the central copper interionic of described polymkeric substance.
Another object of the present invention is to the openly above-mentioned preparation method containing the assorted metal organic coordination polymer of three core copper bunch, comprise the following steps:
(1) pyrazoles and mineral alkali/organic bases are dissolved in suitable quantity of water, obtained solution A;
(2) anhydrous cupric sulfate is dissolved in proper amount of methanol, obtained solution B;
(3) Silver Nitrate is dissolved in appropriate acetonitrile solution, obtained solution C; Wherein the mol ratio of pyrazoles, mineral alkali/organic bases, anhydrous cupric sulfate and Silver Nitrate is 2:2:1:3;
(4) solution A is added in solution B, stir and obtain reaction solution, reacted 20 ~ 30 minutes at 60 DEG C by reaction solution, solution C slowly dropped in reaction solution in above-mentioned reaction process, reaction end is cooled to room temperature, after filtering reacting liquid, filtrate is at room temperature left standstill, until there is a large amount of blue block crystal to generate, isolate crystal, washing, drying, obtains target product.
Preferably, described mineral alkali is NaOH; Described organic bases is trolamine, triethylamine or Tetrabutyl amonium bromide.
Preferably, described polymer-based carbon in the productive rate of copper be 45-56%.
Preferably, described solution A is dissolved in 10ml water obtained by 1.0mmol pyrazoles and 1.0mmol NaOH.
Preferably, described solution B is dissolved in 20ml methyl alcohol obtained by 0.5mmol anhydrous cupric sulfate.
Preferably, described solution C is dissolved in 8ml acetonitrile solution by 1.5mmol Silver Nitrate.
Another object of the present invention is that openly the above-mentioned assorted metal organic coordination polymer containing three core copper bunch is as the application of magnetic material in information storage.
Compared with prior art, the present invention has following beneficial effect:
The invention provides one utilizes metal π effect three core copper bunch to be connected into two-dimensional metallic organic coordination polymer and synthetic method and application, and this synthetic method is simple to operation, and productive rate is higher, and in usual vehicle, solvability is good; Resulting polymers utilizes pyrazoles cheap and easy to get and metal-salt to construct organometallic polymer containing clustering architecture, has potential application prospect as a kind of novel magnetic material in information storage.
Accompanying drawing explanation
Fig. 1 is a kind of molecular structure containing the assorted metal organic coordination polymer of three core copper bunch of the present invention;
Fig. 2 is a kind of X-Y scheme containing the assorted metal organic coordination polymer of three core copper bunch of the present invention;
Fig. 3 is a kind of χ containing the assorted metal organic coordination polymer of three core copper bunch of the present invention
mt – T graphic representation.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but embodiments of the present invention are not limited thereto.
Embodiment 1
Contain an assorted metal organic coordination polymer for three core copper bunch, this polymkeric substance is the handkerchief polymer that Cu-Ag mixes metal, and its chemical general formula is as follows:
[Ag
3(H
2O)
2(NO
3)
6{Cu
3(OH)(pz)
3(Hpz)
1.5(H
2O)
0.5}
2]
n(NO
3)
n·1.5nH
2O；
Wherein, Hpz represents pyrazoles.
Above-mentioned Cu-Ag mixes the elementary cell of nine nuclear polymers, by 2 [Cu
iI 3(μ
3-OH) (μ-pz)
3] unit and 3 [Ag (H
2o)
x(NO
3)
y] unit composition, both are linked together by Ag-π effect.Two pz in each copper bunch unit
-take part in Ag-π coordination.The Ag2 atom at center is by Ag-η
1-pz bridging two copper bunch unit, only have a pz
-group is with η
2pattern and Ag1 or Ag3 Atomic coordinate.Ag
3cu
6cu-O (the NO of duster compound by elongating
3 -) act on the assorted metal organic layer (Fig. 2) with micropore being interconnected into a two dimension (6,3).The layer of these two dimensions is piled up along a direction of principal axis and is defined the three-dimensional micropore supramolecular structure that has 1D passage, and what fill in passage is crystalline water molecules and the free nitrate anion not having coordination, and concrete molecular structure is see Figure of description 1.
The above-mentioned preparation method containing the assorted metal organic coordination polymer of three core copper bunch, comprises the following steps:
(1) 1.0mmol pyrazoles and 1.0mmol NaOH are dissolved in 10ml water, obtained solution A;
(2) 0.5mmol anhydrous cupric sulfate is dissolved in 20ml methyl alcohol, obtained solution B;
(3) 1.5mmol Silver Nitrate is dissolved in 8ml acetonitrile solution, obtained solution C; This acetonitrile solution adopts commercially available acetonitrile, and concentration is generally more than 90%;
(4) solution A is added in solution B, stir and obtain reaction solution, reacted 20 ~ 30 minutes at 60 DEG C by reaction solution, solution C slowly dropped in reaction solution in above-mentioned reaction process, reaction end is cooled to room temperature, after filtering reacting liquid, filtrate is at room temperature left standstill, until there is a large amount of blue block crystal to generate, isolate crystal, washing, drying, obtains target product.
In actual production process, generally filtrate is at room temperature left standstill and within 5 ~ 8 days, just have a large amount of blue block crystal to generate.
Mineral alkali is NaOH.Organic bases is trolamine, triethylamine or Tetrabutyl amonium bromide.
The productive rate of above-mentioned preparation method's gained target product is 45-56% (based on copper).
The invention provides one utilizes metal π effect three core copper bunch to be connected into two-dimensional metallic organic coordination polymer and synthetic method and application, and this synthetic method is simple to operation, and productive rate is higher, and in usual vehicle, solvability is good; Resulting polymers utilizes pyrazoles cheap and easy to get and metal-salt to construct organometallic polymer containing clustering architecture, has potential application prospect as a kind of novel magnetic material in information storage.
Embodiment 2
Structural characterization is carried out to the assorted metal organic coordination polymer containing three core copper bunch of embodiment 1 gained:
(1) structural characterization: choose size suitable monocrystalline, under 123K condition, X ray diffracting data is on the detection instrument of Brucker Apex CCD face, with MoK α radiation
collect with ω scan mode and carry out LP factor correction.The reduction of data utilizes SAINT
+program, absorption correction SADABS program.Use direct method solution structure, then obtain whole non-hydrogen atom coordinate by difference Fourier method, and obtain hydrogen atom position with theoretical hydrogenation method
by method of least squares, structure is revised.Evaluation work completes with SHELXTL routine package on PC.Detailed crystallography and structural modifications data as shown in table 1, structure is as shown in Figure 1.
Table 1 crystallography and structural modifications data
aR
1＝Σ||F
o|-|F
c||/Σ|F
o|,
bwR
2＝[Σw(F
o 2-F
c 2)
2/Σw(F
o 2)
2]
1/2
From above-mentioned ray crystallographic analysis, Cu-Ag organometallic polymer [Ag
3(H
2o)
2(NO
3)
6{ Cu
3(OH) (pz)
3(Hpz)
1.5(H
2o)
0.5}
2]
n(NO
3)
n1.5nH
2o belongs to oblique system, P2
1/c spacer, unit cell parameters is:
α=90.00 °, β=100.735 (3) °, γ=90.00 °.From its molecular structure, three pz sloughing proton
-two cupric ions that bridging is adjacent, the OH at center
-bridging three cupric ions define leg-of-mutton plane three core copper bunch, and two adjacent three core copper bunch pass through Ag
+ion and pz
-between Ag-π coordination two copper bunch are connected into Cu
3ag
6assorted metal cluster unit.Ag
3cu
6cu-O (the NO of duster compound by elongating
3 -) act on the assorted metal organic layer (Fig. 2) with micropore being interconnected into a two dimension (6,3).
(2) Infrared Characterization:
With Bio-Rad FTS-7 type Fourier infrared spectrograph (KBr compressing tablet), take the photograph spectral limit 400-4000cm
-1principal character infrared absorption peak is as follows: 3316 (m), 3132 (w), 2425 (w), 1746 (vw), 1658 (m), 1381 (vw), 1305 (vw), 1183 (m), 1162 (vw), 1127 (s), 1062 (vs), 945 (w), 911 (vw), 884 (w), 784 (w), 761 (w), 626 (m), 605 (w), 465 (m).
(3) electrospray ionization mass spectrum characterizes: be dissolved in by target product in methanol solution, the liquid chromatograph-mass spectrometer of LCQ DECA XP measures.(higher peak value, relative abundance %): 408 (100) [Cu
3(OH) (pz)
3]
2+; 522 (37) [Cu
3(pz)
4(NO
3)]
+; 538 (96) [Cu
3(OH) (pz)
3(Hpz) (NO
3)]
+; 640 (67) [Cu
3(OH) (pz)
3ag (NO
3)
2]
+; 668 (97) [Cu
3(OH) (pz)
3ag (NO
3)
2(H
2o)]
+; 670 (94) [Cu
3(OH) (pz)
4(Hpz) Ag (H
2o)]
+; 696 (55) [Cu
3(OH) (pz)
3ag
2(NO
3)]
3+; 878 (28) [Cu
3(OH) (pz)
3(Hpz) Ag
2(NO
3)
3]
+.
(4) Magnetic Characterization:
Utilize SQUID magnetic measurement instrument MPMS XL-7 outside 1 tesla, have collected this title complex alternating temperature molar susceptibility within the scope of 2-300K after the match.With Pascal ' s constant, diamagnetic correction is carried out to this title complex.And with χ
mt maps to T, and the curve of gained as shown in Figure 3.
As shown in Figure 3, the χ of this assorted organometallic polymer when 300K
mt value is 0.68cm
3mol
-1k, χ
mt reduction be worth along with temperature in 300-50K temperature range constantly reduces; Subsequently in the temperature range of 50-2K, χ
mt value sharply reduces, and this shows to there is anti-ferromagnetic coupling interaction between Cu (II).
The present invention can as magnetic materials application in information storage containing the assorted metal organic coordination polymer of three core copper bunch.
The above, above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1., containing an assorted metal organic coordination polymer for three core copper bunch, it is characterized in that, described polymkeric substance is the handkerchief polymer that Cu-Ag mixes metal, and its chemical general formula is as follows:
[Ag
3(H
2O)
2(NO
3)
6{Cu
3(OH)(pz)
3(Hpz)
1.5(H
2O)
0.5}
2]
n(NO
3)
n·1.5nH
2O；
Wherein, Hpz represents pyrazoles.
2. a kind of assorted metal organic coordination polymer containing three core copper bunch according to claim 1, it is characterized in that, described polymer crystals belongs to oblique system, and spacer is P2
1/ c, unit cell parameters is:
α=90.00 °, β=100.735 (3) °, γ=90.00 °.
3. a kind of assorted metal organic coordination polymer containing three core copper bunch according to claim 1, it is characterized in that, there is anti-ferromagnetic coupling interaction in the central copper interionic of described polymkeric substance.
4. as described in any one of claims 1 to 3 containing a preparation method for the assorted metal organic coordination polymer of three core copper bunch, it is characterized in that, comprise the following steps:
(1) pyrazoles and mineral alkali/organic bases are dissolved in suitable quantity of water, obtained solution A;
(2) anhydrous cupric sulfate is dissolved in proper amount of methanol, obtained solution B;
(3) Silver Nitrate is dissolved in appropriate acetonitrile solution, obtained solution C; Wherein the mol ratio of pyrazoles, mineral alkali/organic bases, anhydrous cupric sulfate and Silver Nitrate is 2:2:1:3;
(4) solution A is added in solution B, stir and obtain reaction solution, reacted 20 ~ 30 minutes at 60 DEG C by reaction solution, solution C slowly dropped in reaction solution in above-mentioned reaction process, reaction end is cooled to room temperature, after filtering reacting liquid, filtrate is at room temperature left standstill, until there is a large amount of blue block crystal to generate, isolate crystal, washing, drying, obtains target product.
5. a kind of preparation method containing the assorted metal organic coordination polymer of three core copper bunch according to claim 4, it is characterized in that, described mineral alkali is NaOH; Described organic bases is trolamine, triethylamine or Tetrabutyl amonium bromide.
6. a kind of preparation method containing the assorted metal organic coordination polymer of three core copper bunch according to claim 4, is characterized in that, described polymer-based carbon in the productive rate of copper be 45-56%.
7. a kind of preparation method containing the assorted metal organic coordination polymer of three core copper bunch according to claim 4, is characterized in that, described solution A is dissolved in 10ml water obtained by 1.0mmol pyrazoles and 1.0mmol NaOH.
8. a kind of preparation method containing the assorted metal organic coordination polymer of three core copper bunch according to claim 4, is characterized in that, described solution B is dissolved in 20ml methyl alcohol obtained by 0.5mmol anhydrous cupric sulfate.
9. a kind of preparation method containing the assorted metal organic coordination polymer of three core copper bunch according to claim 4, it is characterized in that, described solution C is dissolved in 8ml acetonitrile solution by 1.5mmol Silver Nitrate.
10. one kind as described in any one of claims 1 to 3 containing the assorted metal organic coordination polymer of three core copper bunch as the application of magnetic material in information storage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496583A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | 4 silver formate polymer of pyrazoles and preparation method thereof |
| CN117143350A (en) * | 2023-08-29 | 2023-12-01 | 广东工业大学 | Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone |
-
2015
- 2015-04-01 CN CN201510153496.0A patent/CN104892684B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| LING-LING ZHENG ET AL.: "Engineering delocalizing π electronic [CuII3(μ3-OH)(μ-pz)3]2+ species into organometallic frameworks by Ag-π coordination", 《CRYSTENGCOMM》 * |
| 段鹏程等: "银，铜与双吡唑构筑的三棱柱状超分子笼子的合成与结构", 《中国化学会学术年会》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496583A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | 4 silver formate polymer of pyrazoles and preparation method thereof |
| CN117143350A (en) * | 2023-08-29 | 2023-12-01 | 广东工业大学 | Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone |
| CN117143350B (en) * | 2023-08-29 | 2024-03-12 | 广东工业大学 | Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone |
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