CN103833793B - A kind of nickel coordination polymer and preparation method thereof - Google Patents
A kind of nickel coordination polymer and preparation method thereof Download PDFInfo
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- CN103833793B CN103833793B CN201410079798.3A CN201410079798A CN103833793B CN 103833793 B CN103833793 B CN 103833793B CN 201410079798 A CN201410079798 A CN 201410079798A CN 103833793 B CN103833793 B CN 103833793B
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Abstract
The present invention relates to a kind of nickel coordination polymer and preparation method thereof, the molecular formula of coordination compound is: { [Ni2(BPTC)(1,4-bib)2(H2O)2]}n, wherein H4BPTC is 3,4,3,4-biphenyltetracarboxyacid acid, and 1,4-bib is 1,4-diimidazole benzene。Being prepared by H of this coordination compound4BPTC, Isosorbide-5-Nitrae-bib and Ni (NO3)2·6H2O is soluble in water with the mixing of a certain proportion of amount of substance, adjusting pH is 6.5, it is placed in 13ml polyfluortetraethylene pipe, 30min is stirred at room temperature, this polyfluortetraethylene pipe is sealed in stainless steel cauldron, crystallization 72h at 160 DEG C, naturally cool to room temperature, precipitating out light blue granular crystals, drain with distilled water wash final vacuum pump, productivity is more than 78%。This complex structure comprises nickel dimer unit, between dimer metallic nickel ions, shows as weak ferromagnetic interaction, and then can as molecular magnetic materials。
Description
Technical field
The present invention relates to nickel complex, be specifically related to a kind of nickel coordination polymer, particularly a kind of based on nickel (II) ion, 3,4, nickel coordination polymer with weak ferromagnetic interaction that 3', 4'-biphenyltetracarboxyacid acid and Isosorbide-5-Nitrae-diimidazole benzene are constructed and preparation method thereof。
Background technology
Molecular magnetic materials is not only a kind of novel functional material, and relates to the frontier of the cross disciplines such as chemistry, physics, material science and life sciences。Traditional magnetic material is owing to having to pass through pyrolytic semlting, and density is big, Precision Machining difficult forming, and the reasons such as magnetic loss is big are limited by very large in the application aspect such as new and high technology and hard-core technology。Compared to traditional magnetic material, molecular magnet is because of the multiformity of its structure species, prepared by the method for available low temperature synthesis and processing, the combination property can being combined with the aspect such as mechanical, optical, electrical, the features such as magnetic loss is little, need the field of light magnetic material to have very big application prospect in hyperfrequency device, high density storing material, absorbing material, microelectronics industry and aerospace etc., and in the miniaturization of device, low energy consumption, the at a high speed compatibility connect corresponding, biological, have the advantage of its uniqueness。Just because of this, how building the molecular magnet that can produce magnetic order within the scope of effective temperature is one of molecule magnetics and material science facing challenges, is also the important content of molecule magnetics research。
Summary of the invention
The purpose of the present invention is based on the above-mentioned state of the art, it is provided that a kind of can as nickel coordination polymer of molecular magnetic materials and preparation method thereof。
A kind of nickel coordination polymer provided by the invention, molecular formula is: { [Ni2(BPTC)(1,4-bib)2(H2O)2] n, wherein H4BPTC is 3,4,3', 4'-biphenyltetracarboxyacid acid, and 1,4-bib is 1,4-diimidazole benzene。Its structural formula is:
The crystal of this coordination compound belongs to anorthic system, and space group is P-1, and cell parameter is: a=8.1587 (9)b=9.3411(12)c=12.7338(12)α=105.254 (2) °, β=98.139 (2) °, γ=107.777 (2) °。This coordination compound is double-core nickel octahedral coordination environment。Ni1 respectively with three O atom in two different carboxylic acids, two atom N, and a water molecule coordination；Ni2 respectively with the O atom in two different carboxylic acids, an atom N, a hydrone, and an abutment phenol O atom coordination。Ni-O bond distance ranges for 2.038 (4)-2.133 (3)Ni-N bond distance ranges for 2.081 (4)-2.090 (4)Ni1-O1-Ni2 bond angle is 100.50 (14) °, and the distance between double-core Ni1 and Ni2 is 3.229X-ray powder diffraction confirms crystal prototype stable homogeneous。
The preparation method of a kind of nickel coordination polymer provided by the invention, comprises the steps:
(1) it is the 3,4,3' of 122 3800 by mol ratio, 4'-biphenyltetracarboxyacid acid, Isosorbide-5-Nitrae-diimidazole benzene, Ni (NO3)2·6H2O and water mixing, adjusting pH is 6.5, is placed in polyfluortetraethylene pipe；
(2) at least 20min is stirred at room temperature, this polyfluortetraethylene pipe is sealed in stainless steel cauldron, crystallization 72h at 160 DEG C, naturally cool to room temperature, precipitate out light blue granular crystals, drain collection product with distilled water wash final vacuum pump。
Under 1000Oe external magnetic field, draw that polymer exists between nickel ion weak ferromagnetic interaction by matching variable temperature magnetic susceptibility experimental data, it is possible to as molecular magnetic materials。
Advantages of the present invention and effect:
The nickel coordination polymer of the present invention is to obtain under hydrothermal synthesizing condition, and preparation method technique is simple, and sample purity is high, and yield is high。Thermogravimetric analysis shows that its main structure is decomposed more than 263 DEG C, has higher heat stability。
Nickel coordination polymer provided by the invention is based on 3,4,3', 4'-biphenyltetracarboxyacid acid part and assistant ligand 1,4-diimidazole benzene is constructed, under 1000Oe external magnetic field, draw that polymer exists between nickel ion weak ferromagnetic interaction by variable temperature magnetic susceptibility experimental data, it is possible to as molecular magnetic materials。
Accompanying drawing explanation
The crystal structure figure of Fig. 1 nickel coordination polymer of the present invention
Fig. 2 nickel coordination polymer of the present invention is at the X-ray powder diffraction figure of 298K
The thermogravimetric analysis figure of Fig. 3 nickel coordination polymer of the present invention
Fig. 4 nickel coordination polymer of the present invention variable temperature magnetic susceptibility curve chart under 1000Oe external magnetic field
Detailed description of the invention
Embodiment 1. is by 0.1 mM of H4Ni (the NO of BPTC, the Isosorbide-5-Nitrae-bib of 0.2 mM and 0.2 mM3)2·6H2O mixed dissolution is in 7mL water, adjusting pH is 6.5, it is placed in 13ml polyfluortetraethylene pipe, 30min is stirred at room temperature, this polyfluortetraethylene pipe is sealed in stainless steel cauldron, crystallization 72h at 160 DEG C, naturally cool to room temperature, precipitating out light blue granular crystals, drain collection product with distilled water wash final vacuum pump, productivity is 78.2%。
The structure determination of nickel coordination polymer:
Crystal structure determination adopts BrukerApex type X-ray single crystal diffraction instrument, uses through graphite monochromatised Mo-K alpha ray (λ=0.71073) for incident radiation, collect point diffraction with ω-φ scan mode, obtain cell parameter through least square refinement, utilize SHELXL-97 direct method to solve crystal structure from difference Fourier electron density map, and through Lorentz and polarity effect correction。C atom adopts theory hydrogenation, and in hydrone, the hydrogen on O atom is provided by difference Fourier synthesis,And be fixed on parent。Detailed axonometry data are in Table 1。Crystal structure is shown in Fig. 1。
The crystallographic data of table 1 coordination compound
Powder diffraction:
X-ray powder diffraction is it is shown that crystal prototype thing is mutually homogeneous, and experimental diffraction collection of illustrative plates is consistent with the powder diffraction spectrum according to crystal structure simulation, sees Fig. 2。
The thermogravimetric analysis of coordination compound:
Thermal gravimetric analysis results shows this polymer weightlessness about 4.6% gradually between 200 DEG C-263 DEG C, illustrates to deposit water of coordination (theoretical value 4.0%) in the polymer, and this result has proved the existence of hydrone in polymer crystals structure further；Additionally from thermogravimetric analysis Fig. 3 it can also be seen that its agent structure is decomposed more than 263 DEG C, illustrate that polymer has higher heat stability。
The magnetic property of nickel coordination polymer material:
Variable temperature magnetic susceptibility curve as shown in Figure 4, it can be seen that χ during room temperaturemT value is 1.26cm3·K·mol-1, the room temperature magnetic moment (2.0cm of Ni (II) ion is not coupled lower than two independences3Kmol-1)。Along with the reduction of temperature, χmT value slowly raises, and reaches maximum 1.38cm when 7K3·K·mol-1, it was shown that there is local ferromagnetic and interact in double-core nickel interionic, is then rapidly decreased to 1.00cm during 1.8K3·K·mol-1。Additionally, utilize Curie-Weiss law matching χm -1-T(Fig. 4 illustration), it is possible to obtain C=1.25cm3·mol-1, θ=0.61K, positive θ value demonstrates again that there is weak ferromagnetic interaction in polymer between nickel ion。
Claims (3)
1. a nickel coordination polymer, it is characterised in that its structural formula is:
The crystal of this coordination polymer belongs to anorthic system, and space group is P-1, and cell parameter is: α=105.254 (2) °, β=98.139 (2) °, γ=107.777 (2) °；This coordination compound is double-core nickel octahedral coordination environment；Ni1 respectively with three O atom in two different carboxylic acids, two atom N, and a water molecule coordination；Ni2 respectively with the O atom in two different carboxylic acids, an atom N, a hydrone, and an abutment phenol O atom coordination；Ni-O bond distance ranges forNi-N bond distance ranges for Ni1-O1-Ni2 bond angle is 100.50 (14) °, and the distance between double-core Ni1 and Ni2 is
2. the preparation method of nickel coordination polymer as claimed in claim 1, it is characterised in that comprise the steps:
(1) it is the 3,4,3' of 122 3800 by mol ratio, 4'-biphenyltetracarboxyacid acid, Isosorbide-5-Nitrae-diimidazole benzene, Ni (NO3)2·6H2O and water mixing, adjusting pH is 6.5, is placed in polyfluortetraethylene pipe；
(2) at least 20min is stirred at room temperature, this polyfluortetraethylene pipe is sealed in stainless steel cauldron, crystallization 72h at 160 DEG C, naturally cool to room temperature, precipitate out light blue granular crystals, drain collection product with distilled water wash final vacuum pump。
3. nickel coordination polymer as claimed in claim 1 is used as molecular magnetic materials。
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104130292B (en) * | 2014-07-04 | 2017-02-08 | 谭柳 | Three dimensional coordination polymer with double core structure and preparation method thereof |
| CN104130293B (en) * | 2014-07-04 | 2016-07-13 | 海门市凤龙不锈钢制药设备有限公司 | A kind of three-dimensional coordination polymer of mixed ligand and preparation method thereof |
| CN104525133B (en) * | 2015-01-09 | 2016-08-24 | 南开大学 | A kind of for N2metal-organic framework material of O absorption and preparation method thereof |
| CN104844663B (en) * | 2015-04-07 | 2017-08-25 | 山西大学 | A kind of coordination polymer of nickel and preparation method thereof |
| CN105646185A (en) * | 2016-01-12 | 2016-06-08 | 中国石油大学(华东) | Calcium metal-organic coordination polymer and preparation method thereof |
| CN106633097A (en) * | 2017-01-10 | 2017-05-10 | 黄秋颖 | Tetranuclear nickel complex with antiferromagnetic coupling function and synthesis method thereof |
| CN109385270B (en) * | 2018-03-23 | 2019-07-30 | 南京晓庄学院 | A kind of white light emitting material |
| CN108752598A (en) * | 2018-07-11 | 2018-11-06 | 中北大学 | The synthetic method of complex base Cr (VI) fluorescence probe |
| CN109575304B (en) * | 2018-12-13 | 2020-12-25 | 山西大学 | Nickel coordination polymer and preparation method and application thereof |
| CN110256685B (en) * | 2019-05-15 | 2021-11-30 | 中国石油大学(华东) | Nickel-based complex and preparation method and application thereof |
| CN110041534A (en) * | 2019-05-31 | 2019-07-23 | 安庆师范大学 | A kind of nickel complex and preparation method thereof based on rigid 4- imidazoles ylidene ligands |
| CN111909220A (en) * | 2020-08-25 | 2020-11-10 | 河南省科学院化学研究所有限公司 | Nickel (II) metal organic complex based on 3,3',5,5' -biphenyltetracarboxylic acid and preparation method and application thereof |
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| US20050090683A1 (en) * | 2003-10-23 | 2005-04-28 | Ube Industries, Ltd. | Preparation of 2,3,3',4' -biphenyltetracarboxylic acid tetraester |
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| US20050090683A1 (en) * | 2003-10-23 | 2005-04-28 | Ube Industries, Ltd. | Preparation of 2,3,3',4' -biphenyltetracarboxylic acid tetraester |
| CN103467397A (en) * | 2013-08-29 | 2013-12-25 | 山西大学 | Binuclear platinum (II) complex as well as preparation method and application thereof |
Non-Patent Citations (2)
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