CN112029110B - Temperature-induced three-dimensional spin cross coordination polymer and preparation method and application thereof - Google Patents
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract
The application belongs to the technical field of magnetic materials, and particularly relates to a temperature-induced three-dimensional spin cross coordination polymer [ Fe (bpa) { Ag (CN)2}2]·x guestsEach minimum asymmetric unit contains one Fe2+One bpa ligand, two [ Ag (CN)2]‑A counter anion, and x guest molecules, the bpa ligand being 1, 4-bis (4-pyridyl) anthracene. The invention introduces specific guest molecules into the coordination polymer framework to regulate and control the spin cross property, and the obtained coordination polymer realizes high-low spin conversion through the change of temperature, thereby having remarkable application value in the aspects of molecular thermomagnetic switch materials, information storage materials and the like. In addition, the invention also provides a preparation method of the compound, which has the advantages of simple operation, high yield, cost saving, contribution to industrial production and capability of being applied in practice.
Description
Technical Field
The application belongs to the technical field of magnetic materials and providesThe body relates to a temperature-induced three-dimensional spin cross coordination polymer [ Fe (bpa) { Ag (CN)2}2]·x guestsAnd a synthetic method and application thereof.
Background
With the rapid development of the field of microelectronics, electronic components at the molecular level are receiving more and more attention, and become one of the hot spots of the current material science research. The spin cross complex as a typical bistable material has attractive application prospect in the fields of molecular switches, molecular recognition, information storage materials, display devices and the like, and has received wide attention. Molecular bistability refers to the fact that a molecule can exist in two stable electronic states under certain external conditions. Having d4-d7When transition metal ions with electronic configuration are subjected to external stimulation such as temperature, illumination, pressure and the like in an octahedral field, the electronic configuration of the metal is recombined and is converted from a high spin state to a low spin state, and the two states respectively correspond to the situation that the maximum and minimum unpaired electron number appears in the arrangement of electrons in a metal orbital level, so that a series of physicochemical properties such as magnetism, color, dielectric constant, density and the like are changed. Therefore, the material has attractive application prospect in the fields of molecular switches, color development devices, information storage and the like.
In the early 90 s of the 20 th century, Kahn et al made a remarkable contribution to the development of the spin-crossover field. They theorize that increasing intermolecular synergy (bridging to coordination polymers by covalent bonds or increasing intermolecular interaction forces such as hydrogen bonding, pi-pi stacking or van der Waals forces, etc.) would be beneficial in increasing the spin transition temperature of spin-crossed complexes ((T c) Increasing the number of hysteresis steps or increasing the thermal hysteresis width, etc. These are not only important factors for the design of spin-cross complexes, but also very valuable metrics of whether the synthesized materials can be practically used.
Disclosure of Invention
The invention aims to provide an Fe (II) coordination polymer with spin-crossing property, and the spin-crossing property is regulated by introducing a specific guest molecule into a framework. In addition, the invention also provides a preparation method of the compound, which has the advantages of simple operation, high yield, cost saving, contribution to industrial production and capability of being applied in practice.
In order to achieve the purpose, the invention is realized by the following technical scheme:
designing a temperature-induced three-dimensional spin cross coordination polymer with a molecular formula of [ Fe (bpa) { Ag (CN)2}2]·x guestsI.e. one Fe per minimum asymmetric unit2+One bpa ligand, two [ Ag (CN)2]-A counter anion, and x guest molecules: (guests) The bpa ligand is 1, 4-bis (4-pyridyl) anthracene.
Preferably, the guest molecule is at least one of carbon disulfide, ethanol, acetonitrile, benzene, naphthalene, and N, N-dimethylformamide.
Preferably, each minimum asymmetric unit comprises one molecule of ethanol and 1 molecule of N, N-dimethylformamide, i.e., of the formula [ Fe (bpa) { Ag (CN)2}2]DMF. EtOH of formula C33H29N7O2Ag2Fe。
Preferably, the coordination polymer is a crystalline material, is an orthorhombic system,Pccnspace group, cell parameter ofa=14.7444(6)Å，b=30.4531(15)Å，cUnit cell volume =6295.4(5) a =14.0206(7) a3。
The thermogravimetric theory weight loss rate of the coordination polymer is 14.4%, and the actual weight loss rate is 15.1%.
The invention provides a preparation method of the three-dimensional spin cross coordination polymer, which comprises the following steps:
dissolving iron salt in ethanol or acetonitrile, and mixing 1, 4-bis (4-pyridyl) anthracene and K [ Ag (CN)2]Mixing and dissolving in N, N-dimethylformamide, placing the two solutions in an open container, placing the two containers in a closed container with ethanol or acetonitrile at the bottom, and diffusing in the shade at room temperature to obtain coordination polymer [ Fe (bpa) { Ag (CN)2}2]DMF, EtOH orFe(bpa){Ag(CN)2}2]·DMF·MeCN。
And (3) carrying out heat treatment on the obtained product at the temperature of 150-.
Preferably, the iron salt is Fe (ClO)4)2·6H2O。
Preferably, the Fe (ClO)4)2·6H2O, 1, 4-bis (4-pyridyl) anthracene and K [ Ag (CN)2]The amount ratio of (a) to (b) is 1:0.8-1.2:1.6-2.4, more preferably 1:1: 2.
The invention has the advantages that at least:
(1) the invention provides a Hoffman type crystal material with a three-dimensional structure, the coordination polymer can realize complete two-step high-low spin conversion through temperature change, and has remarkable application value in the aspects of molecular thermomagnetic switch materials, information storage materials and the like.
(2) The invention can utilize the thermal stability of the complex frame, and can realize excellent and various spin transformation behaviors of mutation type, multi-step type transformation, magnetic hysteresis width reaching about 60K, spin transformation temperature rise and the like by introducing different organic solvents as guest molecules to carry out temperature-changing magnetic susceptibility test, thereby realizing the regulation and control of the guest molecules on spin cross properties.
(3) The crystal material prepared by the invention can be prepared by a convenient diffusion method, can be placed at room temperature to obtain a product with higher purity, and has the advantages of simple method, convenient conditions and contribution to realizing large-scale production.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of the crystal material of example 1 of the present invention (hydrogen atoms and solvent molecules are omitted).
FIG. 2 is a schematic three-dimensional structure of the crystalline material of example 1 of the present invention (hydrogen atoms and solvent molecules omitted).
FIG. 3 is a PXRD pattern of the crystalline material of example 1 of the present invention.
FIG. 4 is a thermogravimetric analysis of the crystalline material of example 1 of the present invention.
FIG. 5 is an infrared spectrum of the crystalline material of example 1 of the present invention.
FIG. 6 is a graph showing the temperature-varying molar magnetic susceptibility of the crystalline material of example 1 of the present invention.
FIG. 7 is a thermogravimetric analysis of guest molecules introduced in accordance with the present invention.
FIG. 8 is a graph showing the temperature-changing molar magnetic susceptibility test of the hollow-frame coordination polymer of the present invention.
FIG. 9 is a graph of temperature-variable molar magnetic susceptibility testing with ethanol introduced according to the present invention.
FIG. 10 is a graph of temperature-variable molar magnetic susceptibility testing with acetonitrile introduced according to the present invention.
FIG. 11 is a graph of the temperature-variable molar magnetic susceptibility test of benzene introduced in accordance with the present invention.
Figure 12 is a graph of a temperature-variable molar magnetic susceptibility test incorporating carbon disulfide in accordance with the present invention.
FIG. 13 is a graph of temperature-variable molar magnetic susceptibility testing with naphthalene introduced in accordance with the present invention.
FIG. 14 is a graph showing the temperature-changing molar magnetic susceptibility test of the coordination polymer obtained in example 3 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The raw material reagent adopted by the embodiment of the invention is a raw material reagent which is purchased conventionally.
Example 1
A three-dimensional spin cross coordination polymer is prepared by the following steps:
0.05mmol of Fe (ClO)4)2·6H2Dissolving O in 1mL of ethanol, and placing the solution in a small glass test tube with the length of 10cm and the diameter of 0.5 cm; 0.05mmol of organic ligand bpa and 0.1mmol of K [ Ag (CN)2]Mixing, dissolving in 5ml of mixed solution of DMMF, and placing in a glass tube with length of 5cm and diameter of 1.5 cm; will contain Fe (ClO)4)2·6H2Glass vial with O ethanol solution and fittings bpa and K [ Ag (CN)2]The glass tube is placed in a large glass bottle, the gap between the glass tube and the glass bottle is filled with ethanol, and light yellow blocky crystals are obtained on the two glass tube walls after the glass tube is kept stand in the dark for 2 weeks. The crystals were collected and weighed to a mass of 25mg and divided by the theoretical product mass calculated based on the starting bpa ligand, giving a crystal yield of 60%. And carrying out related detection on the obtained light yellow blocky crystal, wherein the specific data are as follows:
single crystal structure: data collection temperatures were 100K, 175K and 250K, respectively, and were collected using a Bruker D8 QUEST X-ray single crystal diffractometer using Mo K α radiation monochromated by a graphite monochromator as the light source (λ = 0.71073 a) and diffraction data were collected over a range of angles in a β - ω scanning mode. And (3) performing full matrix least square method refinement on coordinates and anisotropic thermal parameters of all non-hydrogen atoms by using a SHELX-97 program for all data reduction and structure analysis, and theoretically hydrogenating all hydrogen atoms. Wherein, the single crystal X-ray diffraction result shows that the crystal material of the embodiment belongs to an orthorhombic system, and the space group isPccnThe crystallographic data are shown in table 1.
Each minimum asymmetric unit of the crystal material of the embodiment contains crystallographically independent Fe2+One bpa ligand, two [ Ag (CN)2]-Counter anion, and 1 ethanol and 1 DMF solvent molecule, i.e., [ Fe (bpa) { Ag (CN)2}2]DMF. EtOH of formula: c33H29N7O2Ag2Fe. In the structure, Fe (II) atom is located at coordination center of octahedron, and four N atoms coordinated with Fe at equatorial plane position are respectively from four Ag (CN)2 -Anion, and the two N atoms in the axial direction are from the pyridine rings of the two bpa ligands, respectively. The crystal structure is shown in figure 1, and the three-dimensional interpenetrating Hofmann structure is shown in figure 2.
Powder X-ray diffraction (PXRD): the measurement conditions were tube pressure: 40kV, pipe flow: 400 mA, Cu KαRadiation scanning speed: 2 degree per min−1Step interval: 0.02 deg., scan range (2)θ): 5-50 degrees, and the scanning mode is continuous scanningFig. 3. The result shows that the peak position of the synthesized sample basically corresponds to the single crystal diffraction peak position, and the crystal material of the embodiment has better crystallinity and purity.
Thermogravimetric analysis: weighing 5-10mg of sample, and performing thermogravimetric analysis on the sample by adopting a TG-209 type thermogravimetric analyzer in N2And measuring the thermal stability of the sample under the atmosphere, wherein the temperature range is 25-900 ℃ (10K/min), thereby obtaining the thermogravimetric spectrum of the sample. The results are shown in fig. 4, and the test results show that the theoretical weight loss rate of the crystal is consistent with the actual weight loss rate, and the mass loss is not changed in the range of 420K-540K, which indicates that the frame is stable in the range. Therefore, the complex can be heated to about 430K according to the boiling point of the solvent molecules, so that the framework guest can be removed.
Infrared [ IR (cm)-1)]: the KBr blank of the Bruker-Equinox 55 type infrared spectrometer is recorded at 4000-400 cm−1Infrared spectrum in the range: IR (KBr, cm)−1): 3423(m), 3063(m), 2924(m), 2853(m), 2166(s), 2073(m), 1655(s), 1609(s), 1543(m), 1419(s), 1393(s), 1255(w), 1067(s), 1015(m), 950(w), 814(s), 792(w), 744(s), 643(s), see FIG. 5 for details.
Testing the variable temperature magnetic susceptibility: referring to fig. 6, the complex shows a two-step complete spin transfer behavior below 300K. The magnetic susceptibility is 3.50 cm in the range of normal temperature to 240K3mol-1 The K is basically kept unchanged and basically accords with the theoretical value of the high-spin state of iron (II). The magnetic susceptibility is reduced to 1.97 cm by the rapid decrease at 230K-175K along with the decrease of temperature3mol-1 K. When the temperature is further reduced, the magnetic susceptibility is further reduced to 0.35 cm at 175K-110K3mol-1K, consistent with the low spin state.
Example 2
The spin-cross coordination polymer crystal material [ Fe (bpa) { Ag (CN) ] synthesized in example 12}2]DMF EtOH by thermal treatment at 150 ℃ to give [ Fe (bpa) { Ag (CN)2}2]An empty-frame coordination polymer. The resulting samples were placed in glass vials containing different pure organic reagents (carbon disulfide, ethanol, acetonitrile, benzene, naphthalene), and one week later, testedThe reagent was evaporated into the frame of the sample to give a new sample [ Fe (bpa) { Ag (CN)2}2]·x guests。
Different samples are weighed and subjected to thermogravimetric analysis and temperature-variable magnetic susceptibility test respectively, the results are shown in figure 7, and the amount of the solvent contained in the frame can be calculated according to the weight loss rate respectively. Susceptibility testing was first performed on a solvent-free frame and a one-step full mutant spin transition occurred, accompanied by a thermal hysteresis width of about 9K. For guest carbon disulfide incorporation, [ Fe (bpa) { Ag (CN)2}2]·(0.9)CS2The spin-crossing behavior with zero-field splitting occurs and hysteresis loops of about 18K in width are present. When the guest is ethanol, [ Fe (bpa) { Ag (CN)2}2]EtOH (0.6) exhibits a symmetrical rare five-step spin-cross property. When the guest is acetonitrile, [ Fe (bpa) { Ag (CN)2}2](1.2) MeCN exhibits a two-step spin transition with incomplete hysteresis width of about 20K. For the introduction of aromatic guests, [ Fe (bpa) { Ag (CN)2}2]·(0.5)C6H6The magnetic susceptibility of (a) undergoes an asymmetric two-step spin-transfer behavior, resulting in 57K and 20K wide thermal hysteresis loops, respectively. And [ Fe (bpa) { Ag (CN)2}2](0.3) Napthalene, there is a complex multi-step spin-cross behavior with thermo-hysteresis loop widths of 9K, 6K, 5K and 8K, respectively.
Example 3
0.05mmol of Fe (ClO)4)2·6H2Dissolving O in 1mL of acetonitrile, and placing the solution in a small glass test tube with the length of 10cm and the diameter of 0.5 cm; 0.05mmol of organic ligand bpa and 0.1mmol of K [ Ag (CN)2]Mixing, dissolving in 5mL DMF solution, and placing in a glass tube with length of 5cm and diameter of 1.5 cm; will contain Fe (ClO)4)2·6H2Glass vial with O acetonitrile solution and fittings bpa and K [ Ag (CN)2]The glass tube is placed in a large glass bottle, the gap between the glass tube and the glass bottle is filled with acetonitrile, and after standing in the dark for 2 weeks, a yellow complex with small particles is obtained. Since the particles were too small and did not have a very pronounced gloss, no suitable crystals were introduced for the single crystal test. The sample was subjected to a magnetic susceptibility test,the results are shown in fig. 14, showing two steps accompanied by spin-crossing behavior with hysteresis widths of 5K and 7K, respectively.
Magnetic tests of the complexes show that the complexes have obviously diversified spin-crossing properties and can show bistable state under temperature stimulation. The process of converting the temperature signal into the magnetic signal can be used for sensing equipment, and can also be used as a molecular switch or an information storage material.
While the invention has been described with respect to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
TABLE 1 crystallographic data of the complexed polymer obtained in example 1
Claims (10)
1. A three-dimensional spin-cross coordination polymer characterized by: the molecular formula is [ Fe (bpa) { Ag (CN)2}2]·x guestsEach minimum asymmetric unit contains one Fe2+One bpa ligand, two [ Ag (CN)2]-A counter anion, and x guest molecules, the bpa ligand being 1, 4-bis (4-pyridyl) anthracene.
2. The three-dimensional spin-cross coordination polymer of claim 1, characterized in that: the guest molecule is at least one of carbon disulfide, ethanol, acetonitrile, benzene, naphthalene and N, N-dimethylformamide.
3. The three-dimensional spin-cross coordination polymer of claim 1, characterized in that: each minimum asymmetric unit comprises one ethanol molecule and 1N, N-dimethylformamide molecule, namely the molecular formula [ Fe (bpa) { Ag (CN)2}2]DMF. EtOH of formula C33H29N7O2Ag2Fe。
4. The three-dimensional spin-cross coordination polymer of claim 3, characterized in that: the coordination polymer is a crystal material and is an orthorhombic system,Pccnand (4) space group.
5. The three-dimensional spin-cross coordination polymer of claim 4, characterized in that: the crystal material has unit cell parameters ofa=14.7444(6)Å，b=30.4531(15)Å，cUnit cell volume =6295.4(5) a =14.0206(7) a3。
6. The three-dimensional spin-cross coordination polymer of claim 3, characterized in that: the thermogravimetric actual weight loss ratio of the coordination polymer is 15.1%.
7. A process for preparing a three-dimensional spin-cross coordination polymer according to any of claims 1 to 6, comprising the steps of:
dissolving iron salt in ethanol or acetonitrile, and mixing 1, 4-bis (4-pyridyl) anthracene and K [ Ag (CN)2]Mixing and dissolving in N, N-dimethylformamide, respectively placing the two solutions in an open container, placing the two containers in a closed container with ethanol or acetonitrile at the bottom, and diffusing in the shade at room temperature to obtain the three-dimensional spin cross-coordination polymer.
8. The method of claim 7, further comprising the steps of: the product obtained in the claim 7 is subjected to heat treatment at the temperature of 150 ℃ and 200 ℃ to obtain an empty-frame coordination polymer without solvent molecules, the empty-frame coordination polymer is placed in a container containing new guest molecules, and the guest molecules enter the frame through volatilization, so that the three-dimensional spin cross-coordination polymer containing the new guest molecules is obtained.
9. The method of claim 7, wherein: the iron salt is Fe (ClO)4)2·6H2O, said Fe (ClO)4)2·6H2O, 1, 4-bis (4-pyridyl) anthracene and K [ Ag (CN)2]The mass ratio of (A) to (B) is 1:0.8-1.2: 1.6-2.4.
10. Use of the three-dimensional spin-cross coordination polymer according to any one of claims 1 to 6 in a sensing device, a molecular switch, or an information storage material.
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| CN110078933A (en) * | 2019-04-30 | 2019-08-02 | 华南农业大学 | Novel coordination polymer crystalline material and preparation method thereof and fluorescent applications |
| CN110776649A (en) * | 2019-11-11 | 2020-02-11 | 重庆师范大学 | Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof |
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| CN103588799A (en) * | 2013-12-05 | 2014-02-19 | 南开大学 | Cadmium coordination polymer and preparation method and application thereof |
| CN110078933A (en) * | 2019-04-30 | 2019-08-02 | 华南农业大学 | Novel coordination polymer crystalline material and preparation method thereof and fluorescent applications |
| CN110776649A (en) * | 2019-11-11 | 2020-02-11 | 重庆师范大学 | Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof |
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| Title |
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| A fluorescent anthracene-based metal–organic framework for highly;Wang Jianhong, Li Guangyu,Liu Xiaojing,et.al;《Inorganica Chimica Acta》;20171227;全文 * |
| Extrinsic vs. intrinsic luminescence and their interplay with spin crossover in 3D Hofmann-type coordination polymer;Manuel Meneses-Sánchez,et.al;《Journal of Materials Chemistry C》;20191219;全文 * |
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