CN114524831A - Dysprosium complex and preparation method and application thereof - Google Patents
Dysprosium complex and preparation method and application thereof Download PDFInfo
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- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 70
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010668 complexation reaction Methods 0.000 title description 2
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 13
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- DCKWZDOAGNMKMX-UHFFFAOYSA-N dysprosium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DCKWZDOAGNMKMX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 230000005307 ferromagnetism Effects 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- -1 dysprosium metal salt hexahydrate Chemical class 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- OAJVDTNJHZCKJP-UHFFFAOYSA-N dysprosium hexahydrate Chemical compound O.O.O.O.O.O.[Dy] OAJVDTNJHZCKJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000696 magnetic material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- HFEOHRWLEGXZHW-UHFFFAOYSA-K trichlorodysprosium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Dy+3] HFEOHRWLEGXZHW-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 27
- 230000005291 magnetic effect Effects 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000000914 Dysprosium Chemical class 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract
The invention discloses a dysprosium complex and a preparation method and application thereof. The dysprosium coordination compound has a structural formula as follows: [ Hdmbpy ]][Dy(H2dobdc)2(H2O)]·3H2O，H2The dobdc ligand is a divalent anion of 2, 5-dihydroxyterephthalic acid losing two protons, and the Hdmbpy ligand represents that 4,4 '-dimethyl-2, 2' -bipyridine obtains a monovalent cation of one proton. The dysprosium complex of the invention is composed of H4The dobdc, the dmbpy and the dysprosium nitrate hexahydrate are obtained by a hydrothermal reaction one-step method, reaction raw materials are easy to obtain, the preparation method is simple, and the yield is high. The dysprosium coordination compound has ferromagnetism and typical slow relaxation behavior of a monomolecular magnet under a zero field, and the crystal structure of the dysprosium coordination compound contains hydrophilic pore canals, can keep the structure stable in a water environment, and can be used as a magnetic and proton conduction dual-function materialThe application has higher application value.
Description
Technical Field
The invention relates to a dysprosium complex and a preparation method and application thereof, belonging to the technical field of functional complexes.
Background
Metal organic framework complexes (MOFs) composed of metal cations, secondary building units or cluster compounds and multidentate organic ligands with coordination end groups have the characteristics of diverse compositions, diverse structures and rich functional designs, and have shown huge advantages in the aspects of optical sensing, fuel cells, spintronic devices, drug delivery, heterogeneous catalysis and the like nowadays (chem.Soc.Rev.2018,47, 8611-8638; coord.chem.Rev.2019,378, 365-381). Advanced materials that combine two or more functions in the same complex have attracted more and more researchers. In practical applications, one material can accomplish multiple tasks (J.Am.chem.Soc.2020,142, 3970-3979; J.Mater.chem.C. 2020,8, 16032-.
MOFs constructed by trivalent dysprosium ions and organic ligands have larger ground state spin and stronger intrinsic anisotropy of the dysprosium ions on one hand, are the best candidates of molecular magnetic materials, and have potential application prospects in the aspects of high-density data storage and molecular spin electronic devices (chem.Commun.2016,52, 4804-. On the other hand, the highly modifiable pore surface and the precise crystal structure of the MOFs provide great opportunity for improving proton conduction performance, and simultaneously provide an ideal crystal model for further understanding the mechanism of proton transfer, which can further promote the application of the MOFs in fuel cells (Matter 2020,2, 711-722; energy chem 2020,2, 100029). The inventor of the present invention finds that the existing research on the magnetic and proton conductive dual-function material based on the MOFs has disadvantages, such as poor water stability and low proton conductivity of the material, so that the practicality of the material is limited (eur.j.inorg.chem.2021,2021, 4610-4618; adv.mater.2020,32, e 1907090). Therefore, the novel dysprosium complex with different topological structures is designed and synthesized, a channel beneficial to proton transfer is created, and the dual-function material for realizing magnetism and proton conduction has very important significance.
Disclosure of Invention
In view of the problems in the prior art, a first object of the present invention is to provide a dysprosium complex with stable structure and dual properties of magnetism and high proton conductivity, which can be widely used in information storage and fuel cells as a novel multifunctional material with both magnetism and conductivity.
The second purpose of the invention is to provide a preparation method of the dysprosium complex, which uses simple and easily available raw materials to synthesize the dysprosium complex in one step, and has the advantages of simplicity, easy operation, high yield and low cost.
The third purpose of the invention is to provide an application of the dysprosium complex, wherein the dysprosium complex is used as a ferromagnetic material and shows a slow relaxation behavior of a monomolecular magnet under a zero field; the proton conductive material can show high proton conductivity under high-temperature and high-humidity environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
the dysprosium complex has a simple structure formula as follows: [ Hdmbpy ]][Dy(H2dobdc)2(H2O)]·3H2O, wherein: h2The dobdc ligand represents 2, 5-dihydroxyterephthalic acid (H)4dobdc) a divalent anion deprived of two protons; the hdmppy ligand indicates that 4,4 '-dimethyl-2, 2' -bipyridine (dmbpy) gives a monovalent cation of one proton; dy represents trivalent dysprosium ions.
The dysprosium complex is crystallized in a triclinic system and belongs to a P-1 space group, and the unit cell parameter is
α＝110.0330(10)°，β＝106.1880(10)°，γ＝95.7150(10)，
Selection of H in the invention4The dobdc is used as a ligand, the structure of the dobdc contains carboxyl-COOH and hydroxyl-OH functional groups, on one hand, the dobdc shows various coordination modes, and on the other hand, the dobdc is used as a donor and an acceptor of a hydrogen bond to provide a hydrophilic environment; dmbpy is selected as an auxiliary ligand, a pyridine group in the structure is used as a hydrogen bond receptor, a counter ion is provided after protonation, the hydrophilicity is improved, and the formed dysprosium complex has good water stability.
The dysprosium complex is composed of H2The dobdc ligand, the Hdmbpy ligand, the dysprosium (III) metal center and water molecules jointly form a three-dimensional porous structure containing hydrophilic triangular pore channels, wherein the Hdmbpy and a large number of water molecules occupy the pore channels, rich hydrogen bond channels are formed between the Hdmbpy and the framework, a path is provided for proton transfer, and the three-dimensional porous structure can be used as a potential proton conducting material.
The preparation method of the dysprosium complex comprises the following specific steps of:
stirring and mixing 2, 5-dihydroxy terephthalic acid, 4 '-dimethyl-2, 2' -bipyridyl, dysprosium hexahydrate metal salt and deionized water to obtain an aqueous solution; after being uniformly mixed, the mixture is reacted for 60 to 84 hours at a constant temperature of 135 to 145 ℃, and then the temperature is reduced to 25 to 35 ℃ after 12 to 20 hours, so that the dysprosium complex is prepared.
Keeping the solution at about 140 ℃ for more than 60 hours to provide proper energy so that the ligand and dysprosium ions can form coordinate bonds more easily; the solution is slowly cooled to about 30 ℃ over 12 hours in order to better generate single crystals.
Preferably, the concentration of the 2, 5-dihydroxyterephthalic acid in the aqueous solution is 0.009-0.011 mmol/mL, the concentration of the 4,4 '-dimethyl-2, 2' -bipyridine is 0.01-0.011 mmol/mL, and the concentration of the dysprosium salt hexahydrate is 0.007-0.011 mmol/mL.
Preferably, the ratio of the amounts of the 2, 5-dihydroxyterephthalic acid and 4,4 '-dimethyl-2, 2' -bipyridine to be charged into the reaction is 1 to 1.2: 1.
preferably, the amount of 2, 5-dihydroxyterephthalic acid and dysprosium metal salt hexahydrate mass to be charged to the reaction is in a ratio of 1: 0.76 to 1.2. The crystals precipitated at this ratio are more pure.
Preferably, the dysprosium metal salt hexahydrate is dysprosium nitrate hexahydrate or dysprosium chloride hexahydrate.
The invention also provides application of the dysprosium complex as a magnetic material and/or a proton conducting material.
The dysprosium complex has ferromagnetic interaction and can show slow relaxation behavior of a monomolecular magnet under a zero field.
The dysprosium complex as a proton conducting material can show good stability and higher proton conductivity in different relative humidity ranges and wider temperature ranges.
Preferably, the proton conductivity of the dysprosium complex is 1.86 multiplied by 10 at 30 ℃ and the relative humidity of 75-100 percent-6～1.70×10-4S cm-1Within the range. The proton conductivity is 1.70 x 10 at 30-70 ℃ and relative humidity of 100%-4～1.20×10-3S cm-1Within the range. Especially, the proton conductivity of the dysprosium complex reaches 1.20 multiplied by 10 when the temperature is 70 ℃ and the relative humidity is 100 percent-3S cm-1。
The dysprosium complex has double performances of magnetism and proton conduction, can be independently applied as a magnetic material or a proton conduction material, and can also be simultaneously applied as a magnetic material and a proton conduction material.
Compared with the prior art, the invention has the beneficial effects that: the dysprosium complex has definite microstructure information, presents a specific connection mode of a hydrogen bond, and is beneficial to understanding the proton conduction mechanism; the dysprosium complex is simple in preparation method, easily available in reaction raw materials, high in yield, low in cost and beneficial to industrial production, and can be obtained through one-step reaction; the dysprosium complex prepared by the invention has the characteristics of ferromagnetism and monomolecular magnet, shows good stability and higher proton conductivity in a wider temperature range and higher humidity environment, belongs to a super ion conductor, and can be used as a proton conductive material to be applied to extreme working environments.
Drawings
FIG. 1 is a crystal structure diagram of a dysprosium complex in example 1 of the present invention;
FIG. 2 is a schematic diagram of the three-dimensional porous structure of a dysprosium complex in example 1 of the present invention;
FIG. 3 is an infrared spectrum of a dysprosium complex in example 1 of the present invention;
FIG. 4 is a powder diffraction pattern of dysprosium complex under different conditions in example 1 of the invention;
FIG. 5 is a graph showing DC magnetic susceptibility test of dysprosium complex in example 1 of the present invention;
FIG. 6 is a plot of the imaginary AC susceptibility of a dysprosium complex in accordance with the invention as a function of temperature at zero field in example 1;
FIG. 7 is a graph of the impedance of a dysprosium complex at 75% and 100% relative humidity in example 1 of the invention;
FIG. 8 is a graph of the impedance of a dysprosium complex at different temperatures at a relative humidity of 100% in example 1 of the invention;
FIG. 9 is an Arrhenius diagram of dysprosium complex at different temperatures at a relative humidity of 100% in example 1 of the invention.
Detailed Description
The present invention will be further described with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention clearer, but these examples are only used to illustrate the present invention, and do not constitute any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited to the following examples.
Example 1: dysprosium complex [ Hdmbpy ]][Dy(H2dobdc)2(H2O)]·3H2Preparation of O (also abbreviated Dy-MOF in the present application)
0.1mmol of dysprosium nitrate hexahydrate (0.0457g), 0.103mmol of 2, 5-dihydroxyterephthalic acid (0.0204g, abbreviated as H in the present application)4dobdc) and 0.104mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0192g, dmbpy for short in the application) are added into 10mL of deionized water, mixed uniformly under the condition of stirring, then placed in a reaction kettle of polytetrafluoroethylene for sealing, reacted in an oven at 140 ℃ for 72 hours at constant temperature, and slowly cooled to 30 ℃ for 15 hours to obtain pale yellow blocky crystal Dy-MOF with the yield of 72.0 percent (based on H)4dobdc)。
The crystal obtained in this example was selected and tested using a Bruker Smart-APEXII CCD X-ray single crystal diffractometer. The obtained crystal structure refinement data are shown in table 1 below, part of the bond length is shown in table 2, and the hydrogen bond configuration is shown in table 3.
Table 1: structural refinement data of Dy-MOF
Table 2: partial bond length of Dy-MOF
Table 3: hydrogen bonding configuration of Dy-MOF
Two Dy (III) centers in the single crystal structure of Dy-MOF are connected through carboxylic acid groups to form [ Dy2(CO2)4]A binuclear structural unit (FIG. 1) which is further subjected to H of four different coordination modes2The dobdc ligands are connected to form a three-dimensional porous framework, free Hdmbpy and water molecules occupy the pore channels, and rich hydrogen bond interaction exists between the dobdc ligands and the framework (figure 2)
The Dy-MOF of this example was characterized by IRAffinity-1S infrared spectroscopy, and the results were: 3515.33(w),1639.52(m),1599.98(w),1580.69(w),1495.82(m),1448.57(s),1355.98(m),1242.18(vs),1113.91(w),922.95(w),910.42(w),875.70(w),814.94(s),796.61(m),783.11(w),759.00(w),610.48(w),551.65(m),518.86(w),416.63(w) (fig. 3).
The phase purity and stability of the Dy-MOF of this example were characterized using a Bruker D8 ADVANCE powder diffractometer. As shown in FIG. 4, it can be seen from the comparison of the curve obtained from the experiment and the curve obtained from the simulated crystal data that Dy-MOF prepared by the above method is in a pure phase. In addition, after the material is soaked in an aqueous solution for 7 days, the curve is still consistent, which shows that Dy-MOF has good water stability and provides guarantee for the application of Dy-MOF in proton conducting materials.
Comparative examples 1 to 1
The water added in the example 1 is replaced by N, N-dimethylformamide or a mixed solvent of water and N, N-dimethylformamide, and the rest conditions are unchanged; as a result, no crystals or powder product was produced.
Comparative examples 1 to 2
The reaction temperature in example 1 was changed to 125 ℃ or less, and the remaining conditions were unchanged; as a result, no crystals or powder product was produced.
Comparative examples 1 to 3
The reaction time in example 1 was changed to 60 hours or less, and the remaining conditions were not changed; as a result, no crystals or powder product was produced.
As is clear from comparison of example 1 to comparative examples 1 to 3, in the present invention, if water is replaced with another solvent, the objective dysprosium complex cannot be obtained due to the solvent effect. If the reaction temperature is lowered or the reaction time is shortened, the desired dysprosium complex cannot be obtained. Therefore, the present invention uses water as a solvent, and requires a sufficient reaction temperature and reaction time to supply the energy required for the reaction.
Example 2: preparation of Dy-MOF
0.1mmol of dysprosium chloride hexahydrate (0.0377g) and 0.099mmol of H4dobdc (0.0196g) and 0.1mmol dmbpy (0.0184g) are added into 10mL deionized water, mixed evenly under stirring, then placed in a polytetrafluoroethylene reaction kettle for sealing, reacted in a drying oven at 140 ℃ for 72 hours at constant temperature, and slowly cooled to 30 ℃ for 15 hours to obtain light yellow blocky crystals with the yield of 61.6 percent (based on H)4dobdc)。
Single crystal diffraction analysis was performed on the crystal obtained in this example, and it was confirmed that the obtained pale yellow bulk crystal was Dy — MOF, which was the same substance as that obtained by the preparation method of example 1.
Example 3: preparation of Dy-MOF
0.076mmol of dysprosium nitrate hexahydrate (0.0457g), 0.1mmol of 2, 5-dihydroxyterephthalic acid (0.0198g, abbreviated herein as H)4dobdc) and 0.1mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0184g, in this application)Dmbpy for short) was added to 10mL of deionized water, mixed well with stirring, and then placed in a polytetrafluoroethylene reaction vessel for sealing, reacted in a 135 ℃ oven at a constant temperature for 84 hours, and slowly cooled to 30 ℃ for 12 hours to obtain pale yellow massive crystals with a yield of 63.5% (based on H)4dobdc)。
Single crystal diffraction analysis was performed on the crystal obtained in this example, and it was confirmed that the obtained pale yellow bulk crystal was Dy — MOF, which was the same substance as that obtained by the preparation method of example 1.
Example 4: preparation of Dy-MOF
0.11mmol of dysprosium nitrate hexahydrate (0.0502g) and 0.092mmol of 2, 5-dihydroxyterephthalic acid (0.0182g, abbreviated as H in the present application) were mixed together4dobdc) and 0.11mmol of 4,4 '-dimethyl-2, 2' -bipyridine (0.0203g, dmbpy for short in the present application) were added to 10mL of deionized water, mixed well under stirring, then placed in a polytetrafluoroethylene reaction kettle for sealing, reacted in an oven at 145 ℃ for 60 hours at constant temperature, and slowly cooled to 35 ℃ over 20 hours to give pale yellow bulk crystals with a yield of 67.2% (based on H)4dobdc)。
Single crystal diffraction analysis was performed on the crystal obtained in this example, and it was confirmed that the obtained pale yellow bulk crystal was Dy — MOF, which was the same substance as that obtained by the preparation method of example 1.
In order to test the magnetic properties and the proton conduction properties of the dysprosium complexes prepared by the invention.
Application example 1
The dysprosium complex prepared in the embodiment 1 of the invention has direct current magnetic susceptibility (chi) under the conditions that the field strength is 1kOe and the temperature is 1.8-300KM) The test of (1). As shown in FIG. 5, at 300K, the product of the DC magnetic susceptibility and the temperature (T) is 14.31cm3K mol-1. As the temperature begins to decrease, the value of the product decreases slowly, reaching 12.39cm at 10K3 K mol-1Continuing to decrease the temperature, the product begins to increase rapidly, reaching 13.62cm at 1.8K3 K mol-1Indicating that the binuclear dysprosium ions in the Dy-MOF have ferromagnetic interaction.
Application example 2
The imaginary part alternating current magnetic susceptibility (chi') of the dysprosium complex prepared in the embodiment 1 of the invention is tested under the conditions that the field strength is 0Oe, the temperature is 1.8-5.0K, and the frequency is 1-707 Hz. The imaginary part alternating current magnetic susceptibility of Dy-MOF gradually decreases with the increase of temperature, and shows obvious temperature dependence (figure 7), and curves at different frequencies are not overlapped with each other, so that the slow relaxation characteristic of the typical single-molecule magnet is realized.
Application example 3
The dysprosium complex prepared in inventive example 1 was tested for proton conductivity at 30 ℃ and Relative Humidity (RH) of 75% and 100%, respectively. The proton conductivity (sigma) of dysprosium complex is from 1.87X 10 with the increase of relative humidity-6S cm-1Increased to 1.70X 10-4S cm-1The application of the dysprosium complex serving as a proton conducting material in different humidity environments is demonstrated.
Application example 4
The dysprosium complex prepared in the embodiment 1 of the invention is tested for proton conductivity at 100% RH and at a temperature of 30-70 ℃. The proton conductivity of the dysprosium complex increases gradually with increasing temperature, reaching a maximum of 1.20X 10 at 70 ℃ due to a thermal activation mechanism-3S cm-1Far exceeding 10-4S cm-1Belongs to super ion conductors, and explains that the dysprosium complex can be used as a proton conducting material to be applied at different temperatures.
Application example 5
Activation energy (E) of dysprosium complex prepared in embodiment 1 of the invention at 100% RH and within the temperature range of 30-70 ℃a) From Arrhenius formula σ T ═ σ0exp(Ea/kBT) is calculated. Linear fitting is carried out on the data of 1000/T by ln (sigma T) to obtain EaThe value of (A) is 0.37eV (FIG. 9), which shows that the proton conduction of dysprosium complex follows a hopping mechanism, and protons received on a group hop to another adjacent group through an infinite hydrogen bond network, thereby realizing the rapid transfer of protons.
The dysprosium complex can keep stable structure in a high humidity environment, has ferromagnetism and slow relaxation behavior of a monomolecular magnet under a zero field, shows high proton conductivity in a wider temperature range, can be used as a potential magnetic and proton conductive dual-function material, and has higher application value. And the preparation method is simple, high in yield, low in cost and suitable for large-scale popularization and application.
Claims (10)
1. A dysprosium complex, characterized by: the structure is simple as follows: [ Hdmbpy ]][Dy(H2dobdc)2(H2O)]·3H2O, wherein H2The dobdc ligand represents a divalent anion of 2, 5-dihydroxyterephthalic acid deprived of two protons; the Hdmbpy ligand indicates that 4,4 '-dimethyl-2, 2' -bipyridine gives a monovalent cation of one proton.
2. A dysprosium complex according to claim 1, characterized in that: the dysprosium complex is crystallized in a triclinic system and belongs to a P-1 space group, and the unit cell parameter is
α＝110.0330(10)°，β＝106.1880(10)°，γ＝95.7150(10)，
3. A process for the preparation of a dysprosium complex according to claim 1 or 2, characterized in that: stirring and mixing 2, 5-dihydroxyterephthalic acid, 4 '-dimethyl-2, 2' -bipyridine, dysprosium hexahydrate metal salt and water to obtain an aqueous solution; after the mixture is uniformly mixed, the mixture is subjected to constant temperature reaction for 60 to 84 hours at the temperature of 135 to 145 ℃, and then the mixture is cooled to 25 to 35 ℃ after 12 to 20 hours, so that the dysprosium complex is prepared.
4. A method for the preparation of a dysprosium complex according to claim 3, characterized in that: the concentration of the 2, 5-dihydroxyterephthalic acid in the aqueous solution is 0.009-0.011 mmol/mL, the concentration of the 4,4 '-dimethyl-2, 2' -bipyridyl is 0.01-0.011 mmol/mL, and the concentration of the dysprosium hexahydrate metal salt is 0.007-0.011 mmol/mL.
5. A method for preparing a dysprosium complex according to claim 3, characterized in that: the amount ratio of the 2, 5-dihydroxyterephthalic acid and 4,4 '-dimethyl-2, 2' -bipyridine to be charged into the reaction is 1 to 1.2: 1.
6. a method for the preparation of a dysprosium complex according to claim 3, characterized in that: the mass ratio of 2, 5-dihydroxyterephthalic acid and dysprosium metal salt hexahydrate to be charged into the reaction is 1: 0.76 to 1.2.
7. A method for the preparation of a dysprosium complex according to claim 3, characterized in that: the dysprosium salt hexahydrate is dysprosium nitrate hexahydrate or dysprosium chloride hexahydrate.
8. Use of a dysprosium complex according to claim 1 or 2, characterized in that: as a magnetic material and/or a proton conducting material.
9. Use of a dysprosium complex according to claim 8, characterized in that: has ferromagnetism and shows the typical slow relaxation behavior of a monomolecular magnet under a zero field.
10. Use of a dysprosium complex according to claim 8, characterized in that: the proton conductivity of the dysprosium complex is 1.70 multiplied by 10 at the temperature of 30-70 ℃ and the relative humidity of 100 percent-4～1.20×10-3S cm-1Within the range.
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