CN107417740A - A kind of one-dimensional cobalt complex and its preparation method and application - Google Patents
A kind of one-dimensional cobalt complex and its preparation method and application Download PDFInfo
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 241000675108 Citrus tangerina Species 0.000 claims abstract description 11
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000696 magnetic material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 3
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 230000007704 transition Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000002211 ultraviolet spectrum Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000002659 acromion Anatomy 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention belongs to metal organic complex technical field of magnetic materials, and in particular to a kind of preparation method and applications of one-dimensional cobalt complex.Described one-dimensional cobalt complex, its molecular formula are [Co (3,5pdc) (2,2 ' bpy) (H2O)2]·2H2O, wherein, 3,5pdc=3,5 pyridinedicarboxylic acid roots, 2,2 ' bpy=2,2 ' bipyridyls；The complex is anorthic system, the space groups of P 1, cell parameter is a=9.5342 (16), b=12.347 (3), c=16.635 (3), α=84.762 (14) °, β=73.727 (11) °, γ=86.749 (15) °, V=1871.0 (6)3；Tangerine color flat crystal.The preparation method of cobalt complex of the present invention is simple, and yield is high, environmentally friendly, ferromagnetic coupling between metallic cobalt be present；Cobalt complex of the present invention is easily recycled, reusable；With potential social benefit and economic benefit.
Description
Technical field
The invention belongs to Metal-organic complex technical field of magnetic materials, and in particular to a kind of one-dimensional cobalt complex
Preparation method and applications.
Background technology
Coordinative Chemistry is a science to grow up on the basis of inorganic chemistry, and the main object that it is studied is to match somebody with somebody
Position compound (coordination compounds, abbreviation complex).From earlier 1900s late nineteenth century youth scholar
Since Werner proposes the theory foundation Coordinative Chemistry of often referred to as Werner coordination theory now, it is all the time in inorganization
Learn the forward position of research.Complex refer to self-existent stable compound further combined with atom or ion answering for being formed
Heterocompound.
In recent years, the complex formed by polyacid part and transition metal causes great interest.This kind of complex due to
The diversity of structure, the electron orbit energy level and electronic interaction of complex can be effectively adjusted, therefore in molecular magnet
It is widely used with photoelectric effect etc.（[1] Hill R J, Long D L, Champness N R, et al.
Acc. Chem. Res., 2005, 38: 335-348；[2] Friedrichs O D, O′Keeffe M, Yaghi O M.
Acta Cryst. A,2003,59:22-27；[3] Ye B H, Tong M L, Chen X M. Coord. Chem.
Rev., 2005,249:545-565；[4] Inoue K, Imai H, Ghalsasi P S, et al. Angew. Chem.
Int. Ed., 2001, 40: 4242-4245；[5] Evans O R, Lin W B. Acc. Chem. Res., 2002,
35:511-522）；Some transition metal ions can tend to be coordinated with nitrogen-atoms, therefore nitrogen atom is just more in the polyacid part
Add easy and metallic ion coordination and form the chelate structure of complexity, meanwhile, when containing rigid matrix in part, can often have
The carrying internal stress of effect, construct multidimensional structure（[6] Wang X Q, Liu L M, Jacobson A J. Angew.
Chem. Int. Ed., 2006, 39: 6499-6503；[7] Chen W, Wang J Y, Chen C, et al.
Inorg. Chem., 2003,42:944-946；[8] Pan L, Parker B, Huang X Y, et al. J. Am.
Chem. Soc., 2006, 128: 4180-4181；[9] He J H, Yu J H, Zhang Y T, et al. Inorg.
Chem., 2005,44:9279-9282）.Therefore, on existing Research foundation, stability height, practicality are further developed
Good and environmentally friendly type complex, the development for Material Field is vital.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of one-dimensional cobalt complex, there is provided the preparation of the complex
Method and application.
To achieve these goals, the present invention adopts the following technical scheme that：A kind of one-dimensional cobalt complex, its molecular formula are
[Co (3,5pdc) (2,2 '-bpy) (H2O)2]·2H2O, wherein, 3,5pdc=3,5 pyridinedicarboxylic acid roots, 2,2 '-bpy=2,2 '-
Bipyridyl；The complex is anorthic system, P-1 space groups, and cell parameter is a=9.5342 (16), b=12.347 (3)
, c=16.635 (3), α=84.762 (14) °, β=73.727 (11) °, γ=86.749 (15) °, V=1871.0 (6)3；Tangerine
Color flat crystal.
To achieve these goals, the present invention also provides the preparation method of above-mentioned one-dimensional cobalt complex, specifically includes following
Step.
Step 1, cobalt nitrate is dissolved in a certain amount of distilled water, is prepared into solution A.
Step 2, the pyridinedicarboxylic acid of organic ligand 3,5 and 2 are weighed, 2 '-bipyridyl, are dissolved in a certain amount of distilled water,
It is prepared into solution B.
Step 3, by A, B mix, with liquid-transfering gun add concentration be 1mol/L alkali lye（Solute is triethylamine, and solvent is second
Alcohol）, stir until dissolving, is prepared into solution C.
Step 4, solution C put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, in 180 DEG C -200 DEG C of hot conditions
Under, after isothermal reaction 24 hours, room temperature is cooled in air；After solution system is stable, gained mixed solution is filtered,
Gained solid is washed with water 2-4 times, obtains tangerine color flat crystal, yield 60%.
Described cobalt nitrate, 3,5 pyridinedicarboxylic acids, the molar ratio of 2,2 '-bipyridyl are 1:1:1.
The volumetric usage of distilled water described in step 1 is 10-15 times of cobalt nitrate mole；Distilled water described in step 2
Volumetric usage be 10-15 times of 3,5 pyridinedicarboxylic acids and 2,2 '-bipyridyl total moles dosage.
The mole dosage of the alkali lye is the 5-10 of cobalt nitrate, 3,5 pyridinedicarboxylic acids and 2,2 '-bipyridyl total moles dosage
Times.
Described one-dimensional cobalt complex can be used for preparing magnetic material.
The remarkable result of the present invention.
Cobalt complex prepared by the present invention has one-dimensional chain lamellar structure, there is higher stability, raw material be cobalt nitrate,
3,5 pyridinedicarboxylic acids and 2,2 '-bipyridyl, are prepared using hydro-thermal method, and crystal recovery rate is high, environmentally safe；In the present invention
Pyridinedicarboxylic acid connects adjacent cobalt atom using nitrogen-atoms and a carboxyl oxygen atom, forms one-dimensional chain as bridge ligand
Structure；Its structure is defined as anorthic system, P-1 space groups by single crystal diffraction；Center cobalt ions is hexa-coordinate structure, is formed and omited
Micro- distorted octahedra；Determine the infrared spectrum, uv-vis spectra and variable temperature magnetic susceptibility of complex.
Synthesize and study the geometry of complex and electronic structure is one of important process of Coordinative Chemistry, use this hair
The cobalt complex of bright preparation can be obtained between adjacent cobalt ions and weak ferromagnetic coupling be present, be coupled by the test to variable temperature magnetic susceptibility
The cm of constant J=0.558-1；When using spectrum analysis electronic structure and transition, often due to there may be between various bands of a spectrum
It is overlapping and produce error, with the development of computer hardware and software, turned into point based on the Density Functional Study from the beginning counted
Analyse the effective tool of molecular structure and electronic structure；The present invention also using dependent quantization calculate analyze complex the density of states and
Electron transition；Occurs the new absworption peak of a complex in its ultraviolet spectra（325nm）；After being coordinated due to part pyridine ring
Typically there is blue shift, therefore be assigned as d-d transition, the electronic structure and rail for analyzing complex are calculated using quantization software
Road energy level, it is contemplated that the spin direction of d tracks, calculate d-d transition and appear in 344nm, result of calculation and ultraviolet spectra basic one
Cause.
The preparation method of cobalt complex of the present invention is simple, and yield is high, environmentally friendly, ferromagnetic coupling between metallic cobalt be present
Close；Cobalt complex of the present invention is easily recycled, reusable；With potential social benefit and economic benefit.
Brief description of the drawings
The molecular structure of Fig. 1 complexs.
The structure cell accumulation graph of Fig. 2 complexs.
The variable temperature magnetic susceptibility figure of Fig. 3 complexs（χ M are represented, Δ represents μ eff, and curve is fitting result）.
The ultraviolet spectra of Fig. 4 complexs.
Fig. 5 complex fermi levels（Dotted line）Neighbouring TDOS and the PDOS schematic diagrames of p, d electronics.
Embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1.
0.8 mmol cobalt nitrates are dissolved in 10ml distilled water, are prepared into solution A；Weigh 0.8mmol 3,5- pyridines
Dioctyl phthalate, 0.8mmol 2,2 '-bipyridyl, are dissolved in 18ml distilled water, are prepared into solution B；A, B are mixed, use liquid relief
Rifle adds the alkali lye 12mmol that concentration is 1mol/L（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into molten
Liquid C；In the polytetrafluoroethylliner liner that solution C is put into 40mL hydrothermal reaction kettles, the isothermal reaction 24 under 180 DEG C of constant temperature
After hour, room temperature is cooled in air；Closed stable system rear overnight, filtering, gained solid twice, are obtained with 10mL water washings
It is adapted to the block tangerine color flat crystal of single crystal diffraction.
Single crystal diffraction is carried out to the crystal using Germany's production Bruker P4 single crystal diffractometers, axonometry data are shown in Table 1 He
Table 2, structural formula is shown in Fig. 1.
The crystallographic data and structural analysis parameter of the complex of table 1.
The part bond distance of the complex of table 2（Å）With bond angle（°）.
Embodiment 2.
1mmol cobalt nitrates are dissolved in 10ml distilled water, are prepared into solution A；Weigh 1 mmol 3,5- pyridine diformazans
Acid, 1 mmol 2,2,- bipyridyl, is dissolved in 20ml distilled water, is prepared into solution B；A, B are mixed, added with liquid-transfering gun
Concentration is 1mol/L alkali lye 18mmol（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into solution C；Will
Solution C is put into the polytetrafluoroethylliner liner of 40 mL hydrothermal reaction kettles, isothermal reaction 24 hours under 180 DEG C of constant temperature
Afterwards, it is cooled to room temperature in air；Closed stable system rear overnight, filtering, gained solid twice, are fitted with 10 mL water washings
Close the block tangerine color flat crystal of single crystal diffraction.
The molecular structure of complex, is shown in Fig. 1；As seen from the figure, have two crystallography locus different in complex and
Coordination configuration and its similar Co (II) ion, are hexa-coordinate；Coordination atom is respectively 2,2,Two N atoms on-bpy,
N atoms in 3,5-pdc on pyridine heterocycle, the O atom and two water of coordination molecule of monodentate ligand on 3, a 5-pdc carboxyl,
Form a deformation octahedral coordination environment；By taking Co (1) as an example, in octoploids structure, O (10) and N (2), O (9) and N (3),
O (8) and N (1) is respectively as octahedra relative summit；It can be seen that from crystal structural data, O (10)-Ni (1)-N (2), O
(9)-Ni (1)-N (3) and O (8)-Ni (1)-N (1) angle is respectively 176.30 (12) °, 172.94 (14) ° and 170.17
(13) °, close to 180 °；N (1) O (8) N (2) O (10), N (2) O (9) N (3) O (10) and N (1) O (8) N (3) O (9) plane are inclined
Difference is respectively 0.0196,0.0239 and 0.1523, and the dihedral angle between three planes is respectively 92.4 °, 92.4 °
With 83.5 °；The coordination environment for all illustrating Co is the regular octahedron slightly deformed.
Embodiment 3.
2 mmol cobalt nitrates are dissolved in 20ml distilled water, are prepared into solution A；Weigh 2mmol 3,5- pyridine diformazans
Acid, 2mmol 2,2,- bipyridyl, is dissolved in 40ml distilled water, is prepared into solution B；A, B are mixed, added with liquid-transfering gun
Concentration is 1mol/L alkali lye 60mmol（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into solution C；Will
Solution C is put into the polytetrafluoroethylliner liner of 80 mL hydrothermal reaction kettles, isothermal reaction 24 hours under 200 DEG C of constant temperature
Afterwards, it is cooled to room temperature in air；Closed stable system rear overnight, filtering, gained solid twice, are fitted with 20 mL water washings
Close the block tangerine color flat crystal of single crystal diffraction.
Co ions, 3,5-pdc and 2,2,- bpy ratio is 1:1:1, each 3,5-pdc part passes through on a carboxyl
O and pyridine ring on N be connected to two Co ions, while each Co ions and two 3,5-pdc parts are connected, and are formed with this
The space one-dimensional catenary structure of zigzag；And had neither part nor lot on 3,5-pdc parts the carboxyl of coordination and coordination and free hydrone it
Between hydrogen bond be present, whole complex is thus linked to be three-dimensional structure, crystal structure is shown in Fig. 2.
Embodiment 4.
2 mmol cobalt nitrates are dissolved in 30ml distilled water, are prepared into solution A；Weigh 2mmol 3,5- pyridine diformazans
Acid, 2mmol 2,2,- bipyridyl, is dissolved in 45ml distilled water, is prepared into solution B；A, B are mixed, added with liquid-transfering gun
Concentration is 1mol/L alkali lye 30mmol（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into solution C；Will
Solution C is put into the polytetrafluoroethylliner liner of 80 mL hydrothermal reaction kettles, isothermal reaction 24 hours under 180 DEG C of constant temperature
Afterwards, it is cooled to room temperature in air；Closed stable system rear overnight, filtering, gained solid twice, are adapted to 30mL water washings
The block tangerine color flat crystal of single crystal diffraction.
The infrared spectrum of complex is determined by KBr pressed disc methods：3425(s,br), 3204(s,sh), 1608(s),
1566(s), 1438(m), 1398(m), 1375(s), 1283(w), 1126(w), 771(s), 761(m), 736(m),
652(m)cm–1。
The variable temperature magnetic susceptibility of complex is as shown in Figure 3；It is 5.19 B.M. in 298 K Effect magnetic moment（Feeble field limits）, far
More than the Co (II) (S=3/2) of high-spin only spin values（3.88 B.M.）；With the reduction of temperature, Effect magnetic moment persistently drops
It is low, reach 4.12 B.M. in 23K Effect magnetic moments；The reason for this magnetic behavior is due to as temperature rise has metal ion
To the charge transfer transition of part so that the increase of the actual valence state of Co (II) ion or Co (II) 4T1g ground state have one it is larger
Track contribution；It is mutual by the weak magnetic of 3,5-pdc parts in view of the contribution of Co (II) ion trajectory magnetic moment, and paramagnetic ion
Effect, we are first with the single ion approximation method of isotropism of Oh symmetry backspins rail coupling, to analyze experiment magnetic drop
Warm data.The magnetic susceptibility formula of use is as follows.
T is absolute temperature, and K is Boltzmann constant, and λ is rotation rail coupling constant（The rotation rail coupling of Co (II) free ion
Constant value λ is -176 cm-1）.
Due to weak magnetic interaction, formula between ion be present（1）It must be corrected with Exchange interaction；We
Further it is fitted according to molecular field approximation.
χ is that the exchange actually measured is coupled magnetic susceptibility, χCoIt is to be coupled the magnetic susceptibility in the presence of field, J is between metallic cobalt
Exchange interaction parameter, N are A Fojia get Luo constants, and β is Bohr magneton, and g is the g factors.
Experiment value and theoretical value is reached best fit using least square law technology, obtain corresponding magnetic parameter and fitting because
Sub- F (F=Σ [(XM) obs- (XM) calc]2/(XM)2obs).Fitting result：λ = -170.8 cm-1, g=2.31, J=
0.558 cm-1, F = 2.49×10-5.J >0 shows there is weak ferromagnetic coupling in complex molecule between metal Co.
Embodiment 5.
2 mmol cobalt nitrates are dissolved in 20ml distilled water, are prepared into solution A.Weigh 2mmol 3,5- pyridine diformazans
Acid, 2mmol 2,2,- bipyridyl, is dissolved in 40ml distilled water, is prepared into solution B.A, B are mixed, added with liquid-transfering gun
Concentration is 1mol/L alkali lye 35mmol（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into solution C；Will
Solution C is put into the polytetrafluoroethylliner liner of 40 mL hydrothermal reaction kettles, isothermal reaction 24 hours under 180 DEG C of constant temperature
Afterwards, it is cooled to room temperature in air；Closed stable system rear overnight, filtering, gained solid twice, are adapted to 10mL water washings
The block tangerine color flat crystal of single crystal diffraction.
Complex uv-vis spectra is as shown in Figure 4；Start absworption peak occur when less than 400nm, the suction at its 303nm
Receive peak and two acromions be present（Peak 1, peak 3）；Because the absworption peak that part pyridine ring is not coordinated is generally present in 303nm, after coordination
Violet shift, therefore peak 2 and the absworption peak that acromion 1 is pyridine ring in the uv-vis spectra of complex occurs；Near 240nm
Broad peak be also to be made up of the superposition of the multiple small absworption peaks of part；The absworption peak occurred in complex spectrum at 325nm is cobalt
Absworption peak caused by ion d-d transition.
Embodiment 6.
3mmol cobalt nitrates are dissolved in 30ml distilled water, are prepared into solution A.Weigh 3mmol 3,5- pyridine diformazans
Acid, 3mmol 2,2,- bipyridyl, is dissolved in 60ml distilled water, is prepared into solution B；A, B are mixed, added with liquid-transfering gun
Concentration is 1mol/L alkali lye 50mmol（Solute is triethylamine, and solvent is ethanol）, stir until dissolving, is prepared into solution C；Will
Solution C is put into the polytetrafluoroethylliner liner of 40 mL hydrothermal reaction kettles, isothermal reaction 24 hours under 200 DEG C of constant temperature
Afterwards, it is cooled to room temperature in air；It is closed overnight after, filtering, gained solid twice, obtains suitable monocrystalline and spread out with 20 mL water washings
The block tangerine color flat crystal penetrated.
Using generalized gradient approximation in Density functional（GGA）Method, BLYP mode processing modes are used to electronic correlation item,
From being in harmony fitting precision ＜ 10-6EV, base group are set as DND patterns；By calculating, the density of states (DOS) of complex and p, d ministry of electronics industry
Divide the density of states（PDOS）Display is in Figure 5；As seen from Figure 5, the density of states near fermi energy levels is mainly by p, d electronics structure
Into wherein d density of electronic states is divided due to the coordination of cobalt ions, is mainly split into 5 main peaks（Due to not being positive octahedral
Body, symmetry reduce, and multiple spliting occurs for d tracks）, d electronics has 3 primary electron states near fermi energy levels, it is contemplated that
Spin factor, its transition energy gap occurred is 0.1253 Hatree, equivalent to 344nm in ultraviolet spectra, this and complex
Being positioned relatively close to for UV absorption occurs when less than 400nm, and due to the broadening of d density of electronic states, electron transition meeting
Form wider absorption band.Contrast the d-d jumps of the 344nm of 325nm absworption peak and quantum chemical method in complex ultraviolet spectra
Move, it is believed that quantum chemical method result is coincide substantially with ultraviolet spectrum data.
Claims (6)
1. a kind of one-dimensional cobalt complex, it is characterised in that the molecular formula of the complex is [Co (3,5pdc) (2,2 '-bpy)
(H2O)2]·H2O, wherein, pdc=3,5 pyridinedicarboxylic acid roots, 2,2 '-bpy=2,2 ' bipyridyls；The complex is three tiltedly brilliant
System, P-1 space groups, cell parameter：A=9.5342 (16), b=12.347 (3), c=16.635 (3), α=84.762
(14) °, β=73.727 (11) °, γ=86.749 (15) °, V=1871.0 (6)3；Tangerine color flat crystal.
2. one-dimensional cobalt complex as claimed in claim 1, it is characterised in that specifically include following steps：
Step 1, cobalt nitrate is dissolved in a certain amount of distilled water, is prepared into solution A；
Step 2, the pyridinedicarboxylic acid of organic ligand 3,5 and 2 are weighed, 2 '-bipyridyl, be dissolved in a certain amount of distilled water, prepared
Into solution B；
Step 3, by A, B mix, with liquid-transfering gun add concentration be 1mol/L alkali lye（Solute is triethylamine, and solvent is ethanol）,
Stirring is prepared into solution C until dissolving；
Step 4, solution C put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, it is permanent under 180 DEG C -200 DEG C of hot conditions
After temperature reaction 24 hours, room temperature is cooled in air；After solution system is stable, gained mixed solution is filtered, gained
Solid is washed with water 2-4 times, obtains tangerine color flat crystal, yield 60%.
3. the preparation method of one-dimensional cobalt complex as claimed in claim 2, it is characterised in that described described cobalt nitrate,
3,5 pyridinedicarboxylic acids, the mol ratio of 2,2 '-bipyridyl are 1:1:1.
4. the preparation method of one-dimensional cobalt complex as claimed in claim 2, it is characterised in that distilled water described in step 1
Volumetric usage is 10-15 times of cobalt nitrate mole；The volumetric usage of distilled water described in step 2 be 3,5 pyridinedicarboxylic acids and
10-15 times of the total dosage of 2,2 '-bipyridyl.
5. the preparation method of one-dimensional cobalt complex as claimed in claim 2, it is characterised in that the mole dosage of the alkali lye is
5-10 times of cobalt nitrate, 3,5 pyridinedicarboxylic acids and 2,2 '-bipyridyl total moles dosage.
6. the one-dimensional cobalt complex as described in claim 1-5 is used to prepare magnetic material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727251A (en) * | 2018-05-17 | 2018-11-02 | 商丘师范学院 | One kind being based on magnetic cobalt (II) complex and preparation method thereof of 4,4 '-bipyridyls-itaconic acid derived ligand |
| CN110157004A (en) * | 2019-05-28 | 2019-08-23 | 上海大学 | One-dimensional cobalt coordination polymer and preparation method thereof |
| CN111253445A (en) * | 2020-03-10 | 2020-06-09 | 扬州工业职业技术学院 | Preparation method of porous spherical metal cobalt complex |
-
2017
- 2017-05-18 CN CN201710352863.9A patent/CN107417740A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| YA-HUI ZHAO等: "Syntheses and characterizations of four metal coordination polymers constructed by the pyridine-3,5-dicarboxylate ligand", 《POLYHEDRON》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727251A (en) * | 2018-05-17 | 2018-11-02 | 商丘师范学院 | One kind being based on magnetic cobalt (II) complex and preparation method thereof of 4,4 '-bipyridyls-itaconic acid derived ligand |
| CN110157004A (en) * | 2019-05-28 | 2019-08-23 | 上海大学 | One-dimensional cobalt coordination polymer and preparation method thereof |
| CN111253445A (en) * | 2020-03-10 | 2020-06-09 | 扬州工业职业技术学院 | Preparation method of porous spherical metal cobalt complex |
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