CN106432749A - Two-dimensional metal nickel coordination polymer with mixed ligands and preparation method of two-dimensional metal nickel coordination polymer - Google Patents
Two-dimensional metal nickel coordination polymer with mixed ligands and preparation method of two-dimensional metal nickel coordination polymer Download PDFInfo
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Abstract
The invention provides a two-dimensional nickel coordination polymer with mixed ligands and a preparation method of the two-dimensional nickel coordination polymer with the mixed ligands. The molecular formula of the coordination polymer is C21H22N2 NiO7. The coordination polymer is a P-1 space group of a triclinic crystal system. The space unit parameters are as follows: a=7.72490(10) angstrom, b=10.33790 (10) angstrom, c= 15.6347 (2) angstrom, alpha=107.8604(8) degrees, beta=104.1316(8) degrees, gamma= 98.0857(8) degrees and V=1120.58(2) angstrom<3>. The two-dimensional nickel coordination polymer with the mixed ligands is easy to prepare under hydrothermal conditions, has good stability and high crystallinity, and has a very good potential application prospect in the field of molecular magnets.
Description
Technical field
The invention belongs to the synthesis field of metal organic coordination polymer, it is related to a kind of two-dimensional metallic nickel of mixed ligand
Coordination polymer and preparation method thereof.
Background technology
It is by the organic ligand containing electron donating group and center that metal organic coordination polymer belongs to organic coordination polymer
Metal ion is formed by coordinate bond self assembly.Central ion is typically transition metal ionss, has certain ligancy,
Lifting plate acts on；Organic ligand has multiple coordination sites, plays component effect.In order to obtain various interesting topological structure, recently
People construct supramolecular network structure using two kinds or two or more different ligands during self assembly.
In recent years, when synthesizing coordination polymer with the favor of multidentate ligand extremely chemist.Conventional multidentate ligand
There are multiple tooth Carboxylic acid ligand and multiple tooth containing n-donor ligand, the coordination polymer constructed using multiple tooth Carboxylic acid ligand or multiple tooth containing n-donor ligand
There is good stability, easily prepare and have and be potentially widely applied prospect.The spy that multiple tooth carboxylic acidss part has
Point：（1）Under different pH values can partly or entirely deprotonation, with metal center produce multi-form, different degrees of coordination,
Can simultaneously serve as hydrogen bond receptor and donor.（2）The skeleton of its bending and various coordination mode become multi-link the joining of structure
Position compound selects well.Multiple tooth nitrogenous class part such as 4,4 '-bipyridine ligand, 4,4 '-bipyridyl is that a class is the most frequently used
Rigid bidentate ligand, is most organic bridge ligand of research so far, and metal ion is easy to 4, and 4 '-bipyridyl is formed joins
Position polymer.The reason with multiple tooth Carboxylic acid ligand and 4,4 '-bipyridyl as mixed ligand is their tools when participating in coordination
There is very big cooperative effect, and nitrogen-atoms are different from coordination ability when carboxyl and metallic ion coordination and selectivity, often
Various structures novelty, the coordination polymer of excellent performance can be obtained.(S. L. James,Chem. Soc. Rev.2003,32, 276;A. Y. Robin, K. M. Fromm,Coord. Chem. Rev.2006,250, 2127-2157; B.
Y. Li, F. Yang, G. H. Li, D. Liu, Q. Zhou, Z. Shi, S. H. Feng,Cryst. Growth Des.2011,11, 1475-1485).
Content of the invention
The invention provides two-dimensional metallic nickel coordination polymer of a kind of mixed ligand and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs：A kind of two-dimensional gold of mixed ligand
Belong to nickel coordination polymer, its molecular formula is:C21H22N2NiO7.Described coordination polymer is monoclinic system,P-1 space group.Brilliant
Born of the same parents' parametera=7.72490 (10),b=10.33790 (10),c=15.6347 (2),a=107.8604 (8) °,β=
104.1316 (8) °,γ=98.0857 (8) °,V=1120.58(2) Å3.
A kind of preparation method of the two-dimensional metallic nickel coordination polymer of mixed ligand is：By 4- carboxymethyl -2- ethoxybenzene
Formic acid（RGAA）With 4,4 '-bipyridyl and nickel salts are mixed soluble in water with the amount of a certain proportion of material, add a certain amount of
Sodium hydroxide, be placed in polyfluortetraethylene pipe sealing, put in stainless steel cauldron, reactor is put into GZX 9030MBE electricity
In hot-air blower.Crystallization 3 days at one hundred and twenty degrees centigrade, naturally cool to room temperature, separate out green bulk crystals.
During the metallic nickel coordination polymer being synthesized, find 4- carboxymethyl -2- ethoxybenzoic acid
（RGAA）Deprotonation completely, using the coordination mode of bidentate sequestration.4,4 '-bipyridyl improves chemical combination by monodentate ligand pattern
The dimension of thing and stability.Build the coordination polymer with two-dimensional network structure good stability.
Beneficial effects of the present invention：The metallic nickel coordination polymer of the present invention is to obtain under hydrothermal synthesizing condition, preparation
Method process is simple, good stability, the fault in material being synthesized is few, and degree of crystallinity is high.The polymer of this mixed ligand is in molecule
Field of magnets has extraordinary potential application prospect.
Brief description
Fig. 1, the metallic nickel coordination polymer C of the mixed ligand of the present invention21H22N2NiO7, with the coordination ring of metal center Ni
Border figure.
Fig. 2, the metallic nickel coordination polymer C of the mixed ligand of the present invention21H22N2NiO7, with the coordination of metal center Ni
Two-dimensional layer figure.
Fig. 3, the metallic nickel coordination polymer C of the mixed ligand of the present invention21H22N2NiO7, with the coordination of metal center Ni
Three-dimensional Supramolecular Network structure chart.
Fig. 4, the metallic nickel coordination polymer C of the mixed ligand of the present invention21H22N2NiO7, with the coordination of metal center Ni
Two-dimensional topology figure.
Fig. 5, the infared spectrum of the metallic nickel coordination polymer of the mixed ligand of the present invention.
Fig. 6, the variable temperature magnetic susceptibility curve of the metallic nickel coordination polymer of the mixed ligand of the present invention.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1（C21H22N2NiO7）
By 4- carboxymethyl -2- ethoxybenzoic acid（0.1mmol）With 4,4 '-bipyridyl（0.1mmol）, sodium hydroxide
（0.15mmol）, and Ni (NO3)2·6H2O（0.1mmol）It is dissolved in 8 mL distilled water and put into ptfe autoclave, will be anti-
Kettle is answered to put in GZX 9030MBE electric heating aerator.Setting temperature range is 120 degree, heats 3 days.Dropped with 5 DEG C/h afterwards
It is filtrated to get the coordination polymer C of described mixed ligand to room temperature21H22N2NiO7(referred to as 1).
Then the coordination polymer of above-mentioned mixed ligand is carried out structural characterization
The coordination polymer of this mixed ligand is completed with SHELXTL program bag by mono-crystalline structures diffraction and on PC, cooperation
The crystallographic parameter of thing 1 is shown in Table 1.
Fig. 1 is to obtain structure C by single crystal diffraction method21H22N2NiO7Coordination structure figure.From the figure, it can be seen that it is not right
Claim to contain Ni (II) ion in unit, a RGAA part, one 4,4 '-bipyridine ligand and two free moistures
Son.Ni (II) ion be hexa-coordinate be slightly tilted octahedral configuration and two N atoms and the coordination of four O atom.This two
N atom comes from two independent 4,4 '-bipyridyl nitrogen-atoms, and bond distance's distance of Ni-N is 2.0431 (16) -2.0627
(17)Å.Four oxonium ions come from two independent RGAA part carboxylate oxygen atoms.The scope of bond distance's distance of Ni-O is
2.0708(14)–2.1281(15)Å.
Fig. 2 is with the two-dimensional layer figure of the coordination of metal center Ni.Each RGAA part adopts as shown in the figureμ 2-η 1:η 1:η 1:η 1Coordination mode connects adjacent metallic nickel ions and forms edgebThe one-dimensional catenary structure that axle stretches out, each 4,4 '-
Bipyridine ligand adopts monodentate ligand pattern to connect.Connect adjacent metallic nickel ions and form edgecIt is one-dimensional that axle stretches out
Chain structure, and then form 2 dimension layer structures.
Fig. 3 is the Three-dimensional Supramolecular Network structure chart of the coordination of metal center Ni.As illustrated, we can be found that two kinds
The O H O hydrogen bond of type and two kinds of C H O hydrogen bond.Formed by the oxygen of Free water and RGAA carboxylate oxygen atoms
O H O hydrogen bond, its bond distance is 1.99 (2).In addition all there is the O H O hydrogen bond that the oxygen of Free water is formed.Its bond distance divides
It is not 1.92 and 2.16.Simultaneously, from figure 3, it can be seen that coming from 4, the carbon atom of 4 '-bipyridyl and the oxygen of RGAA
The C H O hydrogen bond that atom is formed.Its bond distance is respectively 2.29,2.54.Additionally there are come from Free water oxygen former
Son and be derived from 4, the carbon atom of 4 '-bipyridyl forms C H O hydrogen bond, and its bond distance and bond angle are 2.42 respectively.Except these
Outside hydrogen bond, also there is two kinds of C H π key.One kind is C10 H10A π(N1-C12-C13-C14-C15- C16)（2.84 Å
）.Another kind of C10 H10B π(N2-C17-C18-C19-C20- C21)（2.82Å）.These supermolecular mechanism power make two-dimensional layer extend to three
The supramolecular structure of dimension.
Fig. 4 is with the two-dimensional topology figure of the coordination of metal center Ni.As illustrated, each RGAA part connects two metals
Nickel ion, each 4,4 '-bipyridine ligand connect two metallic nickel ions, each metallic nickel ions connect 4 parts, therefore
The topological symbol of the coordination polymer of its metallic nickel is (8^4.12^2) (8) of 2,4 connections2.
Fig. 5 is the infared spectrum of the metallic nickel coordination polymer of mixed ligand.The metallic nickel coordination polymer of mixed ligand
Infared spectrum infrared spectrum： (KBr, cm-1): 3437(br), 2974(w), 1610 (vs), 1551 (s), 1421
(vs), 1298 (m), 1249 (m), 1224 (m), 1178 (m), 1110 (m), 1072 (m), 1043 (m),
947 (w), 866 (w), 829 (m), 771 (m), 738 (m), 678 (m), 638 (m), 574 (w), 478
(w).Its characteristic peak isv as(CO2 -) it is 1610 cm−1,v s(CO2 -) it is 1421cm−1,v(- OH) is 3424 cm−1.
Fig. 6 is the variable temperature magnetic susceptibility curve of the metallic nickel coordination polymer of mixed ligand.In 2-300K temperature range, outward
Plus under the magnetic field of 2000Oe, measure experimental result.As shown in fig. 6, by office-weiss law is to coordination polymerχ m -1Bent with T
Line carries out linear fit, simultaneously also to coordination polymerχ m Carry out nonlinear fitting with T curve.In addition, in 300K, coordination compound
Molar susceptibility and temperature product (χ m T) it is 1.1136 cm3mol-1K, the monokaryon Ni being reported with document (S=1,g
=2.0) molar susceptibility and the value of the product of temperature are (1.000 cm3K mol-1) value higher.Temperature from 300 to 30K,
Molar susceptibility is almost unchanged with the value of temperature, but when temperature is reduced to 30K,χ m T value declines rapidly.In 2K,χ m T value also reaches
It is 0.56 cm to minima3mol-1K.The product of the molar susceptibility according to coordination compound and temperature and the variation relation of temperature,
This compound exists and there is anti-ferromagnetism coupling between intramolecular effect or adjacent metallic nickel.By in office-weiss law pair
Coordination polymerχ m -1Carry out linear fit with T curve.From this coordination compound in variable temperature magnetic susceptibility curve, this compound has
Preferably magnetic property.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (5)
1. a kind of mixed ligand two-dimensional metallic nickel coordination polymer it is characterised in that：Chemical molecular formula C21H22N2NiO7.
2. the metallic nickel coordination polymer according to claims 1 it is characterised in that：Described coordination polymer is monocline
Crystallographic system,P-1 space group, cell parametera=7.72490 (10),b=10.33790 (10),c=15.6347 (2),a=
107.8604 (8) °,β=104.1316 (8) °,γ=98.0857 (8) °,V=1120.58(2) Å3.
3. the metallic nickel coordination polymer according to claims 2 it is characterised in that：Ni (II) ion is hexa-coordinate
It is slightly tilted octahedral configuration and two N atoms and four O atom coordinations, this two N atoms come from two independent 4,
4 '-bipyridyl nitrogen-atoms, bond distance's distance of Ni-N is 2.0431 (16) -2.0627 (17), and four oxonium ions come from two
Independent 4- carboxymethyl -2- ethoxybenzoic acid（RGAA）Part carboxylate oxygen atoms, the scope of bond distance's distance of Ni-O is 2.0708
(14)–2.1281(15)Å.
4. the metal cobalt coordination polymer according to claims 1 preparation method it is characterised in that：By 4- carboxymethyl-
2- ethoxybenzoic acid（RGAA）With 4,4 '-bipyridyl and nickel salts mixed with the amount of a certain proportion of material soluble in water,
Add a certain amount of sodium hydroxide, be placed in sealing in polyfluortetraethylene pipe, put in stainless steel cauldron, reactor is put into
In GZX 9030MBE electric heating aerator, crystallization 3 days at one hundred and twenty degrees centigrade, naturally cool to room temperature, separate out green block brilliant
Body.
5. the metallic nickel coordination polymer according to claims 1 preparation method it is characterised in that：Described metallic nickel is joined
Position polymer has potential application foreground in molecule magnetic fields.
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| CN109575304A (en) * | 2018-12-13 | 2019-04-05 | 山西大学 | A kind of nickel coordination polymer and its preparation method and application |
| CN111234243A (en) * | 2019-12-31 | 2020-06-05 | 郑州轻工业大学 | Metal organic framework material, preparation method thereof and immunosensor |
| CN111995760A (en) * | 2020-07-17 | 2020-11-27 | 扬州大学 | Cobalt-metal organic framework nanosheet and preparation method and application thereof |
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| CN111995760A (en) * | 2020-07-17 | 2020-11-27 | 扬州大学 | Cobalt-metal organic framework nanosheet and preparation method and application thereof |
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