CN109810257A - Rigid aromatic polycarboxylic acid complex polymer and method for synthesizing the same - Google Patents
Rigid aromatic polycarboxylic acid complex polymer and method for synthesizing the same Download PDFInfo
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Abstract
本发明提供一种刚性芳香多羧酸配聚物及其合成方法，包括：将配体、模板剂混合反应，制得所述刚性芳香多羧酸配聚物。本发明通过配体和模板剂的引入，构筑了刚性芳香多羧酸配聚物，研究了热稳定性、荧光性能，并探讨了配体和模板剂对构筑配聚物结构的影响，为以后设计合成具有荧光性能和官能锚的孔道金属有机配聚物提供了一些有参考价值的方法。
The invention provides a rigid aromatic polycarboxylic acid complex polymer and a method for synthesizing the same, comprising: mixing and reacting a ligand and a template agent to prepare the rigid aromatic polycarboxylic acid complex polymer. In the present invention, a rigid aromatic polycarboxylic acid complex polymer is constructed by introducing a ligand and a template agent, and the thermal stability and fluorescence properties are studied, and the influence of the ligand and the template agent on the construction of the complex polymer structure is discussed. The design and synthesis of pore metal-organic complex polymers with fluorescent properties and functional anchors provides some valuable methods.
Description
Technical field
The present invention relates to the field of chemical synthesis, match polymers and its synthetic method more particularly to rigid aromatic polycarboxylic acids.
Background technique
Difference of the researchers based on metal-organic framework materials in chemical property, physical property and biological property, synthesis
A large amount of metal-organic framework materials with specific function, are widely applied in scientific experiment and production practices.?
In terms of dyestuff, using phthalocyanine, azo-compound etc. as the metal-organic framework materials of main ligand, dyestuff circle half river is occupied
Mountain.In metal smelt field, around the purport for the ion that extracted metal from ore in the form of complex, propose cyaniding,
The smelting process of the classics such as sulphur pulpating method and water chlorination process.Complex is in sides such as research nuclear fuel, processing waste water, analytical elements simultaneously
Face also plays increasing effect.Wherein catalytic action is its most important functions in terms of chemical functional, and principle is anti-
Object and catalyst (transistion metal compound) is answered to form complex.Such as with Ziegler-Nata (TiCl3-AlEt3) it is the one of representative
Catalyst series affect industrial core link, so that the petrochemical industries such as synthetic rubber, plastics is flourished, metal has
Utilization of the machine framework material in catalysis promotes fully utilization of the mankind to natural resources.Metal-organic framework materials and
Many basic life processes such as the storage and transportation of photosynthesis, respiration, microelement in life entity have direct connection,
Because metal ion involved in these processes is mainly present as a complex.Metal-organic framework materials are in medical direction
Extensive application, the curing cancer drug that scientist has found earliest are cis-platinum metal-organic framework materials (Pt (NH2)2Cl2), it is existing
Still in the significant drug of using effect.In heavy metal ion (lead, mercury etc.), radioactive element (uranium, thorium and plutonium etc.) poisoning side
Face, calcium or sodium salt and its of Chang Liyong EDTA is complexed to form chelate, then is excreted by metabolism, to reach alleviation
Or the purpose eliminated.In short, with the continuous development and deep, life production and social development of the mankind etc. of Coordinative Chemistry research
Numerous areas all be unable to do without the presence of complex.Therefore, Coordinative Chemistry research is significant.
Rigid aromatic polycarboxylic acids have a multiple carboxylic acid groups and rigid ring skeleton, and carboxyl oxygen atom coordination ability by force and
There are space steric effects between carboxyl.Therefore, it can obtain after by Carboxylic acid ligand in conjunction with metal ion with rich space
The coordination polymer of structure, fluorescence, molecular recognition, drug transmission, in terms of have broad application prospects.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide rigid aromatic polycarboxylic acids with polymers and
Its synthetic method.
In order to achieve the above objects and other related objects, the present invention provides a kind of rigid synthesis of the aromatic polycarboxylic acids with polymers
Method, including by ligand, template and metal salt or its hydrate hybrid reaction, the rigid aromatic polycarboxylic acids are made with poly-
Object, the ligand are selected from any one of following combination:
1) metal salt or its hydrate are selected from containing the salt of zinc ion or its hydrate, and the ligand is selected from 2- hydroxyl
Terephthalic acid (TPA) (i.e. H2BDC-OH)；
2) metal salt or its hydrate are selected from containing the salt of zinc ion or its hydrate, and the ligand is selected from 1,3,5-
Three (4- carboxyl phenyl) benzene, 2- amino terephthalic acid (TPA).
Optionally, in the combination 1), the salt containing zinc ion is selected from Zn (NO3)2·6H2O。
Optionally, in the combination 2), the hydrate of the salt containing zinc ion is selected from Zn (CH3COO)2·2H2O。
Optionally, the template is selected from n,N-Dimethylformamide (abbreviation DMF).
Optionally, by the meter of substance, nLigand: nMetal salt or its hydrate=1:(1-3), it can also be 1:2.
Optionally, when 1) metal salt or its hydrate, ligand are selected from combination, the solvent that when reaction uses includes ethyl alcohol
(abbreviation EtOH) and water, by volume, VDMF:VEtOH:Vwater=(4.5-5): (4.5-5): (1-1.5) can also be 4.5:
4.5:1.
Optionally, when 2) metal salt or its hydrate, ligand are selected from combination, the solvent that when reaction uses is pressed for water
Stereometer, VDMF:Vwater=(9-10): (1-2) can also be 9:1.
Optionally, when 1) ligand is selected from combination, reaction temperature is 80-90 DEG C.
Optionally, when 2) ligand is selected from combination, reaction temperature is 115-125 DEG C.
The present invention also provides rigidity aromatic polycarboxylic acids made from the above method to match polymers.
As described above, rigid aromatic polycarboxylic acids of the invention match polymers and its synthetic method, this is had the advantages that
Invention introduces central metal on the basis of ligand and template, has constructed rigid aromatic polycarboxylic acids with polymers, has had studied hot steady
Qualitative, fluorescence property, and ligand and template have been inquired into the influence with polymer configurations is constructed, have for design synthesis later glimmering
The duct metal of optical property and function anchor is organic to provide the method for reference value with polymers.
Detailed description of the invention
Fig. 1 a is shown as the asymmetric cell figure obtained for matching polymers of the embodiment of the present invention 1.
Fig. 1 b is shown as the coordination configuration figure obtained with Zn (II) ion in polymers crystal of the embodiment of the present invention 1.
Fig. 1 c is shown as Zn (II) the ion link composition obtained with polymers of the embodiment of the present invention 1.
Fig. 1 d is shown as tying the duct 3D along c-axis of BDC-OH and the building of Zn (II) chain link in the embodiment of the present invention 1
Composition.
Fig. 2 a is shown as the asymmetric cell figure obtained for matching polymers of the embodiment of the present invention 2.
Fig. 2 b is shown as the coordination context diagram obtained with Zn in polymers crystal of the embodiment of the present invention 2.
It is obtained with polymers tomograph that Fig. 2 c is shown as the embodiment of the present invention 2.
It is obtained with polymers interpenetrating topology diagram that Fig. 2 d is shown as the embodiment of the present invention 2.
It is obtained with polymers hot weight curve that Fig. 3 is shown as the embodiment of the present invention 1.
It is obtained with polymers hot weight curve that Fig. 4 is shown as the embodiment of the present invention 2.
Fig. 5 is shown as H3The solid-state launching light spectrogram of BTB.
Fig. 6 is shown as H2The solid-state launching light spectrogram of BDC-OH.
Fig. 7 is shown as the solid-state launching light spectrogram obtained for matching polymers of the embodiment of the present invention 1.
Fig. 8 is shown as the solid-state launching light spectrogram obtained for matching polymers of the embodiment of the present invention 2.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
The present invention passes through the introducing of ligand and template, has constructed two rigid aromatic polycarboxylic acids with polymers, has had studied heat
Stability, fluorescence property, and ligand and template have been inquired into the influence with polymer configurations is constructed, have for design synthesis later
The duct metal of fluorescence property and function anchor is organic to provide some methods for having reference value with polymers.
Embodiment 1
Compound [Zn4O2(H2O)0.5(BDC-OH)2]·(H2O)0.5Synthesis
H is weighed respectively2BDC-OH(0.2mmol,36.4mg)、Zn(NO3)2·6H2O (0.4mmol, 119mg), in stainless
In steel inner liner of reaction kettle, 10mL (DMF-EtOH-H is then added2O, by volume, DMF:EtOH:H2O=4.5:4.5:1), into
Row stirring and dissolving, reaction temperature are 85 DEG C, and the time is 5 days, and then cooled to room temperature, can be obtained colorless and transparent rodlike crystalline substance
Body, yield are about 54% (based on H2BDC-OH).Main infrared peak (KBr tabletting, cm-1) it is as follows: 3191 (m),
2344(w),1663(s),1592(s),1484(m),1395(s),1232(m),1101(m),938(w),775(m),667(w)。
The present embodiment is obtained referred to as to match polymers 1 with polymers.
Embodiment 2
(1) compound [Zn (BTB) (Me2NH)]·(Me2NH2) synthesis
Zn (CH is weighed respectively3COO)2·2H2O (0.4mmol, 87.8mg), 1,3,5- tri- (4- carboxyl phenyl) benzene
(0.08mmol, 35.07mg), 2- amino terephthalic acid (TPA) (0.12mmol, 21.7mg) add in stainless steel cauldron liner
Enter 10mL (DMF-H2O, v:v/9:1), it is stirred dissolution, reaction temperature is 120 DEG C, and the time is 5 days, then natural cooling
To room temperature, colorless and transparent granule crystal can be obtained, yield is about 57% (based on H3BTB).Main infrared peak (KBr pressure
Piece, cm-1) it is as follows: 3434 (m), 1660 (s), 1610 (vs), 1553 (s), 1405 (vs), 1179 (w), 1108 (w), 1009
(w),1108(w),854(m), 783(vs),698(w),670(w)。
The present embodiment is obtained referred to as to match polymers 2 with polymers.
The mono-crystalline structures of Examples 1 and 2:
Table 1 matches part bond distance's bond angle of polymers 1
Symmetry transformations used to generate equivalent atoms:
#1y+1,-x+y+1,z+5/6 #2x-y,x,z+1/6 #3-x+y+1,-x+1,z+2/3 #4x-y,x,z+7/6 #
5x,y,z-1 #6-x+1,-y,z-1/2 #7y,-x+y,z-7/6 #8-y+1,x-y,z-2/3 #9y,-x+y,z-1/6 #10x,
y,z+1 #11x-y,x-1,z-5/6 #12-x+1,-y,z+1/2
Table 2 matches part bond distance's bond angle of polymers 2
Symmetry transformations used to generate equivalent atoms:
#1x-1/2,-y+1/2,-z+1 #2x,-y+1,z-1/2
[Zn made from embodiment 14O2(H2O)(BDC-OH)2] structural analysis
With polymers 1 with P61It is crystallized in the hexagonal crystal system of space group.Asymmetric cell (as shown in Figure 1a) includes four
Zn (II) ion, two BDC-OH, two μ 3-O atoms and a water of coordination.The Zn1 of hexa-coordinate forms octoploids structure, and five match
Zn2, Zn3 and Zn4 of position form triagonal bipyrimidal configuration (as shown in Figure 1 b).The bond distance of Zn-O is in 0.1968nm-0.2204nm
In range.Four Zn (II) by eight carboxyl oxygens (O1, O2, O3, O4, O6, O7, O8 and O9), two hydroxyl oxygens (O5 and
O10) and two μ 3-O atom (O11 and O12) bridge joints form rare Zn4Cluster chain structure (as illustrated in figure 1 c).Each Zn4Cluster chain
Linear ligands BDC-OH is continued through to bridge to form 3D frame (as shown in Figure 1 d) while see that form diameter is about along c-axis directionRound cellular structure, unordered aqueous solvent, ethyl alcohol and DMF etc. may be filled in duct.
[Zn (BTB) (Me made from embodiment 22NH)].(Me2NH2)] structural analysis
Crystal category orthorhombic system with polymers 2, space group Pbcn.Asymmetric cell (as shown in Figure 2 a) includes two Zn
(II) ion, the ligand of coordination are a BTB and diformazan amine molecule and a free dimethylamine cation.Four-coordination Zn
(II) ion forms tetrahedron, by from three difference BTB ligands three oxygen atoms (O1, O4a and O6b) and one come from
Nitrogen donor (N1) coordination of diformazan amine molecule forms frame (as shown in Figure 2 b).Frame is negatively charged, so having free
The charge balance of dimethylamine cation.Zn-N bond distance be 0.2086 (6) nm, Zn-O key spacing be respectively 0.1900 (4) nm,
0.1982 (4) nm and 0.1919 (4) nm.The three of node and three connection BTB ligand buildings that Zn (II) atom is connected as one
It ties up structure and double cross line is topological (as shown in Fig. 2 c, Fig. 2 d).It include duct with three-dimensional framework single in polymers 2So embodiment 2 uses interpenetrating structure to reduce very big gap and stable frame.
Thermal stability analysis
This experiment using thermogravimetric analyzer respectively to polymers 1 in air atmosphere, with the speed of 10 DEG C/min 25 DEG C-
It heats up within the scope of 800 DEG C, characterizes its thermal stability (as shown in Figure 3).
With the presence that normal temperature condition can be more stable in air of polymers 1.Weight should be lost with the polymers first step about to exist
Before 150 DEG C, the weight lost is 7.16%, and corresponding may be free water, ethyl alcohol equal solvent molecule, at 150 DEG C -530 DEG C
Between weightless 73.67% (theoretical value 71.72%), belong to ligand and start to decompose, skeleton gradually collapses to no longer weightless, last shape
At metal oxide.
This experiment using thermogravimetric analyzer to polymers 2 in air atmosphere, with the speed of 10 DEG C/min at 25 DEG C -800 DEG C
Heating, characterizes its thermal stability (as shown in Figure 4) in range.
With the presence that normal temperature condition can be more stable in air of polymers 2.Weight should be lost with the polymers first step about to exist
Between 60 DEG C -325 DEG C, the weight lost is 15.14% (theoretical value 13.39%), and corresponding is the Me to dissociate in structure2NH2
And the Me of coordination2NH+There is a longer Duan Pingtai between 325 DEG C -430 DEG C in ion etc., shows that the crystal can be in this model
It encloses and is stabilized, weight-loss ratio is mutated after 460 DEG C, is belonged to ligand and is started to decompose, skeleton gradually collapses.
Luminesceence analysis experiment with polymers 1
There are mainly three types of the principle of luminosity of metal-organic coordination polymer: central metallic ions, ligand shine and are based on
Electric charge transfer radiation transistion shines.It is n → π * and π → π * transition as a result, d that the absorption of most of organic ligands, which shines,10Structure
Type metal center ion is difficult to be oxidated or reduced, so it is considered that with polymers 1 and 2 fluorescence mainly by ligand centered on
Excitation state, this excitation state may relate to ligand metal electric charge transfer (LMCT), match internal electric charge transfer (ILCT) ginseng
With.
Ligand H3When BTB is with the excitation of 335nm wavelength, occur emission peak (as shown in Figure 5) at 400nm；Ligand H2BDC-OH
Emission peak is in 450nm (as shown in Figure 6), excitation wavelength 375nm；The fluorescence of the two may be derived from π → π * or n of intramolecular
→ π * electron transition.Based on this, we are characterized and have been analyzed to the solid fluorescence property with polymers 1 at room temperature.
With polymers 1 in the case where wavelength is the ultraviolet excitation of 300nm, fluorescent emission is 437nm (as shown in Figure 7), with ligand H2BDC-OH
Compare, blue shift 13nm, the fluorescence with polymers 1 may be H2BDC-OH is with internal electric charge transfer (ILCT) and ligand and gold
Belong to the influence of coordination effect between ion.By photoluminescent property phenetic analysis, it is good to illustrate that embodiment 1,2 belongs to have
The coordination polymer of fluorescence property.
Experiment is analyzed in luminesceence analysis with polymers 2
With polymers 2 in the case where wavelength is the ultraviolet excitation of 388nm, strong blue-fluorescence (such as Fig. 8 is produced at 435nm
It is shown), with ligand H3The emission peak of BTB compares (400nm), red shift 35nm, but spectral peak is almost the same, this explanation matches polymers 2
Transmitting, the influence of ligand metal electric charge transfer (LMCT) may be attributed to.
In conclusion the present invention passes through the introducing of ligand, template, central metal, rigid aromatic polycarboxylic acids is constructed and have matched
Polymers has studied thermal stability, fluorescence property, and has inquired into ligand and template to constructing the influence with polymer configurations, for
Design synthesis has the duct metal of fluorescence property and function anchor is organic to provide the method for reference value with polymers afterwards.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105479A (en) * | 2009-01-23 | 2011-06-22 | 韩华石油化学株式会社 | Scaffold materials-transition metal hydride complexes, intermediates therefor and method for preparing the same |
| KR20180108221A (en) * | 2017-03-24 | 2018-10-04 | 연세대학교 산학협력단 | Method for preparing carbon-metal organic frameworks composite using microwave |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105479A (en) * | 2009-01-23 | 2011-06-22 | 韩华石油化学株式会社 | Scaffold materials-transition metal hydride complexes, intermediates therefor and method for preparing the same |
| KR20180108221A (en) * | 2017-03-24 | 2018-10-04 | 연세대학교 산학협력단 | Method for preparing carbon-metal organic frameworks composite using microwave |
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