CN109749091A - Organic cyclic annular supermolecule of a kind of sky blue fluorescence cadmium and the preparation method and application thereof - Google Patents
Organic cyclic annular supermolecule of a kind of sky blue fluorescence cadmium and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides organic cyclic annular supermolecule of a kind of sky blue fluorescence cadmium and the preparation method and application thereof, structural formula such as formula III:Preparation method are as follows: (1) by raw material H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3And solvent acetonitrile and water are mixed to form reaction system, are placed in closed container；(2) reaction system is placed in 30~70min of stirring at room temperature, then takes out stirrer, is encapsulated in stainless steel sleeve, be placed in baking oven and be warming up to 110~135 DEG C, reacted 4~6 days, natural cooling, filtering, air drying obtains colourless rhabdolith.The yield of the organic cyclic annular supermolecule of the sky blue fluorescence cadmium prepared using preparation method of the invention is about 77%, and the material can be used for preparing light sensitivity composite material and apply in terms of.
Description
Technical field
The invention belongs to heavy metals and advanced function Material Field, and in particular to a kind of sky blue fluorescence cadmium is organic cyclic annular super
Molecule and the preparation method and application thereof.
Background technique
The cyclic annular supramolecular aggregation constructed by interactions such as coordinate bond, hydrogen bonds, is widely present in nature, weight
The type wanted is the organic cyclic complex of metal-, for example it is known that ferroheme be chela that ferrous ion and porphyrin ring are formed
Close object；The chlorophyll that the magnesium ion coordination of key effect is played in the photosynthesis of plant is also macrocyclic complex.Some rings
Shape complex has the properties such as molecular recognition, photoelectric heat, develops important in inhibiting to new material.In general, human eye pair
Sky blue (or dark green) near 490nm and the orange-colored light near 590nm are especially sensitive, therefore photopic vision sky blue or scotopia
Sky blue (fluorescence) material, is widely used in industry fields such as decoration, environmental protection.
Modern times create novel substance scientific domain, and cyclic complex preparation cooperates from mononuclear complex to double-core or multicore
Object development, metal core is more, and difficulty is bigger in technology of preparing, presently most used metal core, is that rhodium, palladium, platinum etc. are at high cost
Noble metal, and transition metal cheap and easy to get is relatively fewer.Also, it is known that annular metal-organic coordination compound in, technology is difficult
Degree determines that majority is the cyclic complex of single organic ligand, and mixed body or three kinds of component annular metal-organic coordination compound phases
To less.
Cadmium is common heavy metal element distributed more widely in nature, the compound of cadmium be widely used in plating, fuel,
The fields such as electronics and nuclear industry；Meanwhile a considerable amount of cadmiums are discharged into environment by waste water and dregs, it is easier to be adsorbed by crops
Characteristic generates larger range of pollution in turn.By short-cut method, Cd in solution is probed into2+The project of ion enrichment is by ring
The concern of the fields such as border, life, chemistry scientists.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of sky blue fluorescence cadmium is organic
Cyclic annular supermolecule, the novel substance can be used for preparation and the cation detection of light sensitivity composite material.
To achieve the above object, the invention provides the following technical scheme: a kind of organic cyclic annular supermolecule of sky blue fluorescence cadmium,
The chemical composition of the organic cyclic annular supermolecule of the sky blue fluorescence cadmium is [Cd2(H2etc)2(phen)2(H2O)2], the component
H2etc2-It is quaternary carboxylic acid H4Etc, structure such as Formulas I are sloughed obtained by 2 protons, each H2etc2-2 metal Cd of bridging2+From
Son, coordination structure is as shown in formula III；Component phen structure such as Formula II, each phen chelate 1 metal Cd2+Ion is coordinated mould
Formula is as shown in formula III；Each Cd2+Ion with 4 O atoms and 2 N Atomic coordinates from four components, takes six to match respectively
Bit pattern [CdO4N2]；
The organic cyclic annular supermolecule of above-mentioned sky blue fluorescence cadmium uses following preparation method: with H4etc、phen·H2O、 Cd
(NO3)2·4H2O and HNO3As raw material, using the mixed solution of acetonitrile and water as solvent, prepared using solvent-thermal process method,
Specifically comprise the following steps:
(1) by raw material H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3And solvent acetonitrile and water are mixed to form instead
System is answered, is placed in closed container；The H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3The mass ratio of the material be 1:
Volume ratio 1:1~9 of 1:1~3:4~10, the solvent acetonitrile and water；
(2) reaction system is placed in 30~70min of stirring at room temperature, then takes out stirrer, be encapsulated in stainless steel sleeve, sets
It is warming up to 110 DEG C~135 DEG C in baking oven, reacts 4~6 days, natural cooling, filtering, air drying obtains colourless rodlike crystalline substance
Body.
Further, H described in step (1)4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3The mass ratio of the material be
1:1:1:4.2；The volume ratio 1:9 of the solvent acetonitrile and water.
Further, H in reaction system4The amount concentration of the parent material of etc is 5mmol/L.
Further, reaction temperature is 120 DEG C, after the drying refers to that crystal is washed with water in step (2), in air certainly
It is so dry.
Photosensitized composite material can be applicable to using the organic cyclic annular supermolecule of sky blue fluorescence cadmium made from above-mentioned preparation method
In preparation and cation detection etc..
Compared with prior art, the invention has the following beneficial effects:
The organic cyclic annular supermolecule of sky blue fluorescence cadmium provided by the invention, by metal Cd2+Ion and organic ligand H2etc2-
Big ring is formed by Cd-O and Cd-N coordinate bond with phen, the distance between Cd ... Cd is in cyclic structureTwo
H2etc2The distance between two ether O atoms of component areThe big ring of nanometer can be considered as；Wherein, it is deposited in macrocyclic structure
In two kinds of [Cd (H2Etc)] helical structure unit, respectively left hand helix structural unit and right-handed helix structural unit, the two are used
Cross shared Cd2+Form cyclic annular meso helical structure；The big ring of nanometer is further constructed by interannular O-H ... O strong hydrogen bonding
Rare dual interspersed one-dimensional supermolecule polymeric chain.
The organic cyclic annular supermolecule of gained cadmium of the invention is stabilized in water, acetonitrile equal solvent, is decomposed at 350 DEG C or so,
Thermal stability with higher；At room temperature, which excites in ultraviolet light 415nm, and it is glimmering that sky blue is emitted at 493 nm
Light；During methyl methacrylate (MMA) polymerization, the super molecular compound is adulterated, has obtained shining in 365nm ultraviolet light
The compound organic glass (doped-PMMA) for penetrating lower transmitting sky blue fluorescence, it is photosensitive to show that the new crystalline material can be used for preparing
Property composite material and apply in terms of, and from the experimental results, the resulting cadmium of the present invention is organic cyclic annular super
The detection liquid of molecule preparation, to Ag+And Cr3+The detection of ion has certain selectivity.
In addition, the yield of the organic cyclic annular supermolecule of the sky blue fluorescence cadmium prepared is about using preparation method of the invention
It is 77%.Meanwhile the organic cyclic annular supermolecule of sky blue fluorescence cadmium provided by the invention, environmental pollution improvement, new material are opened
Hair and application etc. all have positive meaning and value.
Detailed description of the invention
Fig. 1 is the organic cyclic annular supermolecule [Cd of sky blue fluorescence cadmium2(H2etc)2(phen)2(H2O)2] crystal structure figure:
(on) big ring and meso helical structure, (under) [Cd2(H2etc)2] structural unit by interannular O-H ... O strong hydrogen bonding (O ... O away from
From for) the dual interspersed one-dimensional supermolecule polymeric chain constructed；
Fig. 2 is the infrared spectrogram of the organic cyclic annular supramolecular complex of sky blue fluorescence cadmium；
Fig. 3 is the photo under the organic cyclic annular supramolecular complex 365nm ultraviolet light of colourless sky blue fluorescence cadmium；
Fig. 4 is the X-ray powder diffraction style figure of the organic cyclic annular supramolecular complex of sky blue fluorescence cadmium；
Fig. 5 is the hot weight curve of the organic cyclic annular supramolecular complex of sky blue fluorescence cadmium；
Fig. 6 is solid state fluorescence spectrogram under the organic cyclic annular supramolecular complex room temperature of sky blue fluorescence cadmium；
Fig. 7 be sky blue fluorescence doping organic glass (doped-PMMA) of preparation in natural light (white background) and
The comparison photo of (black background) under 365nm ultraviolet light；
Fig. 8 is the ultraviolet-visible absorption spectroscopy that the organic cyclic annular supermolecule water soluble liquid of sky blue fluorescence cadmium detects metal ion
Figure.
Specific embodiment
Combined with specific embodiments below, the method for the present invention is described in detail.X- is carried out to final product in the present invention
Ray single crystal diffraction test, parses to obtain its accurate electronic structure；And a series of characterizations are carried out to final product, it is such as infrared, glimmering
Light, X-ray powder diffraction, thermogravimetric etc. determine that its chemical composition is [Cd2(H2etc)2(phen)2(H2O)2].Matched with master
H4Etc dosage be according to calculate yield, i.e., according to product form in H2etc2-Substance amount accounting, calculating should theoretically obtain
Cyclic annular oversubscription protonatomic mass, the ratio that the product quality actually obtained accounts for the former is yield.
One, the preparation of the organic cyclic annular super molecular compound of cadmium-of the present invention
Embodiment 1
Material is taken by following specific quality or volume: H4Etc (17.3mg, 0.05mmol), phenH2O (9.9 mg,
0.05mmol), Cd (NO3)2·4H2O (15.4mg, 0.05mmol), CH3CN (1mL), H2O (9mL), HNO3(30uL, 7mol/
L,0.21mmol).Above-mentioned material is placed in 25mL reaction kettle, stir about 60min, after being warming up to 120 DEG C, reaction 5 days, from
It is so cooled to room temperature, obtains crystal prototype, it is filtered from mother liquor, distill water washing, spontaneously dried in air.
It in crystal prototype, selects and takes suitable monocrystalline, X-ray single crystal diffraction analysis is carried out to it, parse to obtain its crystal
Structure (see Fig. 1).In dissymmetrical structure, there are a kind of independent Cd of crystallography2+Ion, each Cd2+Ion and 4 O atoms
[CdO is formed with 2 N atoms4N2] hexa-coordinate mode.By metal Cd2+Ion and N, O- organic ligand H2etc2-It is logical with phen
It crosses Cd-O and Cd-N coordinate bond and forms big ring, two H2etc2-The distance between two ether O atoms (O10 ... O10A) of component areThe distance between Cd ... Cd is in cyclic structureIt may be viewed as nanoscale macrocyclic complex.
In cyclic structure, there are two kinds of [Cd (H2Etc)] helical structure unit, respectively left hand helix structural unit and the right side
Hand helical structure unit, the used shared Cd of the two2+Form cyclic annular meso helical structure；The macrocyclic complex, passes through interannular
(O7 ... O8 distance is O7-H1 ... O8 strong hydrogen bonding), further construct rare dual interspersed one-dimensional supermolecule
Indissoluble has obvious structure-activity relationship in polymeric chain, interspersed paradigmatic structure and higher thermal stability and common solvent.
The crystal prototype of the organic cyclic annular supermolecule of cadmium, carries out powder diffraction survey with Shimadzu XRD-6100 type x-ray diffractometer
Examination, the peak for testing map match well with the peak energy of crystal structure simulation map (software Mercury), illustrate gained crystalline
Product structure is identical as single crystal data resulting structures, sample purity height (see Fig. 4).
The Thermogravimetric Data of crystallized sample analysis shows that, the moisture of the organic cyclic annular supermolecule of the Cd- about abjection coordination at 270 DEG C
Son, weightless about 2.9% (calculated value 2.7%)；With object phen abjection or skeletal disintegration after 350 DEG C.Thermogravimetric Data shows
This cadmium organic macrocycle supermolecule has relatively high thermal stability (see Fig. 5).
The ring-type supramolecular chemistry formula is Cd2C56H36N4O20, formula weight 1309.73, wherein C, H, N element are analyzed
(%): C, 51.42；H,2.81；N,4.25；Calculated value (%): C, 51.36；H,2.77；N,4.28.FT-IR (KBr, cm-1):
3438(m),3395(m),3080(m),1712(vs),1695(vs),1611(m), 1573(vs),1544(vs),1435
(vs),1382(vs),1281(vs),1201(s),1013(vs),841(s),774(s), 728(s).Illustrate: elemental analysis value
It is measured by Perkin-Elmer2400 elemental analyser；Infrared spectroscopy is by Nicolet Impact410FTIR spectrometer with KBr
It is bottom in 400-4000cm-1It is measured in range.
Rhabdolith sample, it is almost colourless transparent under natural light, but sky blue fluorescence is presented under 365nm ultraviolet light
(see Fig. 3).The solid state fluorescence spectrum of crystal product is tested at room temperature, statistics indicate that under 415nm ultraviolet excitation, big ring
Supramolecular complex emits sky blue fluorescence at 493nm (see Fig. 6).
The present embodiment is repeated as many times, and the quality for actually obtaining cyclic annular supermolecule is maintained at 19.3~25.2mg, is based on H4etc
Calculate yield be 58.9%~77.0%.
Embodiment 2
Material is taken by following specific quality or volume: H4Etc (17.3mg, 0.05mmol), phenH2O(9.9 mg,
0.05mmol),Cd(NO3)2·4H2O (46.2mg, 0.15mmol), CH3CN (3mL), H2O (7mL), HNO3(70uL, 7mol/
L,0.49mmol).Above-mentioned material is placed in 25mL reaction kettle, stir about 30min, it is natural after being warming up to 110 DEG C, reaction 6 days
It is cooled to room temperature, obtains rhabdolith, it is filtered out from mother liquor, distill water washing, air at room temperature spontaneously dries.
Powder product X-ray diffraction characterizes (see Fig. 4), and it is similar to Example 1 to obtain data.Illustrate to be made with embodiment 2
Crystal structure do not change, product purity is high.
The present embodiment is repeated as many times, the quality for actually obtaining cyclic annular supermolecule is maintained at 15.8~20.4mg, is based on
H4Etc calculate yield be 48.2%~62.3%.
Embodiment 3
Material is taken by following specific quality or volume: H4Etc (17.3mg, 0.05mmol), phenH2O(9.9 mg,
0.05mmol),Cd(NO3)2·4H2O (23.1mg, 0.075mmol), CH3CN (5mL), H2O (5 mL), HNO3(50uL,7mol/
L,0.35mmol).Above-mentioned material is placed in 25mL reaction kettle, stir about 70min, it is natural after being warming up to 135 DEG C, reaction 4 days
It is cooled to room temperature, obtains rhabdolith, it is filtered out from mother liquor, distill water washing, spontaneously dried in air at room temperature.
Powder product X-ray diffraction characterizes (see Fig. 4), and it is similar to Example 1 to obtain data.Illustrate to be made with embodiment 3
Crystal structure do not change and product is purer.
The present embodiment is repeated as many times, the quality for actually obtaining cyclic annular supermolecule is maintained at 18.9~22.3mg, is based on
H4Etc calculate yield be 57.7%~68.1%.
Two, the application of the organic cyclic annular supermolecule of sky blue fluorescence cadmium
2.1) the organic cyclic annular supermolecule of sky blue fluorescence cadmium is used to prepare organic glass (doped-PMMA)
The organic cyclic annular supermolecule 10mg of the sky blue fluorescence cadmium is weighed, it is sufficiently finely ground spare.In the examination of 20mL clean dried
Guan Zhong is separately added into 1.5ml methyl methacrylate (MMA), 25mg dibenzoyl peroxide (BPO, free radical excitation) and
0.5mL dibutyl phthalate (DBP, plasticizer).It after shaking up, is placed in water-bath, heating water bath works as liquid to 65 DEG C or so
When body is at more sticky shape, stop heating, and be cooled to 40 DEG C or so.
Sufficiently finely ground cyclic annular supermolecule portion-wise with caution is added in the test tube, after sufficiently shaking up, is again placed in water-bath
Pot heating, and constantly shaking continues to be heated to 85 DEG C or so, keeps the temperature 20 minutes left sides to keep powder crystal to be in uniform dispersity
The right side, polymerization reaction are completed, and are cooled to room temperature to get the organic glass composite material (doped- doped with the ring-type supermolecule is arrived
PMMA).The composite material emits sky blue fluorescence (Fig. 7) under 365nm burst of ultraviolel.
2.2) the organic cyclic annular supermolecule solution of sky blue fluorescence cadmium is to Ag+、Cr3+The detection of ion
In 20mL vial, the detection solution of the organic cyclic annular supermolecule (being abbreviated as CdOC) of cadmium-is prepared, finely ground CdOC is brilliant
Body powder is dissolved in 10mL water, is shaken, is shaken up, and ultrasonic disperse 10min obtains suspension, and suspension is aged three days, steady to solution
It is fixed, take upper layer clear solution as detection liquid.
Ag is weighed respectively+、Cr3+、Cu2+、Cd2+、Mg2+、Ni2+、Co2+、Zn2+And Pb2+Nitrate is in clean with number
Vial in, pipette ultrapure water in in number vial with pipette, compound concentration 0.01molL-1Cation
Solution shakes up and down, shakes up, and ultrasonic 25min dissolution is spare.
By T6 ultraviolet-uisible spectrophotometer instrument (Beijing Pu Xi all purpose instrument Co., Ltd), visited in 4.0 quantitative mL
It surveys in liquid, is separately added into the different metal cationic solution 1.0mL with number, test ultraviolet-visible absorption spectroscopy figure (figure respectively
8).CdOC detection liquid spectrum, which can be seen that itself visible region in 400nm or more, absorption.Metal cation-CdOC is mixed
It closes in solution absorption spectra, Ag+Near the mixture solution UV absorption blue shift to 260nm of-CdOC, variation is apparent；Cr3+-
The mixture solution of CdOC has absorption at 407nm and 573nm in visible region.Therefore the organic cyclic annular supermolecule system of new cadmium-
Standby detection liquid, can be used for Ag+And Cr3+The selectivity of ion detects.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of organic cyclic annular supermolecule of sky blue fluorescence cadmium, which is characterized in that the organic cyclic annular oversubscription of the sky blue fluorescence cadmium
The chemical composition of son is [Cd2(H2etc)2(phen)2(H2O)2], the component H2etc2-It is quaternary carboxylic acid H4Etc, structure is such as
Formulas I is sloughed obtained by 2 protons, each H2etc2-2 metal Cd of bridging2+Ion, coordination structure is as shown in formula III；Component
Phen structure such as Formula II, each phen chelate 1 metal Cd2+Ion, coordination mode is as shown in formula III；Each Cd2+Ion point
Not with 4 O atoms and 2 N Atomic coordinates from four components, hexa-coordinate mode [CdO is taken4N2]；
2. a kind of preparation method of the organic cyclic annular supermolecule of sky blue fluorescence cadmium as described in claim 1, which is characterized in that institute
The organic cyclic annular supermolecule of sky blue fluorescence cadmium is stated with H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3As raw material, with second
The mixed solution of nitrile and water is prepared using solvent-thermal process method, is specifically comprised the following steps: as solvent
(1) by raw material H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3And solvent acetonitrile and water are mixed to form reactant
System, is placed in closed container；The H4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3The mass ratio of the material be 1:1:1~
Volume ratio 1:1~9 of 3:4~10, the solvent acetonitrile and water；
(2) reaction system is placed in 30~70min of stirring at room temperature, then takes out stirrer, be encapsulated in stainless steel sleeve, is placed in baking
It is warming up to 110 DEG C~135 DEG C in case, reacts 4~6 days, natural cooling, filtering, air drying obtains colourless rhabdolith.
3. the preparation method of the organic cyclic annular supermolecule of sky blue fluorescence cadmium according to claim 2, which is characterized in that step
(1) H described in4etc、phen·H2O、Cd(NO3)2·4H2O and HNO3The mass ratio of the material be 1:1:1:4.2；The solvent second
The volume ratio 1:9 of nitrile and water.
4. the preparation method of the organic cyclic annular supermolecule of sky blue fluorescence cadmium according to claim 2, which is characterized in that reaction
H in system4The amount concentration of the parent material of etc is 5mmol/L.
5. the preparation method of the organic cyclic annular supermolecule of sky blue fluorescence cadmium according to claim 2, which is characterized in that step
(2) reaction temperature is 120 DEG C in, after the drying refers to that crystal is washed with water, is spontaneously dried in air.
6. a kind of application of the organic cyclic annular supermolecule of sky blue fluorescence cadmium, which is characterized in that will be any using claim 2~5
Preparation and cation detection etc. of the organic cyclic annular supermolecule of sky blue fluorescence cadmium made from the method in photosensitized composite material
The application of aspect.
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| CN110628037A (en) * | 2019-09-12 | 2019-12-31 | 重庆师范大学 | Yellow fluorescent mixed manganese supramolecular polymer and preparation method and application thereof |
| CN110776649A (en) * | 2019-11-11 | 2020-02-11 | 重庆师范大学 | Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof |
| CN110885450A (en) * | 2019-12-09 | 2020-03-17 | 重庆师范大学 | Green fluorescent cadmium-organic coordination polymer and preparation method and application thereof |
| CN111019150A (en) * | 2019-12-13 | 2020-04-17 | 重庆师范大学 | Two-dimensional interpenetrating formed three-dimensional cadmium coordination polymer and preparation method and application thereof |
| CN111234252A (en) * | 2020-02-24 | 2020-06-05 | 重庆师范大学 | Cadmium-organic supermolecule fluorescent polymer and preparation method and application thereof |
| CN111253586A (en) * | 2020-03-09 | 2020-06-09 | 重庆师范大学 | Cadmium-based metal-organic framework material and preparation method and application thereof |
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| CN110105584B (en) * | 2019-05-23 | 2022-01-07 | 河南理工大学 | Porous cadmium/copper-doped complex and preparation method and application thereof |
| CN110628037A (en) * | 2019-09-12 | 2019-12-31 | 重庆师范大学 | Yellow fluorescent mixed manganese supramolecular polymer and preparation method and application thereof |
| CN110628037B (en) * | 2019-09-12 | 2021-10-26 | 重庆师范大学 | Yellow fluorescent mixed manganese supramolecular polymer and preparation method and application thereof |
| CN110776649A (en) * | 2019-11-11 | 2020-02-11 | 重庆师范大学 | Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof |
| CN110776649B (en) * | 2019-11-11 | 2021-10-26 | 重庆师范大学 | Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof |
| CN110885450A (en) * | 2019-12-09 | 2020-03-17 | 重庆师范大学 | Green fluorescent cadmium-organic coordination polymer and preparation method and application thereof |
| CN111019150A (en) * | 2019-12-13 | 2020-04-17 | 重庆师范大学 | Two-dimensional interpenetrating formed three-dimensional cadmium coordination polymer and preparation method and application thereof |
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