CN104277065B - Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion - Google Patents
Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion Download PDFInfo
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- CN104277065B CN104277065B CN201410443247.0A CN201410443247A CN104277065B CN 104277065 B CN104277065 B CN 104277065B CN 201410443247 A CN201410443247 A CN 201410443247A CN 104277065 B CN104277065 B CN 104277065B
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Abstract
The invention provides a kind of coordination compound, its preparation method, fluorine ion sensing device and method of detection fluorion represented by chemical formula 1, chemical formula 1:In chemical formula 1, m is the integer of 05, and n is the integer of 04, R1、R2And R3All independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2‑C30Ether, substituted or unsubstituted C2‑C30Ester group, substituted or unsubstituted C1‑C30Alkyl, substituted or unsubstituted C2‑C30Thiazolinyl, substituted or unsubstituted C2‑C30Alkynyl, substituted or unsubstituted C3‑C30Cycloalkyl, substituted or unsubstituted C1‑C30Alkoxyl, substituted or unsubstituted C3‑C30Cycloalkyloxy, substituted or unsubstituted C5‑C30Aryl, substituted or unsubstituted C5‑C30Aryloxy group and substituted or unsubstituted C3‑C30The group of heteroaryl composition.
Description
Technical field
The present invention relates to a kind of coordination compound and preparation method thereof, particularly to a kind of cooperation that can be used as fluorine ion sensing device
Thing and preparation method thereof.
Background technology
Anion has great importance in biology, medical science and environmental science, about the design of anion acceptor
Synthesis has caused the broad interest of people.In recent decades, people design and have synthesized various anion acceptor,
Optionally identify some important aniones.Fluorion, as minimum anion, has the chemical property of uniqueness, is that human body must
The trace element needed, such as significant to the clinical treatment of the preventing and treating of dental caries and osteoporosis etc., incorrect picked-up
Then cause fluorosis.The detection of fluorion identifies and medical science, environmental science and Food Science is suffered from important meaning.
Summary of the invention
It is an object of the present invention to provide a kind of coordination compound.
Another object of the present invention is to provide a kind of coordination compound that can be used as fluorine ion sensing device.
A further object of the present invention is to provide the preparation method of a kind of coordination compound that can be used as fluorine ion sensing device.
It is still another object of the present invention to provide a kind of method detecting fluorion.
Coordination compound according to the present invention is represented by chemical formula 1:
Chemical formula 1:
In chemical formula 1, m is the integer of 0-5, and n is the integer of 0-4, R1、R2And R3All independently selected from deuterium, tritium, halogen
Element, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2-C30Ether, substituted or unsubstituted C2-C30Ester
Base, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Thiazolinyl, substituted or unsubstituted C2-C30
Alkynyl, substituted or unsubstituted C3-C30Cycloalkyl, substituted or unsubstituted C1-C30Alkoxyl, substituted or unsubstituted
C3-C30Cycloalkyloxy, substituted or unsubstituted C5-C30Aryl, substituted or unsubstituted C5-C30Aryloxy group and substituted or
Unsubstituted C3-C30The group of heteroaryl composition.
R1、R2And R3All can independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or
Unsubstituted C2-C6Ether, substituted or unsubstituted C2-C6Ester group, substituted or unsubstituted C1-C6Alkyl, substituted or
Unsubstituted C2-C6Thiazolinyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted
Or unsubstituted C1-C6Alkoxyl, substituted or unsubstituted C3-C10Cycloalkyloxy, substituted or unsubstituted C5-C20Aryl,
Substituted or unsubstituted C5-C20Aryloxy group and substituted or unsubstituted C3-C20The group of heteroaryl composition.
R1、R2And R3All can independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or
Unsubstituted C2-C4Ether, substituted or unsubstituted C2-C4Ester group, substituted or unsubstituted C1-C4Alkyl, substituted or
Unsubstituted C2-C4Thiazolinyl, substituted or unsubstituted C2-C4Alkynyl, substituted or unsubstituted C3-C6Cycloalkyl, substituted
Or unsubstituted C1-C4Alkoxyl, substituted or unsubstituted C3-C6Cycloalkyloxy, substituted or unsubstituted C5-C12Aryl,
Substituted or unsubstituted C5-C12Aryloxy group and substituted or unsubstituted C3-C12The group of heteroaryl composition.
R1And R3All can be independently selected from-F ,-Cl ,-NH2、-NO2、-OR4With-COOR4The group of composition, R2Can be selected from
Methyl, ethyl and the group of propyl group composition, wherein, R4It is C1-C30Alkyl, C3-C30Cycloalkyl or C5-C30Aryl.Further, R4
Can be C1-C6Alkyl, C3-C10Cycloalkyl, C5-C20Aryl.Closer, R4Can be C1-C4Alkyl, C3-C6Cycloalkyl,
C5-C12Aryl, such as methyl, ethyl, propyl group, butyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, phenyl, naphthyl.
The preparation method of the coordination compound according to the present invention includes: make part
With AlCl3With alcohol R2OH reaction obtains described coordination compound.
This preparation method may also include prepares partStep, preparation
PartStep include: makeObtain with ethanol synthesis
To intermediate 1；Intermediate 1 and hydrazine reaction is made to obtain intermediate 2；Make intermediate 2 withDuring reaction obtains
Mesosome 3；Make intermediate 3 and polyphosphoric acids react and obtain intermediate 4；Make intermediate 4 react with Boron tribromide and obtain part
Fluorine ion sensing device according to the present invention includes above-mentioned coordination compound.
In detection solution according to the present invention, the method for fluorion includes: described coordination compound is joined described solution
In；Measure ultraviolet-visible or the ultra-violet absorption spectrum of described solution, or measure the fluorescence spectrum of described solution, or observe described
The color of solution；Color according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution becomes
Change and determine that described solution contains fluorion.
In detection solution according to the present invention, the method for fluorion includes: dissolved in a solvent by described coordination compound, with
Obtain the first solution；Second solution is gradually added in the first solution, to obtain mixed solution；It is being gradually added into the first solution
During, measure ultraviolet-visible or the ultra-violet absorption spectrum of mixed solution, or the fluorescence spectrum of measurement mixed solution, or observe
The color of mixed solution；According to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or the face of mixed solution
Complexion changed determines that the second solution contains fluorion.
Accompanying drawing explanation
Fig. 1 shows the CH to the ligand 1 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The uv-visible absorption spectra arrived, illustration therein be wavelength be at 320nm and 416nm, absorbance along with add F-Equivalent value
Changing trend diagram；
Fig. 2 shows the CH to the part 2 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The uv-visible absorption spectra arrived, illustration therein be wavelength be at 327nm and 423nm, absorbance along with add F-Equivalent value
Changing trend diagram；
Fig. 3 shows the CH to the part 3 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The ultra-violet absorption spectrum arrived；
Fig. 4 shows the CH to the part 4 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The ultra-violet absorption spectrum arrived；
Fig. 5 shows the CH to the part 5 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The ultra-violet absorption spectrum arrived；
Fig. 6 shows the CH to the part 7 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The ultra-violet absorption spectrum arrived；
Fig. 7 shows the CH to the part 8 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The ultra-violet absorption spectrum arrived；
Fig. 8 shows the CH to the ligand 1 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The fluorescence spectrum figure arrived, illustration therein be wavelength be at 386nm, 399nm and 411nm, fluorescence intensity along with add F-Equivalent
The changing trend diagram of value；
Fig. 9 shows the CH to the part 3 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The fluorescence spectrum figure arrived；
Figure 10 shows the CH to the part 4 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The fluorescence spectrum figure arrived, in figure, the photo in left side demonstrates and does not drips F-Time solution, in figure right side photo demonstrate dropping
F-Time solution；
Figure 11 shows the CH to the part 5 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The fluorescence spectrum figure arrived；
Figure 12 shows the CH to the part 8 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-?
The fluorescence spectrum figure arrived；
Figure 13 shows the CH to the part 2 according to the present invention2Cl2/CH3CN (1:2, v/v) solution is separately added into
The F of 3.8eq (equivalent)-、Br-、I-、H2PO4 -And CH3COO-After the uv-visible absorption spectra that obtains, and show part 2
CH2Cl2/CH3CN (1:2, v/v) solution and add the F of 3.8eq-、Br-、I-、H2PO4 -And CH3COO-After the photograph of solution
Sheet；
Figure 14 shows the CH to the coordination compound 1 according to the present invention2Cl2/CH3CN (1:2, v/v) solution drips respectively
[Bu4N] R (R=Br-,I-,F-,H2PO4 -And CH3COO-The uv-visible absorption spectra obtained after), and show coordination compound 1
CH2Cl2/CH3CN (1:2, v/v) solution and add F-、Br-、I-、H2PO4 -And CH3COO-After the photo of solution；
Figure 15 shows the CH to the coordination compound 1 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-
The uv-visible absorption spectra obtained, illustration therein be wavelength be at 368nm and 423nm, absorbance along with add F-Equivalent
The changing trend diagram of value；
Figure 16 shows the CH to the coordination compound 5 according to the present invention2Cl2/CH3CN (1:2, v/v) solution constantly drips F-
The ultra-violet absorption spectrum obtained；
Figure 17 shows the CH to the coordination compound 1 (2 μMs) according to the present invention2Cl2/CH3In CN (1:2, v/v) solution constantly
Dropping F-The fluorescence spectrum figure (excitation wavelength is 285nm) obtained, illustration therein be wavelength be fluorescence at 374nm and 508nm
Intensity is along with adding F-The changing trend diagram of equivalent value, in figure, the photo in left side demonstrates and does not drips F-Time solution, in figure right side
Photo demonstrate and dripped F-Time solution；
Figure 18 shows the CH to the coordination compound 5 (2 μMs) according to the present invention2Cl2/CH3In CN (1:2, v/v) solution constantly
Dropping F-The fluorescence spectrum figure (excitation wavelength is 370nm) obtained, in figure, the photo in left side demonstrates and does not drips F-Time solution,
In figure, the photo on right side demonstrates and has dripped F-Time solution.
Detailed description of the invention
Coordination compound according to the present invention is represented by chemical formula 1, and it is a kind of double-core bridging aluminum complex.
Chemical formula 1:
In chemical formula 1, m is the integer of 0-5, (R1)mM R of the hydrogen atom on expression substituted benzene ring1Substituent group.Work as m
During equal to 0, there is not the substituent R of hydrogen atom on substituted benzene ring1.M can be 1,2,3,4 or 5.
R1Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2-C30Ether
Base, substituted or unsubstituted C2-C30Ester group, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30
Thiazolinyl, substituted or unsubstituted C2-C30Alkynyl, substituted or unsubstituted C3-C30Cycloalkyl, substituted or unsubstituted
C1-C30Alkoxyl, substituted or unsubstituted C3-C30Cycloalkyloxy, substituted or unsubstituted C5-C30Aryl, substituted or
Unsubstituted C5-C30Aryloxy group and substituted or unsubstituted C3-C30The group of heteroaryl composition.
In one exemplary embodiment, R1Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C6Ether, substituted or unsubstituted C2-C6Ester group, substituted or unsubstituted C1-C6Alkyl, take
Generation or unsubstituted C2-C6Thiazolinyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl,
Substituted or unsubstituted C1-C6Alkoxyl, substituted or unsubstituted C3-C10Cycloalkyloxy, substituted or unsubstituted C5-
C20Aryl, substituted or unsubstituted C5-C20Aryloxy group and substituted or unsubstituted C3-C20The group of heteroaryl composition.
In one exemplary embodiment, R1Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C4Ether, substituted or unsubstituted C2-C4Ester group, substituted or unsubstituted C1-C4Alkyl, take
Generation or unsubstituted C2-C4Thiazolinyl, substituted or unsubstituted C2-C4Alkynyl, substituted or unsubstituted C3-C6Cycloalkyl,
Substituted or unsubstituted C1-C4Alkoxyl, substituted or unsubstituted C3-C6Cycloalkyloxy, substituted or unsubstituted C5-
C12Aryl, substituted or unsubstituted C5-C12Aryloxy group and substituted or unsubstituted C3-C12The group of heteroaryl composition.
In chemical formula 1, n is the integer of 0-4, (R3)nN R of the hydrogen atom on expression substituted benzene ring3Substituent group.Work as n
During equal to 0, there is not the substituent R of hydrogen atom on substituted benzene ring3.M can be 1,2,3 or 4.
R3Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2-C30Ether
Base, substituted or unsubstituted C2-C30Ester group, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30
Thiazolinyl, substituted or unsubstituted C2-C30Alkynyl, substituted or unsubstituted C3-C30Cycloalkyl, substituted or unsubstituted
C1-C30Alkoxyl, substituted or unsubstituted C3-C30Cycloalkyloxy, substituted or unsubstituted C5-C30Aryl, substituted or
Unsubstituted C5-C30Aryloxy group and substituted or unsubstituted C3-C30The group of heteroaryl composition.
In one exemplary embodiment, R3Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C6Ether, substituted or unsubstituted C2-C6Ester group, substituted or unsubstituted C1-C6Alkyl, take
Generation or unsubstituted C2-C6Thiazolinyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl,
Substituted or unsubstituted C1-C6Alkoxyl, substituted or unsubstituted C3-C10Cycloalkyloxy, substituted or unsubstituted C5-
C20Aryl, substituted or unsubstituted C5-C20Aryloxy group and substituted or unsubstituted C3-C20The group of heteroaryl composition.
In one exemplary embodiment, R3Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C4Ether, substituted or unsubstituted C2-C4Ester group, substituted or unsubstituted C1-C4Alkyl, take
Generation or unsubstituted C2-C4Thiazolinyl, substituted or unsubstituted C2-C4Alkynyl, substituted or unsubstituted C3-C6Cycloalkyl,
Substituted or unsubstituted C1-C4Alkoxyl, substituted or unsubstituted C3-C6Cycloalkyloxy, substituted or unsubstituted C5-
C12Aryl, substituted or unsubstituted C5-C12Aryloxy group and substituted or unsubstituted C3-C12The group of heteroaryl composition.
In chemical formula 1, R2Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, substituted or not
Substituted C2-C30Ether, substituted or unsubstituted C2-C30Ester group, substituted or unsubstituted C1-C30Alkyl, substituted or
Unsubstituted C2-C30Thiazolinyl, substituted or unsubstituted C2-C30Alkynyl, substituted or unsubstituted C3-C30Cycloalkyl, replacement
Or unsubstituted C1-C30Alkoxyl, substituted or unsubstituted C3-C30Cycloalkyloxy, substituted or unsubstituted C5-C30Virtue
Base, substituted or unsubstituted C5-C30Aryloxy group and substituted or unsubstituted C3-C30The group of heteroaryl composition.
In one exemplary embodiment, R2Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C6Ether, substituted or unsubstituted C2-C6Ester group, substituted or unsubstituted C1-C6Alkyl, take
Generation or unsubstituted C2-C6Thiazolinyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl,
Substituted or unsubstituted C1-C6Alkoxyl, substituted or unsubstituted C3-C10Cycloalkyloxy, substituted or unsubstituted C5-
C20Aryl, substituted or unsubstituted C5-C20Aryloxy group and substituted or unsubstituted C3-C20The group of heteroaryl composition.
In one exemplary embodiment, R2Can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, take
Generation or unsubstituted C2-C4Ether, substituted or unsubstituted C2-C4Ester group, substituted or unsubstituted C1-C4Alkyl, take
Generation or unsubstituted C2-C4Thiazolinyl, substituted or unsubstituted C2-C4Alkynyl, substituted or unsubstituted C3-C6Cycloalkyl,
Substituted or unsubstituted C1-C4Alkoxyl, substituted or unsubstituted C3-C6Cycloalkyloxy, substituted or unsubstituted C5-
C12Aryl, substituted or unsubstituted C5-C12Aryloxy group and substituted or unsubstituted C3-C12The group of heteroaryl composition.
In one exemplary embodiment, R1And R3All can be independently selected from-F ,-Cl ,-NH2、-NO2、-OR4With-
COOR4The group of composition, wherein, R4It is C1-C30Alkyl, C3-C30Cycloalkyl or C5-C30Aryl, R2Can be selected from methyl, ethyl and
The group of propyl group composition.Further, R4Can be C1-C6Alkyl, C3-C10Cycloalkyl, C5-C20Aryl.Closer, R4Can
To be C1-C4Alkyl, C3-C6Cycloalkyl, C5-C12Aryl, such as methyl, ethyl, propyl group, butyl, cyclopropyl, cyclobutyl, ring penta
Base, cyclohexyl, phenyl, naphthyl.
Unsubstituted C described here1-C30The example of alkyl includes but not limited to methyl, ethyl, propyl group, isobutyl group, secondary
Butyl, amyl group, isopentyl, hexyl, heptyl, octyl group, nonyl and dodecyl.C1-C30At least one hydrogen atom of alkyl is permissible
By D atom (deuterium, tritium), halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic acid
Base or its salt, phosphoric acid or its salt, C1-C30Alkyl, C1-C30Alkoxyl, C2-C30Thiazolinyl, C2-C30Alkynyl, C5-C20Aryl, C3-C20
Heteroaryl ,-N (Q1)(Q2) or-Si (Q3)(Q4)(Q5) replace.Here, Q1To Q5All can independently be hydrogen atom, D atom
(deuterium, tritium), halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic group or its salt,
Phosphoric acid or its salt, C1-C30Alkyl, C1-C30Alkoxyl, C2-C30Thiazolinyl, C2-C30Alkynyl, C5-C20Aryl or C3-C20Heteroaryl.
Unsubstituted C described here2-C30The example of thiazolinyl includes vinyl, acrylic, cyclobutenyl etc..Unsubstituted
C2-C30At least one hydrogen atom in thiazolinyl can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
Unsubstituted C described here2-C30The example of alkynyl includes acetenyl, propinyl, phenylene-ethynylene, naphthyl second
Alkynyl, isopropyl-acetylene base, tert-butyl acetylene base and dibenzenyl base.Unsubstituted C2-C30At least one hydrogen in alkynyl
Atom can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
C described here3-C30The example of cycloalkyl includes cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl and suberyl.Not
Substituted C3-C30At least one hydrogen atom in cycloalkyl can be referenced substituted C1-C30The substituent group that alkyl describes is taken
Generation.
Unsubstituted C described here1-C30The example of alkoxyl include methoxyl group, ethyoxyl, propoxyl group, isopropoxy,
Butoxy and amoxy.C1-C30At least one hydrogen atom of alkoxyl can be referenced substituted C1-C30The replacement that alkyl describes
Base is replaced.
Unsubstituted C described here3-C30The example of cycloalkyloxy includes ring propoxyl group, cyclobutoxy group and cyclopentyloxy.
C3-C30At least one hydrogen atom of cycloalkyloxy can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
Unsubstituted C described here5-C30Aryl refers to the carbocyclic, aromatic systems containing at least one ring.At least two
Ring can condense each other, maybe can be connected to each other by singly-bound.Term " aryl " refers to aroma system, such as phenyl, naphthyl or
Anthryl.C5-C30At least one hydrogen atom in aryl can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
Substituted or unsubstituted C5-C30The example of aryl includes but not limited to: phenyl, C1-C10Alkyl phenyl (such as, ethylo benzene
Base), halogenophenyl (such as, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, Dichlorobenzene base), cyano-phenyl, dicyano phenyl, three
Fluorine methoxyphenyl, xenyl, halogenated biphenyl base, cyanobiphenyl base, C1-C10Alkyl biphenyl base, C1-C10Alkoxyl xenyl,
O-tolyl, a tolyl and p-methylphenyl, adjacent cumenyl, a cumenyl and to cumenyl,Base, phenoxy group benzene
Base, (alpha, alpha-dimethyl benzene) phenyl, (N, N'-dimethyl) aminophenyl, (N, N'-diphenyl) aminophenyl, pentalene
Base, indenyl, naphthyl, halo naphthyl (such as, fluoro naphthyl), C1-C10Alkyl naphthyl (such as, methyl naphthyl), C1-C10Alkoxyl
Naphthyl (such as, methoxyl group naphthyl), cyanonaphthyl, anthryl,Base, heptalenyl, acenaphthenyl, week naphthyl, fluorenyl, anthraquinonyl, first
Base anthryl, phenanthryl, benzo [9,10] phenanthryl, pyrenyl, 1,2-benzo phenanthryl, ethyl-1,2-benzo phenanthryl, base, base, chloro
Base, pentaphene base, pentacenyl, neighbours' phenylene, hexaphene base, hexacenyl, rubicenyl, base, ter naphthyl, heptaphene
Base, heptaphenyl and pyranthrene base.
Unsubstituted C described here5-C30The example of aryloxy group includes phenoxy group, naphthoxy, biphenylyloxy, dinaphthalene oxygen
Base, anthracene epoxide etc..C5-C30At least one hydrogen atom of aryloxy group can be referenced substituted C1-C30The substituent group that alkyl describes
Replaced.
Unsubstituted C described here3-C30Heteroaryl includes at least one hetero atom selected from N, O, P and S.Extremely
Few two rings can condense each other, maybe can be connected to each other by singly-bound.Unsubstituted C3-C30The example of heteroaryl can include
Pyrazolyl, imidazole radicals, oxazolyl, thiazolyl, triazolyl, tetrazole radical, di azoly, pyridine radicals, pyridazinyl, pyrimidine radicals, triazine
Base, carbazyl, indyl, quinolyl and isoquinolyl.C3-C30At least one hydrogen atom in heteroaryl can be referenced replacement
C1-C30The substituent group that alkyl describes is replaced.
Unsubstituted ether described here is to have-A1-O-A2The group of structure, wherein ,-A2Be unsubstituted alkyl,
Unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A1-be unsubstituted alkylidene,
Unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arlydene or unsubstituted inferior heteroaryl.In ether at least one
Individual hydrogen atom can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
Unsubstituted ester group described here is to have-A3COOA4Or A5COOA6The group of-structure, wherein ,-A4It is not take
The alkyl in generation, unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A3-it is singly-bound, not
Substituted alkylidene, unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arlydene or unsubstituted inferior heteroaryl ,-
A5It is unsubstituted alkyl, unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A6-be
Singly-bound, unsubstituted alkylidene, unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arlydene or unsubstituted Asia
Heteroaryl.At least one hydrogen atom in ester group can be referenced substituted C1-C30The substituent group that alkyl describes is replaced.
In chemical formula 1, R1It is connected on phenyl ring.Specifically, R1May be coupled to 2 of phenyl ring, 3,4,5
Or the carbon atom of any position in 6.Preferably, R1The carbon atom of 4 be connected on phenyl ring, R in this position1
Sterically hindered less, and the easily fabricated coordination compound according to the present invention.Less preferred, R13 be connected on phenyl ring
Carbon atom with a position in 5.More less preferred, R1A position in 2 be connected on phenyl ring and 6
Carbon atom.
In chemical formula 1, R3It is connected on phenyl ring.Specifically, R3May be coupled to the C atom that O atom is connected to
The carbon atom of any position in ortho position, meta, para-position.Preferably, R3It is connected to the carbon atom of para-position, in this position
R3Sterically hindered less, and the easily fabricated coordination compound according to the present invention.Less preferred, R3It is connected to ortho position on phenyl ring
Or the carbon atom of meta.
Coordination compound according to the present invention can be any one in following coordination compound 1 to coordination compound 6.
Coordination compound 1:
Coordination compound 2:
Coordination compound 3:
Coordination compound 4:
Coordination compound 5:
Coordination compound 6:
The preparation method of the coordination compound according to the present invention is described below.Root can be prepared according to following reaction scheme 1
Coordination compound according to the present invention.
Reaction scheme 1:
More particularly, part is madeWith AlCl3With alcohol R2OH reaction obtains
Coordination compound according to the present invention.
Part can be prepared according to following reaction scheme 2
Reaction scheme 2:
More particularly, make as raw materialIntermediate 1 is obtained, in then making with ethanol synthesis
Mesosome 1 and hydrazine reaction generate intermediate 2, intermediate 2 with as raw materialReaction generates intermediate 3, so
After make intermediate 3 and polyphosphoric acids react generation intermediate 4, last intermediate 4 reacts with Boron tribromide and generates part
Anion sensors mainly includes that antenna group (or referred to as conjugated group), connector and chromophore (or are referred to as
Signal group).Antenna group interacts with sensing ion (anion) or combines sensing ion, i.e. receive signal.Add lustre to base
After receiving the signal (that is, with antenna Interaction of substituents) of antenna group, there is color change, spectrum change (such as in group
Visible-ultra-violet absorption spectrum or change in fluorescence) or electrochemical properties change, by instrument or naked eyes direct feeling to this change
Change, to reach the purpose of the identification to relevant ions and detection.Connector is in order to antenna group and chromophore to be connected
Come.
The Main Function of antenna group is that measured ion is treated in sensing, needs there is a strong interaction with treating measured ion, and not with phase
Other similar ions are had an effect.For preparing the part of the coordination compound of the present invention
There is the phenolic hydroxyl group as antenna group, and by the stability of ring hydrogen bond control hydrogen bond, solely to F-Response, and not with its
His ionic interaction.
Chromophore mainly produces color change, visible-ultra-violet absorption spectrum or the group of change in fluorescence, and these changes are permissible
Arrived by instrument or direct visual perception, thus can be by antenna group and F-Interaction be converted into discernible signal, reach
To F-Identification and detection.For preparing the part of the coordination compound of the present inventionTool
Having 1, the heterocycle of 3,4-oxadiazoles groups can pass through as chromophore, its obvious color change, absorbance and change in fluorescence
Naked eyes and instrument are observed simply.Obvious color change caused by chromophore can be arrived by direct visual perception, extinction
Degree change can be observed by spectrogrph, and change in fluorescence can be detected by fluorescent optical sensor, for preparing joining of the present invention
The part of compound takes into account this several respects, and efficient, height selectively achieves the sensing to fluorion.
R in the above-mentioned part preparing the coordination compound of the present invention1And/or R3Selection to fluorion described above
Sensing capabilities does not has substantial effect, it is only possible to have above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence
The effect of fine setting.Additionally, described above is R1May be coupled to any position in 2 of phenyl ring, 3,4,5 or 6
Carbon atom, R3The carbon that may be coupled to any position in the ortho position of C atom that O atom is connected to, meta, para-position is former
Son.R1The position being connected to and/or R3The fluorine ion sensing performance described above of described part is not had by the position being connected to
There is substantial effect, it is only possible to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence are had the work of fine setting
With.
Additionally, there is the phenol epoxide as antenna group according to the coordination compound of the present invention, and control hydrogen bond by ring hydrogen bond
Stability, solely to F-Response, and not with other ionic interactions.Coordination compound according to the present invention has 1,3,4-and dislikes
The heterocycle of oxadiazole can pass through naked eyes and instrument as chromophore, its obvious color change, absorbance and change in fluorescence
Observe simply.Obvious color change caused by chromophore can be arrived by direct visual perception, and absorbance change can be led to
Cross spectrogrph to observe, and change in fluorescence can be detected by fluorescent optical sensor, take into account this several sides according to the coordination compound of the present invention
Face, efficient, height selectively achieves the sensing to fluorion.
Substituent R in chemical formula 11、R2And/or R3Selection fluorine ion sensing performance described above is not had essence
Property impact, it is only possible to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence are had the effect of fine setting.Additionally,
Described above is in chemical formula 1, R1May be coupled to the carbon of any position in 2 of phenyl ring, 3,4,5 or 6
Atom, R3May be coupled to the carbon atom of any position in the ortho position of C atom that O atom is connected to, meta, para-position.R1Institute
The position being connected to and/or R3The position being connected to does not has substantive shadow to the fluorine ion sensing performance of the coordination compound of the present invention
Ring, it is only possible to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence are had the effect of fine setting.
Fluorine ion sensing device according to the present invention can include the coordination compound according to the present invention.Fluorion according to the present invention passes
Sensor can be the coordination compound according to the present invention.
In detection solution according to the present invention, the method for fluorion comprises the steps that the coordination compound of the present invention (such as, with solution
Form) join in described solution；Ultraviolet-visual spectrometer is used to measure ultraviolet-visible or the uv absorption light of described solution
Spectrum, or the fluorescence spectrum of described solution, or the color of the described solution that detects by an unaided eye is measured by fluorescence spectrophotometer；According to ultraviolet-
Visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution color change determines that described solution contains
Fluorion.
In detection solution according to the present invention, the method for fluorion comprises the steps that and the coordination compound of the present invention is dissolved in solvent
In, to obtain the first solution；Second solution is added in the first solution, to obtain mixed solution；Use ultraviolet-visual spectrometer
Measure the ultraviolet-visible of mixed solution or ultra-violet absorption spectrum relative to the ultraviolet-visible of the first solution or ultra-violet absorption spectrum
Change, or measure the fluorescence spectrum of mixed solution relative to the change of the fluorescence spectrum of the first solution by fluorescence spectrophotometer, or
Detect by an unaided eye the color of mixed solution relative to the change of the color of the first solution；According to ultraviolet-visible or uv absorption light
The change of change, the change of fluorescence spectrum or the color of spectrum determines that the second solution contains fluorion.
In detection solution according to the present invention, the method for fluorion comprises the steps that and the coordination compound of the present invention is dissolved in solvent
In, to obtain the first solution；Second solution is gradually added in the first solution, to obtain mixed solution；It is being gradually added into first
During solution, use ultraviolet-visual spectrometer to measure ultraviolet-visible or the ultra-violet absorption spectrum of mixed solution, or use fluorescence
The fluorescence spectrum of spectrometer measurement mixed solution, or the color of the mixed solution that detects by an unaided eye；Inhale according to ultraviolet-visible or ultraviolet
The color change receiving the change of spectrum, the change of fluorescence spectrum or mixed solution determines that the second solution contains fluorion.
It is more fully described coordination compound according to the present invention and preparation method thereof below in association with example.
Preparation example 1: the preparation of part 2
Part 2 is prepared according to following reaction scheme 3.
Reaction scheme 3:
First, synthetic intermediate 1-1 (5-chloro-2-methoxybenzoic acid ethyl ester) as steps described below: weigh 5-chloro-2-first
P-methoxybenzoic acid 5g (0.027mmol), in 250mL bis-neck bottle, adds 90mL dehydrated alcohol, concentrated sulphuric acid 14mL, and backflow 24 is little
Time, it is extracted with ethyl acetate and obtains yellow oily liquid 5.4g, productivity 90%.
Then, synthetic intermediate 2-1 (5-chloro-2-methoxybenzoyl hydrazine) as steps described below: weigh 5-chloro-2-methoxy
Yl benzoic acid ethyl ester 5.4g (0.023mmol), in 250mL bis-neck bottle, adds 90mL dehydrated alcohol, the hydrazine hydrate of 80%
3.6mL, N2Protection backflow 24 hours, is obtained by extraction yellow oily liquid with dichloromethane, and (eluent is too short silicagel column
CH2Cl2And petroleum ether), obtain faint yellow solid 3.9g, productivity 85%.1H NMR(400MHz；CDCl3), δ: 8.9 (s, 1H),
8.19-8.17(m,1H),7.47-7.43(t,1H),7.09-7.06(t,1H),6.97-6.95(m,1H),4.2(s,2H),3.9
(s,3H)。
Then, synthetic intermediate 3-1 (4-(2-(5-chloro-2-methoxyphenyl) carbohydrazide) benzoic acid as steps described below
Methyl ester): weigh 5-chloro-2-methoxybenzoyl hydrazine 4.0g (0.02mol) and to phosgene essence of Niobe 3g (0.02mol) in
In 250mL bis-neck bottle, add anhydrous THF 80mL, proceed to oil bath reacting by heating 3h after ice-water bath reaction 1h, be cooled to room temperature, add
Water produces a large amount of precipitation, sucking filtration, by recrystallizing methanol, obtains white needle-like crystals 5.8g, productivity 80%.1H NMR(400MHz；
CDCl3), δ: 11.05 (s, 1H), 10.34 (s, 1H), 8.14-8.08 (q, 3H), 7.99-7.97 (m, 2H), 7.54-7.50 (t,
lH),7.11-7.07(t,1H),4.13(s,3H),3.95(s,3H).ESI,m/z:362.1。
Afterwards, as steps described below synthetic intermediate 4-1 (4-(and 5-(5-chloro-2-methoxyphenyl)-1,3,4-oxadiazoles-
2-) essence of Niobe): weigh intermediate 3-1 (1.11g, 0.003mol) and 10g polyphosphoric acids in two neck bottles, add Isosorbide-5-Nitrae-
Dioxane 60mL reacting by heating 24h, is cooled to room temperature, and a large amount of precipitation of the generation that adds water, sucking filtration, (eluent is too short silicagel column
CH2Cl2And petroleum ether), obtain white powder 0.5g, productivity 50%.1H NMR(400MHz；CDCl3),δ:8.23-8.21(t,
4H),8.02(s,1H),7.51-7.48(d,lH),7.05-7.03(d,1H),4.01(s,3H),3.98(s,3H)。13C NMR
(CDCl3):166.08,163.81,162.68,156.54,132.89,132.78,130.22,129.88,127.65,
126.86,125.85,114.01,113.42,56.42,52.45.ESI,m/z:345.2。
Finally, synthetic ligands 2 (4-(5-(5-chlorine-2-hydroxyl phenyl)-1,3,4-oxadiazoles-2-) benzene as steps described below
Methyl formate): weigh intermediate 4-1 (0.3g, 1mmol) in two neck bottles, add dichloromethane 30mL.Ice bath drips tribromo
Changing the dichloromethane solution 20mL of boron 1mL (2mmol), time for adding is 10-20min, lucifuge reaction 3h, obtains white opacity
Liquid.After completion of the reaction, a small amount of methanol of careful dropping and 20mL water in white opacity liquid, extract with 30mL dichloromethane, rotate
Evaporate solvent and obtain white powder, obtain white crystal 0.2g, productivity 70% by recrystallizing methanol.mp.142-144℃.1H
NMR(400MHz；DMSO-d6): δ 10.65 (s, 1H ,-OH), 8.26 (d, J=8.0Hz, 2H, phenyl), 8.17 (d, J=
8.0Hz, 2H, phenyl), 7.97 (s, 1H, phenyl), 7.53 (d, J=12.0Hz, lH, phenyl), 7.13 (d, J=8.0Hz, 1H,
Phenyl), 3.91 (s, 3H ,-COOCH3).13C NMR(125MHz,CDCl3):δ170.65,168.19,167.93,160.57,
138.36,137.56,135.46,135.34,133.43,132.37,132.28,132.15,128.34,124.31,116.35。
Elementary analysis measured value (C16H12ClN2O4Value of calculation, %) C, 58.13 (58.11)；H,3.72(3.35)；N,8.39(8.47)；
ESI,m/z:330。
Preparation example 2: the preparation of ligand 1
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1
Outside, prepare ligand 1 according to the method essentially identical with preparation example 1.Product is white needles (70%).mp.140-142
℃.1H NMR(400MHz；CDCl3): δ 10.13 (s, 1H ,-OH), 8.23 (s, 4H, phenyl), 7.89 (d, J=12.0Hz, 1H,
Phenyl), 7.48 (t, J=1.6Hz, 1H, phenyl), 7.16 (d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, benzene
Base), 3.91 (s, 3H ,-COOCH3).13C NMR(125MHz,CDCl3):δ165.98,164.67,162.49,157.82,
134.01,133.21,130.36,127.04,126.95,126.58,120.02,117.74,107.83,52.521.Element divides
Analysis measured value (C16H12N2O4Value of calculation, %) C, 65.13 (64.86)；H,4.68(4.08)；N,9.42(9.46)；ESI,m/z:
296。
Ligand 1:
Preparation example 3: the preparation of part 3
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1,
During preparing intermediate 3-1 use Benzenecarbonyl chloride. replace to phosgene essence of Niobe outside, according to preparation example 1 base
This identical method prepares part 3.Product is white needles (80%).1H NMR(400MHz；CDCl3):δ10.19(s,
1H ,-OH), 8.15 (d, J=2H), 8.13 (d, J=12.0Hz, 1H, phenyl), 7.8 (t, J=1.6Hz, 3H, phenyl), 7.46
(d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, phenyl), 7.02 (s, 1H)；ESI,m/z:238.
Part 3:
Preparation example 4: the preparation of part 4
In addition to using Benzenecarbonyl chloride. to replace phosgene essence of Niobe during preparing intermediate 3-1, press
Part 4 is prepared according to the method essentially identical with preparation example 1.Product is pale pink needle-like solid (75%).1H NMR(400MHz；
CDCl3): δ 10.19 (s, 1H ,-OH), 8.15 (d, J=2H), 8.13 (d, J=12.0Hz, 1H, phenyl), 7.8 (t, J=
1.6Hz, 3H, phenyl), 7.46 (d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, phenyl), 7.02 (s, 1H)；
ESI,m/z:272。
Part 4:
Preparation example 5: the preparation of part 5
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1,
Use during preparing intermediate 3-1 p-benzoyl chloro for outside to phosgene essence of Niobe, according to system
The method essentially identical for example 1 prepares part 5.Product is pale yellow powder (70%).1H NMR(400MHz；CDCl3):δ
10.19 (s, 1H ,-OH), 7.86 (d, J=2H), 7.76 (d, J=12.0Hz, 1H, phenyl), 7.37 (t, J=1.6Hz, 1H, benzene
Base), 7.06 (d, J=8.0Hz, lH, phenyl), 6.96 (t, J=0.4Hz, 1H, phenyl), 6.70 (s, 1H), 4.01 (s, 2H ,-
NH2)；ESI,m/z:253.
Part 5:
Preparation example 6: the preparation of part 6
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1,
During preparing intermediate 3-1 use paranitrobenzoyl chloride replace to phosgene essence of Niobe outside, according to system
The method essentially identical for example 1 prepares part 6.Product is pale yellow powder (75%).1H NMR(400MHz；CDCl3):δ9.97
(s, 1H ,-OH), 8.36 (d, 4H), 7.81 (d, J=12.0Hz, 1H, phenyl), 7.45 (t, J=1.6Hz, 1H, phenyl), 7.1
(d, J=8.0Hz, lH, phenyl), 6.99 (t, J=0.4Hz, 1H, phenyl), 6.70 (s, 1H)；ESI,m/z:283.
Part 6:
Preparation example 7: the preparation of part 7
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1,
During preparing intermediate 3-1 use parachlorobenzoyl chloride replace to phosgene essence of Niobe outside, according to preparation
The essentially identical method of example 1 prepares part 7.Product is white powder (80%).1H NMR(400MHz；CDCl3):δ10.11(s,
1H ,-OH), 8.07 (d, 2H), 7.75 (d, J=12.0Hz, 1H, phenyl), 7.50 (t, J=1.6Hz, 3H, phenyl), 7.34 (d,
J=8.0Hz, lH, phenyl), 7.02 (t, J=0.4Hz, 1H, phenyl)；ESI,m/z:272.
Part 7:
Preparation example 8: the preparation of part 8
Except using 2-methoxybenzoic acid to replace the chloro-2-methoxybenzoic acid of 5-during preparing intermediate 1-1,
Use during preparing intermediate 3-1 to fluorobenzoyl chloride replace to phosgene essence of Niobe outside, according to preparation
The essentially identical method of example 1 prepares part 8.Product is khaki powder (74%).1H NMR(400MHz；CDCl3):δ10.08
(s, 1H ,-OH), 8.08 (d, 3H), 7.78 (d, J=12.0Hz, 1H, phenyl), 7.41 (t, J=1.6Hz, 1H, phenyl), 7.19
(d, J=8.0Hz, lH, phenyl), 7.07 (t, J=0.4Hz, 1H, phenyl), 7.97 (t, J=0.4Hz, 1H, phenyl)；ESI,m/
z:256。
Part 8:
Preparation example 9: the preparation of coordination compound 1
Weigh 0.13g (0.4mmol) ligand 1, add methanol 30mL, be heated to solution clarification, be slowly added dropwise containing 0.027g
(0.2mmol)AlCl3Methanol solution 20mL, stirring reaction 1h, regulate pH value of solution=6, have a large amount of white precipitate to generate immediately,
Filtered while hot, obtains light yellow solid；In the chloroformic solution of light yellow solid, slowly spread methanol, obtain yellow bulk crystals
0.1g, productivity 76%.
1HNMR(400MHz；CDCl3): 8.10-8.08 (d, 8H), 7.60-7.58 (d, 12H), 7.33-7.29 (t, 4H),
6.79-6.72(m,8H),4.07(s,12H),3.51(s,6H).Elementary analysis measured value (C66H50Al2N8O18Value of calculation, %):
C,60.92(61.11)；H,4.02(3.89)；N,8.42(8.64).ESI, m/z:617 [Al (C16H12N2O4)2]+, 648 [Al
(C16H12N2O4)2(CH3O)]+, 706 [Al2(C16H12N2O4)2(CH3O)2]+。
Preparation example 10: the preparation of coordination compound 2
In addition to using ethanol to replace methanol as solvent, prepare meat according to the method essentially identical with preparation example 9
Color solid；In the chloroformic solution of salmon coloured solid, slowly spread ethanol, obtain yellow bulk crystals 0.1g, productivity 78%.
1HNMR(400MHz；CDCl3): 8.04-8.02 (d, 8H), 7.69-7.52 (d, 12H), 7.32-7.26 (t, 4H),
6.76-6.73(m,8H),4.06(s,12H),3.52-3.48(q,4H),0.82-0.80(t,6H).Elementary analysis measured value
(C68H54Al2N8O18Value of calculation, %): C, 61.25 (61.63)；H,4.11(4.11)；N, 8.92 (8.46) .ESI, m/z:617
[Al(C16H12N2O4)2]+, 719 [Al2(C16H12N2O4)2(CH3CH2O)(CH2O)]+, 1016 [Al2(C16H12N2O4)3(CH3CH2O)
(CH2O)]+。
Preparation example 11: the preparation of coordination compound 3
In addition to using part 3 to replace ligand 1, prepare pink solid according to the method essentially identical with preparation example 9；
In the chloroformic solution of pink solid, slowly spread methanol, obtain light yellow bulk crystals 0.08g, productivity 78%.
1HNMR(400MHz；CDCl3): 8.16-8.15 (d, 3H), 7.88-7.87 (d, 2H), 7.60-7.52 (m, 22H),
7.43-7.39(t,9H),3.51(s,6H).Elementary analysis measured value (C58H42Al2N8O10Value of calculation, %): C, 65.45
(65.41)；H,3.93(3.98)；N,10.67(10.52).ESI, m/z:501 [Al (C14H10N2O2)2]+, 532 [Al
(C14H10N2O2)2(CH3O)]+, 590 [Al2(C14H10N2O2)2(CH3O)2]+。
Preparation example 12: the preparation of coordination compound 4
Except use part 3 replace ligand 1 and use ethanol replace methanol as solvent in addition to, according to preparation example 9 base
This identical method prepares light pink solid；In the chloroformic solution of light pink solid, slowly spread ethanol, obtain light yellow
Bulk crystals 0.08g, productivity 79%.
1HNMR(400MHz；CDCl3): 8.15-8.13 (d, 3H), 7.58-7.56 (d, 2H), 7.52-7.38 (m, 22H),
7.17-6.73(t,9H),3.51(q,4H),0.82-0.80(t,6H).Elementary analysis measured value (C60H46Al2N8O10Calculate
Value, %): C, 65.93 (66.13)；H,4.24(4.11)；N,10.25(10.54).ESI,m/z:501[Al(C14H10N2O2)2]+,
1094[Al(C14H10N2O2)4(CH3 CH2O)2]+。
Preparation example 13: the preparation of coordination compound 5
In addition to using part 4 to replace ligand 1, prepare orange solids according to the method essentially identical with preparation example 9；
In the chloroformic solution of orange solids, slowly spread methanol, obtain yellow bulk crystals 0.1g, productivity 80%.
1HNMR(400MHz；CDCl3): δ 8.08 (d, 8H), 7.93 (d, 8H), 7.85 (s, 4H), 7.82 (t, 4H), 7.49
(d,4H),7.40(s,4H),3.53(s,6H)。ESI,m/z:569[Al(C14H8ClN2O2)2]+。
Preparation example 14: the preparation of coordination compound 6
In addition to using part 7 to replace ligand 1, prepare orange solids according to the method essentially identical with preparation example 9；
In the chloroformic solution of orange solids, slowly spread methanol, obtain yellow bulk crystals 0.1g, productivity 81%.
1HNMR(400MHz；CDCl3): δ 8.02 (d, 8H), 7.93 (d, 8H), 7.91 (d, 4H), 7.65 (t, 4H), 7.48
(t,4H),7.39(d,4H),3.51(s,6H)。ESI,m/z:569[Al(C14H8ClN2O2)2]+。
Evaluation Example 1: ligand 1, the ultraviolet-visible detection of 2,3,4,5,7 and 8 pairs of fluorions or ultraviolet detection
Each with 10 by ligand 1,2,3,4,5,7 and 8-5～10-6Mol/L (such as 10-5Mol/L) concentration is dissolved in
CH2Cl2/CH3With obtained solution in CN (1:2, v/v) mixed solvent, then constantly dropping tetrabutyl fluorination in each solution
Ammonium, uses ultraviolet-visual spectrometer (UV-Vis) to measure ultraviolet-visible or the ultra-violet absorption spectrum of each solution simultaneously, thus obtains
Obtain the ultraviolet-visible shown in Fig. 1 to Fig. 7 or ultra-violet absorption spectrum.Arrow in Fig. 1 to Fig. 7 all represent along with in solution fluorine from
The increase of sub-content, the change of absorbance.
As shown in Figures 1 to 7, along with the increase of content of fluoride ion, the visible ultra-violet absorption spectrum of system is that regularity becomes
Change.Wherein, absworption peak (π-π * transition) intensity between 300～350nm declines, and occurs new suction between 350～450nm
Receive peak (n-π * transition), and gradually strengthen.Additionally, the color of solution is also become light yellow from colourless.This explanation ligand 1,2,3,
4,5,7 and 8 all have sensing and recognition reaction to fluorion, are a kind of well fluorion chemical sensors.This sensing is made
Detect with not only by instrument, and can be arrived by direct visual perception.
Evaluation Example 2: ligand 1, the fluoroscopic examination of 3,4,5 and 8 pairs of fluorions
Each with 10 by ligand 1,3,4,5 and 8-5～10-6Mol/L (such as 10-5Mol/L) concentration is dissolved in
CH2Cl2/CH3With obtained solution in CN (1:2, v/v) mixed solvent, then constantly dropping tetrabutyl fluorination in each solution
Ammonium, uses fluorescence spectrophotometer to measure the fluorescence spectrum of each solution simultaneously, thus obtains the fluorescence spectrum shown in Fig. 8 to Figure 12.
Arrow in Fig. 8 to Figure 12 all represents along with the increase of content of fluoride ion in solution, the change of emissive porwer.
As shown in Fig. 8 to Figure 12, along with the increase of content of fluoride ion, the fluorescence spectrum of system is regularity change.This says
Bright ligand 1,3,4,5 and 8 pairs of fluorions have sensing and recognition reaction, are a kind of well fluorion chemical sensors.Especially
It is part 4, is not dripping F-Time, solution substantially launches blue-fluorescence；Drip F-Afterwards, moving to right and green occurs in fluorescence spectrum
The emissive porwer in territory, zone significantly increases so that solution transmitting green fluorescence on the whole.This explanation part 4 can serve as a kind of high
The fluorion chemical sensor of effect.
Evaluation Example 3: part 2 is to the Selective recognition of fluorion and sensing
CH to the part 2 according to the present invention2Cl2/CH3CN (1:2, v/v) solution (concentration 10-5～10-6Mol/L, such as
10-5Mol/L) F is dripped in respectively-、Br-、I-、H2PO4 -And CH3COO-After (solution added is colourless), use ultraviolet
Visible spectrophotometer (UV-Vis) measures the uv-visible absorption spectra of each solution, thus obtains the ultraviolet-visible shown in Figure 13
Absorption spectrum.
As shown in figure 13, the CH of part 2 indicated by the solid line2Cl2/CH3CN solution and add Br-、I-、H2PO4 -With
CH3COO-After the uv-visible absorption spectra of solution the most mutually the same on profile, and add F-After the purple of solution
Outward-visible absorption spectra occurs in that notable change (shown in dotted line).Additionally, the CH of part 22Cl2/CH3CN solution and addition
Br-、I-、H2PO4 -And CH3COO-After solution be colourless, and add F-After solution be faint yellow.This illustrates part 2
Have high selectivity to fluorion, this high selectivity makes F-Detection do not disturbed by other ion.Can be by molten
The change of liquid color identifies fluorion quickly and easily, it is not necessary to by any analytical tool, and this is also the advantage of part of the present invention.
Evaluation Example 4: coordination compound 1 and the ultraviolet detection of 5 pairs of fluorions and coordination compound 1 to the Selective recognition of fluorion and
Sensing
Each with 10 by coordination compound 1 and 5-5～10-6Mol/L (such as 10-5Mol/L) concentration is dissolved in CH2Cl2/
CH3With obtained solution in CN (1:2, v/v) mixed solvent, in each solution, then constantly drip tetrabutyl ammonium fluoride, simultaneously
Use ultraviolet-visual spectrometer (UV-Vis) to measure the uv-visible absorption spectra of each solution, thus obtain Figure 15 and Figure 16
Shown uv-visible absorption spectra.Arrow in Figure 15 and Figure 16 all represents along with the increase of content of fluoride ion in solution, inhales
The change of luminosity.
As shown in Figure 15 and Figure 16, along with the increase of content of fluoride ion, the absorption spectrum of system is regularity change.Its
In, the absworption peak near 360nm declines, and the absworption peak of about 400nm strengthens, and this explanation coordination compound 1 and 5 pairs of fluorions have
Sensing and recognition reaction, be a kind of well fluorion chemical sensor.
CH to the coordination compound 1 according to the present invention2Cl2/CH3CN (1:2, v/v) solution is separately added into [Bu4N] R (R=
Br-,I-,F-,H2PO4 -And CH3COO-), then use ultraviolet-visual spectrometer (UV-Vis) to measure the ultraviolet-visible of each solution
Absorption spectrum, thus obtain the uv-visible absorption spectra shown in Figure 14.
As shown in figure 14, the CH of coordination compound 12Cl2/CH3CN solution and add Br-、I-And H2PO4 -After the purple of solution
Outer absorption spectrum is roughly the same on profile, and adds CH3COO-And F-After the ultra-violet absorption spectrum of solution occur in that notable change
Change.Add CH3COO-And F-After the change of solution be different.Along with CH3COO-Addition, the absworption peak at 360nm
It is gradually reduced, and new absworption peak occurs at 320nm and gradually strengthens.And along with F-Addition, the absworption peak at 360nm show
Write and decline, and new absworption peak occurs at 400nm and is gradually increased.Additionally, the CH of coordination compound 12Cl2/CH3CN solution and
Add Br-、I-、H2PO4 -And CH3COO-After solution be colourless, and add F-After solution be faint yellow.This explanation is joined
Compound 1 has high selectivity to fluorion, can be changed by solution colour and identify fluorion quickly and easily, it is not necessary to by appointing
What analytical tool.In addition, it is possible to by the change of absorption spectrum, to CH3COO-It is identified and detects.
Evaluation Example 5: coordination compound 1 and the fluoroscopic examination of 5 pairs of fluorions
Each concentration with 2 μMs in coordination compound 1 and 5 is dissolved in CH2Cl2/CH3With system in CN (1:2, v/v) mixed solvent
Obtain solution, in each solution, then constantly drip tetrabutyl ammonium fluoride, use fluorescence spectrophotometer to measure each solution simultaneously
Fluorescence spectrum, thus obtain the fluorescence spectrum shown in Figure 17 and Figure 18.Arrow in Figure 17 and Figure 18 all represents along with in solution
The increase of content of fluoride ion, the change of emissive porwer.
As shown in figs. 17 and 18, along with the increase of content of fluoride ion, the fluorescence spectrum of system is regularity change.This
Illustrate that coordination compound 1 and 5 pairs of fluorions have sensing and recognition reaction, be a kind of well fluorion chemical sensor.
About coordination compound 1, as shown in figure 17, along with F-Addition, its luminescence at 508nm is gradually lowered, and
Form a new emission peak at 374nm and gradually strengthen.In terms of outside glow color, do not dripping F-Time, solution is overall
Upper transmitting blue-green fluorescent；Drip F-Afterwards, blue-green fluorescent disappears, and solution almost no longer launches visible ray, but launches
Sightless 374nm ultraviolet.This explanation coordination compound 1 can serve as a kind of efficient fluoride ion fluorescent sensor.
About coordination compound 5, as shown in figure 18, along with F-Addition, its luminescence at 423nm is gradually lowered and weakens, and
At 508nm, form a new emission peak and gradually strengthen, weakening at the degree 423nm to be far smaller than of this enhancing.
In terms of outside glow color, do not dripping F-Time, solution shows strong blue-fluorescence；Drip F-Afterwards, fluorescence spectrum occurs
Move to right and the emissive porwer of green area significantly increases so that solution transmitting green fluorescence on the whole.This explanation coordination compound 5 is permissible
It is used as a kind of efficient fluoride ion fluorescent sensor.
Claims (9)
1. a coordination compound, it is characterised in that described coordination compound is represented by chemical formula 1:
Chemical formula 1:
In chemical formula 1, m is the integer of 0-5, and n is the integer of 0-4, R1And R3All independently selected from deuterium, tritium, halogen, cyano group,
Amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2-C6Ester group, substituted or unsubstituted C1-C6Alkyl and replacement
Or unsubstituted C1-C6The group of alkoxyl composition, R2Selected from C1-C6Alkyl,
Wherein, substituted C2-C6Ester group, substituted C1-C6Alkyl and substituted C1-C6Alkoxyl refers at least one hydrogen therein
Atom is by D atom, halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic group
Or its salt, phosphate or its salt, methyl, methoxyl group or-N (Q1)(Q2) substituted C2-C6Ester group, C1-C6Alkyl and C1-C6Alcoxyl
Base,
Q1And Q2All independently be hydrogen atom, D atom or methyl.
Coordination compound the most according to claim 1, it is characterised in that R1And R3All independently selected from deuterium, tritium, halogen, cyano group,
Amino, nitro, hydroxyl, carboxyl, substituted or unsubstituted C2-C4Ester group, substituted or unsubstituted C1-C4Alkyl and replacement
Or unsubstituted C1-C4The group of alkoxyl composition, R2Selected from C1-C4Alkyl,
Wherein, substituted C2-C4Ester group, substituted C1-C4Alkyl and substituted C1-C4Alkoxyl refers at least one hydrogen therein
Atom is by D atom, halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic group
Or its salt, phosphate or its salt, methyl, methoxyl group or-N (Q1)(Q2) substituted C2-C4Ester group, C1-C4Alkyl and C1-C4Alcoxyl
Base,
Q1And Q2All independently be hydrogen atom, D atom or methyl.
Coordination compound the most according to claim 1, it is characterised in that R1And R3All independently selected from-F ,-Cl ,-NH2、-
NO2、-OR4With-COOR4The group of composition, R2Selected from the group of methyl, ethyl and propyl group composition, wherein, R4It is C1-C4Alkyl.
Coordination compound the most according to claim 1, it is characterised in that described coordination compound is following coordination compound 1 to coordination compound 6
In any one:
Coordination compound 1:
Coordination compound 2:
Coordination compound 3:
Coordination compound 4:
Coordination compound 5:
Coordination compound 6:
The preparation method of coordination compound the most according to claim 1, it is characterised in that including: make part
With AlCl3With alcohol R2OH reaction obtains coordination compound according to claim 1.
Preparation method the most according to claim 5, it is characterised in that also include preparing part
Step, prepare partStep include:
MakeIntermediate 1 is obtained with ethanol synthesis；
Intermediate 1 and hydrazine reaction is made to obtain intermediate 2；
Make intermediate 2 withReaction obtains intermediate 3；
Make intermediate 3 and polyphosphoric acids react and obtain intermediate 4；
Make intermediate 4 react with Boron tribromide and obtain partIntermediate 1:
Intermediate 2:
Intermediate 3:
Intermediate 4:
7. a fluorine ion sensing device, it is characterised in that include coordination compound according to claim 1.
8. the method for fluorion in the detection solution of a non-diagnostic purpose, it is characterised in that described method includes:
Coordination compound according to claim 1 is joined in described solution；
Measure ultraviolet-visible or the ultra-violet absorption spectrum of described solution, or measure the fluorescence spectrum of described solution, or observe described
The color of solution；
Color change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution comes really
Whether fixed described solution contains fluorion.
9. the method for fluorion in the detection solution of a non-diagnostic purpose, it is characterised in that described method includes:
Coordination compound according to claim 1 is dissolved in a solvent, to obtain the first solution；
Second solution is gradually added in the first solution, to obtain mixed solution；
During being gradually added into the second solution, measure ultraviolet-visible or the ultra-violet absorption spectrum of mixed solution, or measure mixed
Close the fluorescence spectrum of solution, or observe the color of mixed solution；
Color change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or mixed solution comes really
Whether fixed second solution contains fluorion.
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