CN101333225B - Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications - Google Patents
Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications Download PDFInfo
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Abstract
The invention discloses a cyclic n-heterocyclic double-carbene metal complex which is connected through alkyl chain, a preparation method and the application. The n-heterocyclic double-carbene of the invention is shown in the right formula, wherein, n is 1-6; R1 and R2 are independent or combined and refer to hydrogen or C1-C6 organic groups; the C1-C6 organic groups are selected among alkyl, branched chain alkyl, cycloalkyl, alkenyl, cyclic alkenyl, alkynyl, aryl, aryl alkyl, heterocyclic or alkoxy. The n-heterocyclic double-carbene metal complex of the invention is prepared through the reaction between substituted imidazole salt or benzimidazolium salt and metal compounds and is mainly used for the preparation of fluorescent materials. Experiments show that the n-heterocyclic double-carbene silver complex has stronger fluorescence emission intensity and more obvious fluorescence changes than the corresponding ligand, so that the n-heterocyclic double-carbene silver complex can be used to produce fluorescent materials and fluorescent molecular switch recognition system and applied to the fluorescent chemical field.
Description
About subsidizing the statement of research or exploitation
The present invention carries out under the subsidy of state natural sciences fund (fund number be 20672081) and Tianjin natural science fund (fund number be 07JCYBJC00300).
Technical field
The invention belongs to the Organometallic Chemistry technical field, relate to the synthetic of the N-heterocyclic carbine metal title complex that connects by alkyl chain, in particular ring-type nitrogen heterocyclic ring double carbine metal complex and preparation method thereof and application.
Background technology
After Cabbeen was determined as a kind of reaction intermediate, it was just playing the part of a key player in organic chemistry.Wherein N-heterocycle carbine metal complexes more and more was subject to people's attention in the last few years, and this field becomes one of vitochemical in recent years research focus.After people such as Fischer were incorporated into Cabbeen in the inorganic and Organometallic Chemistry in the sixties in last century, metal carbene had just obtained application widely in organic synthesis (as reagent and catalyzer) and polymer chemistry.The reactive behavior of N-heterocyclic carbine is very high, they can not only with most of transition metal with lower valency or high valence state complexing, and can with the complexing of part main group element.Have a lot of similaritys though N-heterocyclic carbene ligand and other have the part (as the phosphine part) of two lone electrons, it shows higher catalytic activity in a series of catalyzed reactions, can high-level efficiency catalyzed alkene replacement(metathesis)reaction as catalyzer 1.This class catalyzer is the reaction such as synthetic of hydrogen silicification reaction, linked reaction, hydrogenation of olefin reaction and the furan nucleus of catalyzed alkene smoothly.Because the metal carbene carbon bond is stable especially, make this class catalyzer have good thermostability and water tolerance, in catalytic process, do not need with excessive part, and can load on the resin as 2, make the homogeneous reaction immobilization.The N-heterocycle carbine is as catalyzer, and they do not destroy functional group, and just can react in room temperature.So people's prophesy nitrogen Cabbeen aspect catalysis has the trend that replaces the phosphine part.R group on the N-heterocycle carbine N atom has abundant variation, both can be superpolymer, also can be chiral radicals, can also be other coordinating group.These have indicated that all the N-heterocyclic ligand has vast potential for future development in catalytic applications.
The N-heterocycle carbine metal complexes that has synthesized a large amount of novel structures recently for over ten years.The physical and chemical performance of these title complexs has been done many researchs, and finding this class title complex except doing also has very high using value at aspects such as fluorescent material and fluorescence molecule switches the catalyzer.The fluorescence molecule switch is having some outstanding advantages to the analysis of object with in detecting, can embody the existence of object intuitively by the variation of fluorescence intensity, and it has high sensitivity, even individual molecule also can be detected.Believe that the N-heterocycle carbine can be applied along with the expansion of the deep and research range of research in growing field.
Summary of the invention
The present invention at first relates to nitrogen heterocyclic ring double carbine metal complex, particularly the nitrogen heterocyclic ring double carbine silver complex.
The present invention also relates to preparation method as the dication heterocyclic precursor of this type of organometallic complex of preparation.
The preparation method of dication heterocyclic precursor of the present invention refers to earlier with the synthetic corresponding alkyl benzimidazole of bromoalkane (or bromination Bian, anthracene methyl chloride etc.) and imidazoles (or benzoglyoxaline), benzyl imidazole, anthracene Methylimidazole etc.Generate two imidazoles (or benzoglyoxaline) halogenide with the saturated dihalide reaction again, carry out anion exchange reaction by ammonium hexafluorophosphate again and obtain corresponding hexafluorophosphate.
The invention further relates to the method that under protection of inert gas, prepares nitrogen heterocyclic ring double carbine metal complex, and measured and data characterization by x-ray diffractometer.
The present invention has further related to the application of nitrogen heterocyclic ring double carbine metal complex in the preparation fluorescent material.
For finishing above-mentioned every goal of the invention, the invention provides following technical scheme:
Nitrogen heterocyclic ring double carbine metal complex with following chemical general formula:
ML
q(Y)
m
Wherein, M is the metallic cation of silver;
L represents the two Cabbeens of the N-heterocycle that connects by alkyl chain;
Q is 1 or 2;
Y represents halogen anion or hexafluoro-phosphate radical negative ion;
M represents the number of negative ion, and its value is 1 or 2.
Nitrogen heterocyclic ring double carbine of the present invention is selected from the compound of being represented by following formula:
Wherein n is 2～6, R
1, R
2Be independently or combine and be hydrogen or C
1-C
6Organic radical, C
1-C
6Organic radical is selected from alkyl, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, alkoxyl group, aryl, arylalkyl or nitrogen heterocyclic ring.
C wherein
1-C
6Organic radical is selected from alkyl, for example C
2H
5, C
6H
13Branched-chain alkyl is isobutyl-, normal-butyl or neo-pentyl for example; Cycloalkyl is cyclopropane methyl or tetramethylene ethyl for example; Alkenyl is vinyl, propenyl or allyl group for example; Cycloalkenyl group is cyclopropenyl radical for example; Alkynyl is ethynyl for example; Alkoxyl group is oxyethyl group for example; Aryl is benzyl, menaphthyl, anthracene methyl for example; Nitrogen heterocyclic ring and substitutive derivative thereof, for example ethyl imidazol(e), normal-butyl imidazoles, benzyl imidazole, ethyl benzo imidazole, normal-butyl benzo imidazoles or 1-picolyl benzoglyoxaline etc.
Halogen is selected from fluorine, chlorine, bromine, iodine, preferred iodide ion.
The preferred nitrogen heterocyclic ring double carbine metal silver complex of the present invention is selected from the compound of following formula:
Wherein n is 2～6, and R is independently or combines and be hydrogen or C
1-C
6Organic radical, C
1-C
6Organic radical is selected from alkyl, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, arylalkyl, nitrogen heterocyclic ring (as pyridine ring) or alkoxyl group.C wherein
1-C
6Organic radical is selected from alkyl, for example C
2H
5, C
6H
13, branched-chain alkyl for example isobutyl-or neo-pentyl; Alkynyl is ethynyl for example; Alkoxyl group is oxyethyl group for example; Aryl is benzyl, menaphthyl or anthracene methyl for example.Nitrogen heterocyclic ring and substitutive derivative thereof, for example ethyl imidazol(e), anthracene Methylimidazole, benzyl imidazole, ethyl benzo imidazole, normal-butyl benzo imidazoles or 1-picolyl benzoglyoxaline etc.
Disclosed nitrogen heterocyclic ring double carbine metal complex is a relation arranged side by side among the present invention, does not have the branch of preferential primary and secondary.
The preparation method of nitrogen heterocyclic ring double carbine metal complex of the present invention comprises:
(1) C that in organic solvent, replaces with difference
1-C
6Haloalkyl chain and imidazoles or substituted benzimidazole reaction, products therefrom generate the two imidazoles or the bisbenzimidazole halogenide of alkyl bridged linkage again with the saturated dihalide reaction;
(2) in organic solvent, products therefrom and ammonium hexafluorophosphate are carried out anionresin, obtain the two imidazoles or the bisbenzimidazole hexafluorophosphate of corresponding alkyl bridged linkage;
(3) under protection of inert gas; the alkyl chain nitrogen heterocyclic ring double carbine hexafluorophosphate metallizing thing that step (2) is obtained is the ratio of 0.5-2～1-5mol with the mol ratio; preferred 1: the 1.1-1.5 ratio; join in the reaction vessels; after the high-purity organic solvent dissolving that dewaters, under 0 ℃～100 ℃ temperature, reacted 12～24 hours, filter; naturally volatilization obtains the carbine metal title complex.
Substituted imidazole of the present invention or substituted benzimidazole are preferably 1-ethyl imidazol(e), 1-benzyl imidazole, 1-anthracene Methylimidazole, 1-ethyl benzo imidazole, 1-picolyl benzoglyoxaline, 1-n-propyl benzo imidazoles, 1-sec-butyl benzo imidazoles or 1-normal-butyl benzo imidazoles.Wherein said C
2-C
6The haloalkyl chain is a glycol dibromide, 1, and 3-dibromopropane, 1,4-two butyl iodides, pentamethylene bromide or 1,6-two iodohexanes.
Metallic compound of the present invention is selected from wherein a kind of in silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide, cuprous halide, cuprous iodide, Red copper oxide, Quilonum Retard, nickel acetate, Cu Suan Palladium, zirconium white, yttrium oxide, the lanthanum trioxide.Preferred Silver monoacetate, silver carbonate, mercury halide, Red copper oxide, nickel acetate or Cu Suan Palladium.Be more preferably silver suboxide, silver carbonate, Glacial acetic acid mercury or cuprous iodide.
Organic solvent of the present invention is selected from tetrahydrofuran (THF), methylene dichloride, 1,2-ethylene dichloride, 1,4-dioxane, methyl alcohol, ethanol, acetone, ether, acetonitrile, nitroethane, N, the mixture of one or more in dinethylformamide, the dimethyl sulfoxide (DMSO).
Preferred acetone, methyl alcohol, methylene dichloride, 1,2-ethylene dichloride, N, dinethylformamide, 1,4-dioxane or dimethyl sulfoxide (DMSO) are more preferably tetrahydrofuran (THF) (THF), 1,4-dioxane, acetonitrile, methyl alcohol or methylene dichloride.Wherein mixed solvent is the mixing solutions of acetonitrile and methylene dichloride.
The present invention further discloses the feasibility of the two carbine metal title complexs of N-heterocycle as the raw material of preparation fluorescent material.Experimental results show that: the two carbine metal title complexs of N-heterocycle (typical example is the two carbene silver complexes of N-heterocycle) fluorescent emission intensity is stronger than corresponding part, and change in fluorescence is obvious.At 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 230nm condition in the solution, and the fluorogram of title complex (preparation example 15) and respective ligand (preparation example 14) is seen Fig. 4.Wherein-the expression title complex ... the fluorescence emission spectrogram of expression part.
The two carbine metal title complexs of the N-heterocycle that the present invention proposes are a kind of senior fluorescent materials that can stable existence under standard state, have Adjustable structure and put in order, prepare succinct, the tangible advantage of fluorescence photosensitive effect, can be used for making fluorescent material and fluorescence molecule switch identification system, be expected to be applied in the fluorescence chemical field.
Description of drawings
Fig. 1 is 1, the crystalline structure figure of 6-two [3-ethyl-1-benzoglyoxaline] hexane iodide;
Fig. 2 is for containing the white crystal structure iron of silver complex (preparation example 15);
Fig. 3 is for containing the pale yellow crystals structure iron of silver complex (preparation example 16);
Fig. 4 is at 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 230nm condition in the solution, the fluorogram of title complex (preparation example 15) and respective ligand (preparation example 14) thereof.Wherein-the expression title complex ... the fluorescence emission spectrogram of expression part.
Fig. 5 is the structural formula of nitrogen heterocyclic ring double carbine metal complex.
Table 1 is compound (preparation example 8) and the crystal parameters that contains silver complex (preparation example 15,16).
Table 1
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, what be illustrated especially is, initial substance trichloromethane, the pyridine, 1 of preparation The compounds of this invention, 3-dibromopropane, 1,4-butyleneglycol, 1,6-hexylene glycol, sulfur oxychloride, ethyl imidazol(e), benzyl imidazole, anthracene Methylimidazole, ethyl benzo imidazole, normal-butyl benzo imidazoles, ammonium hexafluorophosphate etc. all can have been bought or easily made by known method from the market.
The used reagent of preparation The compounds of this invention all derives from upright chemical industry company limited of Tianjin unit, and rank is an analytical pure.
What need in addition to be illustrated is: all experimental implementation utilization Schlenk technology, solvent is through the normal process purifying.To be useful on reagent synthetic and that analyze all be analytical pure, not through further handling.Fusing point is measured by the Boetius block apparatus.
1H and
13C{
1The H}NRM spectrum is by mercury variable V x300 spectrophotometer record, between measurement zone: 300MHz and 75MHz.Chemical shift, δ is with reference to the TMS mensuration of international standard.
This type of metal-organic hydrogen spectrum scaling method of the present invention is made solvent with deuterochloroform or deuterated dimethyl sulfoxide, with the dissolving of synthetic title complex, uses 300MH
ZNmr determination hydrogen spectrum.
Preparation example 1
1, add 1 in the 4-dioxane, (2.000g is 6.5mmol) with 1-ethyl imidazol(e) (1.360g for 4-two butyl iodides, 14.2mmol), stirred 5 days down at 90 ℃, separate out faint yellow precipitation, filter, use washing with acetone, obtain 1, the pale yellow powder of 4-two [3-ethyl-1-imidazoles] butane iodide.Productive rate: 2.949g (90.7%), Mp:126 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.44(t，J＝5.6，6H，CH
3)，1.88(m，4H，CH
2)，4.48(m，8H，CH
2)，7.38(s，1H，4or?5-imiH)，7.41(s，1H，4or?5-imiH)，9.48(s，2H，2-imiH)(imi＝imidazole)。
Its experiment flow is as shown below:
Preparation example 2
1, add 1 in the 4-dioxane, (2.000g is 6.5mmol) with 1-benzyl imidazole (2.250g for 4-two butyl iodides, 14.2mmol), stirred 5 days down at 90 ℃, separate out yellow mercury oxide, filter, with the ethyl acetate washing, obtain 1, the yellow powder of 4-two [3-Bian Ji-1-imidazoles] butane iodide.Productive rate: 2.583g (63.9%), Mp:150 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.76(m，4H，CH
2)，4.14(t，4H，CH
2)，5.42(s，4H，CH
2)，7.42(m，10H，PhH)，7.79(s，1H，4or?5-imiH)，7.82(s，1H，4or?5-imiH)，9.27(s，2H，2-imiH)(imi＝imidazole)。
Its experiment flow is as shown below:
Preparation example 3
1, add 1 in the 4-dioxane, 4-two butyl iodides (1.500g, 4.8mmol) and 1-picolyl benzoglyoxaline (2.218g, 10.6mmol), stirred 5 days down at 90 ℃, separate out yellow mercury oxide, filter, use washing with acetone, obtain 1, the yellow powder of 4-two [3-picolyl-1-benzoglyoxaline] butane iodide.Productive rate: 3.010g (85.3%), Mp:238-240 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ2.06(m，4H，CH
2)，4.69(t，4H，CH
2)，5.95(s，4H，CH
2)，7.37(m，2H，PhH)，7.68(m，6H，PhH?or?PyH)，7.96(m，4H，PhH?orPyH)，8.14(m，2H，PyH)，8.43(d，2H，PyH)，9.99(s，2H，2-benzimiH)(benzimi＝benzimidazole)。
Its experiment flow is as shown below:
Preparation example 4
1, add 1 in the 4-dioxane, (2.000g is 6.5mmol) with 1-anthracene Methylimidazole (3.694g for 4-two butyl iodides, 14.3mmol), stirred 5 days down at 90 ℃, separate out yellow mercury oxide, filter, with the ether washing, obtain 1, the yellow powder of 4-two [3-anthracene methyl isophthalic acid-imidazoles] butane iodide.Productive rate: 2.432g (45.6%), Mp:220-226 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.88(m，4H，CH
2)，4.05(t，4H，CH
2)，6.38(s，4H，CH
2)，7.66(m，10H，AnH?and?imiH)，8.20(d，4H，AnH)，8.35(d，4H，AnH)，8.83(d，4H，AnH)，9.33(s，2H，2-imiH)(imi＝imidazole，An＝Anthracene)。
Its experiment flow is as shown below:
Preparation example 5
1, add 1 in the 4-dioxane, (4.000g is 0.019mol) with 1-ethyl imidazol(e) (4.189g for the 3-dibromopropane, 0.042mol), stirred 5 days down at 90 ℃, separate out white precipitate, filter, use washing with acetone, obtain 1, the white powder of 3-two [3-ethyl-1-imidazoles] propane bromide.Productive rate: 6.653g (85.2%), Mp:136-138 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.46(t，J＝5.6，6H，CH
3)，1.77(m，2H，CH
2)，4.43(m，8H，CH
2)，7.40(s，1H，4or?5-imiH)，7.46(s，1H，4or?5-imiH)，9.55(s，2H，2-imiH)(imi＝imidazole)。
Its experiment flow is as shown below:
Preparation example 6
1, add 1 in the 4-dioxane, (4.000g is 0.019mol) with 1-Bian Ji imidazoles (6.613g for the 3-dibromopropane, 0.042mol), stirred 5 days down at 90 ℃, separate out white precipitate, filter, with the ether washing, obtain 1, the white powder of 3-two [3-Bian Ji-1-imidazoles] propane bromide.Productive rate: 5.418g (53.8%), Mp:196-198 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.74(m，2H，CH
2)，4.22(t，4H，CH
2)，5.39(s，4H，CH
2)，7.41(m，10H，PhH)，7.77(s，1H，4or?5-imiH)，7.80(s，1H，4or?5-imiH)，9.32(s，2H，2-imiH)(imi＝imidazole)。
Its experiment flow is as shown below:
Preparation example 7
1, add 1 in the 4-dioxane, the 3-dibromopropane (4.000g, 0.019mol) and 1-normal-butyl benzo imidazoles (7.284g, 0.042mol), stirred 5 days down at 90 ℃, separate out white precipitate, filter, use washing with acetone, obtain 1, the white powder of 3-two [3-normal-butyl-1-benzoglyoxaline] propane bromide.Productive rate: 7.612g (69.8%), Mp:196-198 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.41(t，J＝5.6，6H，CH
3)，1.50(m，10H，CH
2)，4.44(m，8H，CH
2)，7.63(m，4H，PhH)，8.01(d，J＝2.7，2H，PhH)，8.07(d，J＝2.7，2H，PhH)，9.66(s，2H，2-benzimiH)(benzimi＝benzimidazole)。
Its experiment flow is as shown below:
Preparation example 8
1, add 1 in the 4-dioxane, 6-two iodohexanes (4.000g, 0.012mol) and the 1-ethyl benzo imidazole (3.834g, 0.026mol), stirred 5 days down at 90 ℃, separate out white precipitate, filter, use washing with acetone, obtain 1, the white powder of 6-two [3-ethyl-1-benzoglyoxaline] hexane iodide.Productive rate: 4.746g (63.4%), Mp:292 ℃.
Under the protection of rare gas element (nitrogen); in acetonitrile (30mL), add 1,6-two [3-ethyl-1-benzoglyoxaline] hexane iodide (0.200g; 0.3mmol) and red mercury iodide (0.144g; 0.3mmol), this aaerosol solution refluxed 20 hours at 40 ℃, and filtrate is concentrated to 15mL; filter; standing over night obtains the white crystal of different anions part, and this compound is stable under air and moist condition.Mp：184℃。
1H?NMR(300MH
Z，DMSO-d
6)：δ1.36(m，4H，CH
2)，1.51(t，J＝5.7，6H，CH
3)，1.87(m，4H，CH
2)，4.47(m，8H，CH
2)，7.66(m，4H，PhH)，8.06(m，4H，PhH)，9.75(s，2H，2-benzimiH)(benzimi＝benzimidazole)。
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 1.
Preparation example 9
With 1, (3.000g, (2.140g, methyl alcohol 13.1mmol) (100mL) solution mixes 4-two [3-ethyl-1-imidazoles] butane iodide, at room temperature stirs 24h, separates out white powder for (100mL) solution of methyl alcohol 6.0mmol) and ammonium hexafluorophosphate.Filter, solid is washed with methyl alcohol, obtains 1, the white powder of 4-two [3-ethyl-1-imidazoles] butane hexafluorophosphate.Productive rate: 2.080g (64.68%), Mp:118 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.46(t，J＝5.6，6H，CH
3)，1.91(m，4H，CH
2)，4.54(m，8H，CH
2)，7.42(s，1H，4or?5-imiH)，7.48(s，1H，4or?5-imiH)，9.49(s，2H，2-imiH)(imi＝imidazole)。
Its experiment flow is as shown below:
Preparation example 10
In methyl alcohol (100mL), add 1, and 4-two [3-Bian Ji-1-imidazoles] butane iodide (3.500g, 5.6mmol), under stirring at room, add ammonium hexafluorophosphate (2.000g, 12.3mmol) methyl alcohol (100mL) solution, at room temperature stir 24h, separate out white precipitate.Filter, solid is washed with methyl alcohol, obtains ligand 1, the white powder of 4-two [3-Bian Ji-1-imidazoles] butane iodide hexafluorophosphate.Productive rate: 2.430g (65.7%), Mp:140-142 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.74(m，4H，CH
2)，4.11(t，4H，CH
2)，5.45(s，4H，CH
2)，7.40(m，10H，PhH)，7.81(s，1H，4?or?5-imiH)，7.85(s，1H，4or?5-imiH)，9.30(s，2H，2-imiH)(imi＝imidazole)。
Its schema is as follows:
Preparation example 11
With 1, (2.340g, (1.020g, methyl alcohol 6.2mmol) (100mL) solution mixes 4-two [3-anthracene methyl isophthalic acid-imidazoles] butane iodide, at room temperature stirs 24h, separates out yellow powder for (100mL) solution of methyl alcohol 2.8mmol) and ammonium hexafluorophosphate.Filter, solid is washed with methyl alcohol, obtains 1, the white powder of 4-two [3-anthracene methyl isophthalic acid-imidazoles] butane hexafluorophosphate.Productive rate: 1.477g (77.8%), Mp:226 ℃.
1H?NMR(300MH
Z，DMSO-d
6)：δ1.89(m，4H，CH
2)，4.07(t，4H，CH
2)，6.35(s，4H，CH
2)，7.68(m，10H，AnH?and?imiH)，8.23(d，4H，AnH)，8.38(d，4H，AnH)，8.86(d，4H，AnH)，9.31(s，2H，2-imiH)(imi＝imidazole，An＝Anthracene)。
Its schema is as follows:
Preparation example 12
With 1, (4.000g, (3.640g, methyl alcohol 0.02mol) (100mL) solution mixes 3-two [3-ethyl-1-imidazoles] propane bromide, at room temperature stirs 24h, separates out white powder for (100mL) solution of methyl alcohol 0.01mmol) and ammonium hexafluorophosphate.Filter, solid is washed with methyl alcohol, obtains 1, the white powder of 3-two [3-ethyl-1-imidazoles] propane hexafluorophosphate.Productive rate: 4.160g (79.1%).Mp：159℃。
1H?NMR(300MHZ，DMSO-d
6)：δ1.48(t，J＝5.6，6H，CH
3)，4.45(m，8H，CH
2)，7.42(s，1H，4or?5-imiH)，7.49(s，1H，4or?5-imiH)，9.56(s，2H，2-imiH)(imi＝imidazole)。
Its schema is as follows:
Preparation example 13
With 1, (3.000g, (1.955g, methyl alcohol 12mmol) (100mL) solution mixes 3-two [3-normal-butyl-1-benzoglyoxaline] propane bromide, at room temperature stirs 24h, separates out white powder for (100mL) solution of methyl alcohol 5.5mmol) and ammonium hexafluorophosphate.Filter, solid is washed with methyl alcohol, obtains 1, the white powder of 3-two [3-normal-butyl-1-benzoglyoxaline] propane hexafluorophosphate.Productive rate: 3.000g (80.9%).Mp：208-210℃。
1H?NMR(300MH
Z，DMSO-d
6)：δ1.44(t，J＝5.6，6H，CH
3)，1.53(m，10H，CH
2)，4.46(m，8H，CH
2)，7.66(m，4H，PhH)，8.07(d，J＝2.4，2H，PhH)，8.10(d，J＝2.4，2H，PhH)，9.65(s，2H，2-benzimiH)(benzimi＝benzimidazole)。
Its schema is as follows:
Preparation example 14
With 1, (4.000g, (2.822g, methyl alcohol 17.3mmol) (100mL) solution mixes 3-two [3-Bian Ji-1-imidazoles] propane bromide, at room temperature stirs 24h, separates out white powder for (100mL) solution of methyl alcohol 7.9mmol) and ammonium hexafluorophosphate.Filter, solid is washed with methyl alcohol, obtains 1, the white powder of 3-two [3-Bian Ji-1-imidazoles] propane hexafluorophosphate.Productive rate: 4.000g (80.1%).Mp：159℃。
1H?NMR(300MHZ，DMSO-d
6)：δ1.75(m，2H，CH
2)，4.26(t，4H，CH
2)，5.42(s，4H，CH
2)，7.45(m，10H，PhH)，7.79(s，1H，4or5-imiH)，7.81(s，1H，4or?5-imiH)，9.36(s，2H，2-imiH)(imi＝imidazole)。
Its schema is as follows:
Preparation example 15
Under the protection of rare gas element (nitrogen); in methylene dichloride (30mL), add 1,3-two [3-Bian Ji-1-imidazoles] propane hexafluorophosphate (0.200g; 0.3mmol) and silver suboxide (0.073g; 0.3mmol), this aaerosol solution refluxed 18 hours at 40 ℃, and filtrate is concentrated to 15mL; filter; standing over night obtains the white crystal of title complex, and this title complex is stable under air and moist condition.Mp：239℃。
1H?NMR(300MH
Z，DMSO-d
6)：δ1.78(m，2H，CH
2)，4.32(t，4H，CH
2)，5.47(s，4H，CH
2)，7.53(m，10H，PhH)，7.75(s，1H，4or5-imiH)，7.84(s，1H，4or?5-imiH)(imi＝imidazole)。
Its schema is as follows:
Crystalline structure is seen Figure of description 2.
Preparation example 16
Under the protection of rare gas element (nitrogen); in acetonitrile (30mL), add 1; 3-two [3-normal-butyl-1-benzoglyoxaline] propane hexafluorophosphate (0.200g; 0.3mmol) and silver carbonate (0.089g, 0.3mmol), this aaerosol solution refluxed 24 hours at 40 ℃; be filled in the test tube; test tube is put in the ether spreads, obtain the pale yellow crystals of title complex, this title complex is stable under air and moist condition.Mp：286℃。
1H?NMR(300MH
Z，DMSO-d
6)：δ1.43(t，J＝5.6，12H，CH
3)，1.55(m，20H，CH
2)，4.50(m，16H，CH
2)，7.70(m，8H，PhH)，8.12(d，J＝2.4，4H，PhH)，8.17(d，J＝2.7，4H，PhH)。
Its schema is as follows:
Crystalline structure is seen Figure of description 3.
Application example 17
To prepare example 15 prepared complex crystals, be made into certain density dichloromethane solution (1 * 10
-5Mol/L).Test by fluorescent liquid: the part of the fluorescence emission spectrum strength ratio correspondence of title complex is stronger, and change in fluorescence is obvious.At 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 230nm condition in the solution, the fluorogram Figure of description 4. of title complex and respective ligand thereof (preparation example 14) wherein-the expression title complex ... the fluorescence emission spectrogram of expression part.
Crystal data and structure refinement parameter are included in the supportive information.Carry out on Bruker SMART 1000CCD diffractometer, experimental temperature is 293 (2) K, under 50kV and 20mA, with Mo-K α radiation
Operation is carried out data gathering and reduction with SMART and SAINT software, and the scope of θ is 1.8＜θ＜25 °.Use the SADABS program and carry out experience absorption rectification.Crystalline structure is solved by direct method, with the SHELXTL bag whole non-hydrogen atom coordinate anisotropy thermal parameters is carried out the complete matrix least-squares refinement.
In sum, among the embodiment that content of the present invention is not confined to, the knowledgeable people in the same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment comprises within the scope of the present invention.
Claims (3)
1. the nitrogen heterocyclic ring double carbine metal complex that has following chemical formula:
2. method for preparing the described nitrogen heterocyclic ring double carbine metal complex of claim 1; it is characterized in that: under the protection of inert nitrogen gas; in the 30mL methylene dichloride, add 0.200g1,3-two [3-Bian Ji-1-imidazoles] propane hexafluorophosphate and 0.073g silver suboxide; this aaerosol solution refluxed 18 hours at 40 ℃; filtrate is concentrated to 15mL, filters standing over night; obtain the white crystal of title complex, this title complex is stable under the condition of air and humidity.
3. the application of the described nitrogen heterocyclic ring double carbine metal complex of claim 1 in the preparation fluorescent material.
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| CN101851210A (en) * | 2010-05-26 | 2010-10-06 | 南京工业大学 | Terphenyl bridged bis-benzimidazole quaternary ammonium compound, and synthesis method and application thereof |
| CN102030714B (en) * | 2010-12-17 | 2013-06-26 | 西安医学院 | Method for preparing water soluble bis-benzimidazole salt |
| CN102206226B (en) * | 2011-04-14 | 2013-10-23 | 天津师范大学 | N-heterocyclic carbine metal complex connected with trimethyl benzene, and preparation method thereof |
| CN102442952B (en) * | 2011-11-07 | 2014-01-08 | 天津师范大学 | Cyclic N-heterocyclic carbene metal complex, and preparation method and application thereof |
| CN102584864B (en) * | 2012-01-12 | 2014-09-17 | 天津师范大学 | Azacyclo-carbene metal crown ether and application of azacyclo-carbene metal crown ether to identification of objects |
| CN102807591B (en) * | 2012-07-30 | 2014-09-17 | 天津师范大学 | Double benzimidazole ligand based metal complex and preparation method and application thereof |
| CN103242300B (en) * | 2013-04-15 | 2014-06-25 | 天津师范大学 | N-heterocyclic carbene metal complex based on quinoxaline as well as preparation method and application thereof |
| CN103497208B (en) * | 2013-09-30 | 2016-04-20 | 天津师范大学 | Based on Benzimidazole bidentate ligand metal complexes and preparation method thereof and purposes |
| CN103665009A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,4-di-(1-H-benzimidazolyl) butane-silver(I) complex and preparation method thereof |
| CN103665007B (en) * | 2013-11-22 | 2016-06-08 | 河南工程学院 | 1,1-bis-(1-H-benzimidazolyl) methane-Yin (I) coordination compound and preparation method |
| CN103724270A (en) * | 2013-12-11 | 2014-04-16 | 天津师范大学 | Alkyl chain chaining-based N-heterocyclic carbene metal complex as well as preparation method and application thereof |
| CN104230965B (en) * | 2014-09-04 | 2016-04-06 | 天津师范大学 | The preparation of ring-type silver complex and the application in identification object thereof |
| CN104926843A (en) * | 2015-05-13 | 2015-09-23 | 天津师范大学 | Azacyclocarbene trinuclear metallic silver complex and preparation method and application thereof |
| CN105311020B (en) * | 2015-11-25 | 2017-12-15 | 临沂大学 | A kind of bisbenzimidazole aminated compounds and preparation method thereof |
| CN105287522B (en) * | 2015-11-25 | 2017-12-15 | 临沂大学 | Purposes of the bisbenzimidazole aminated compounds in antimicrobial agents are prepared |
| CN105566358B (en) * | 2016-01-20 | 2017-12-05 | 天津师范大学 | Application of the cyclic N-heterocyclic carbene metal complex in aromatic selectivity identification |
| CN106117147B (en) * | 2016-06-24 | 2018-10-02 | 天津师范大学 | Miscellaneous tall and erect class compound of naphtho- and the preparation method and application thereof |
| CN109251320B (en) * | 2018-05-18 | 2021-07-16 | 东华大学 | Polyion liquid with ionic bond as framework and preparation method thereof |
| CN109053689B (en) * | 2018-07-30 | 2020-09-22 | 天津师范大学 | Tetrabenzimidazole salt compound and preparation method and application thereof |
| CN111821811B (en) * | 2019-04-19 | 2022-05-27 | 天津大学 | Dication ionic liquid containing ether bond and nitrogen heterocycle and having physical and chemical absorption effects and method for trapping sulfur dioxide |
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