CN104926843A - Azacyclocarbene trinuclear metallic silver complex and preparation method and application thereof - Google Patents

Azacyclocarbene trinuclear metallic silver complex and preparation method and application thereof Download PDF

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CN104926843A
CN104926843A CN201510239597.XA CN201510239597A CN104926843A CN 104926843 A CN104926843 A CN 104926843A CN 201510239597 A CN201510239597 A CN 201510239597A CN 104926843 A CN104926843 A CN 104926843A
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preparation
core
silver
title complex
heterocyclic carbine
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柳清湘
丁悦
蔡康晴
魏庆
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Tianjin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D235/08—Radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses an azacyclocarbene trinuclear silver (I) metallic complex taking diethylamine bridged bis-benzimidazolium salt as a precursor and a preparation method of the complex. The preparation method comprises the steps: under protection of inert gas, adding bis[2-[N-ethyl benzimidazolyl) ethyl] amine hexafluorophosphate (1) and a metallic compound in a molar ratio of (0.1-1mol): (0.1-1mol) into a reaction vessel; carrying out reaction on the mixture for 24 hours at a temperature of 40 DEG C by being dissolved by using a water-removing high purity organic solvent; filtering and naturally volatilizing the mixture to obtain the carbene metallic complex. The azacyclocarbene trinuclear silver (I) metallic complex taking diethylamine bridged bis-benzimidazolium salt as the precursor is mainly applied to the technical field of fluorescent recognition.

Description

N-heterocyclic carbine three core argent title complex and preparation method thereof and application
About the statement subsidizing research or exploitation
The present invention is state natural sciences fund (fund number is 21172172), Tianjin Natural Science Fund In The Light (fund number is 11JCZDJC22000), Tianjin innovation team of institution of higher education training plan (fund number is TD12-5038) and Tianjin Normal University's research for application and development fund (fund number: 52XK1202) carry out under subsidizing.
Technical field
The invention belongs to Organometallic Chemistry technical field, Synthesis and characterization is with two [2-(N-ethyl benzo imidazole base) ethyl] amine hexafluorophosphate 1as N-heterocyclic carbine three core silver (I) title complex [(L prepared by part 1ag 3] (PF 6) 3( 2).In addition, measure and describe part 1with 2fluorescence emission spectrum.
Background technology
The research recent two decades of transition metal complex has obtained considerable progress.Active organic reaction intermediate and metal form title complex thus are settled out, and can study the spectrum of Cabbeen, structure and reaction mechanism further.People start to contact coordination compound very early, and be mostly used as everyday use at that time, raw material is also obtained by natural substantially, such as sterilant blue stone and be used as dyestuff Prussian blue.The earliest 1798 are started to the research of title complex.French chemist t s ell prepares CoCl36NH3 with divalent cobalt, ammonium chloride and ammoniacal liquor first, and finds metal and Cl, the H such as chromium, nickel, copper, platinum 2o, CN, CO and C 2h 4also similar compound can be generated.1893, Swiss chemists Werner summarized the theory of forefathers, proposed a series of key concepts such as modern coordinate bond, ligancy and structure of coordination compound first, successfully explained the Effective Conductivity of a lot of title complex, isomery and magnetic.Since then, coordination chemistry has just had development in essence.Modern coordination chemistry no longer sticks to the donor and accepter relationship of electron pair, but to a great extent by means of the development of molecular orbital theory, the novel type title complex that begins one's study is as sandwich coordination compound and duster compound.
After since 1991, Arduengo first time, separation obtained stable free N-heterocycle carbine (NHC), the research of N-heterocyclic carbene metal title complex obtains at recent two decades and develops fast.By imidazole salts and benzoglioxaline salt as carbene precursor, polytype metal complexes can be synthesized.Research shows that N-heterocyclic carbene metal title complex is to warm, and water and air has satisfactory stability, is better than the metal complex catalysts of Phosphine ligands in many aspects.Therefore, they are widely used in catalyzed reaction.
Summary of the invention
The object of the present invention is to provide by the bis-benzimidazole salt of the diethylamide bridging N-heterocyclic carbine three core metal complexes as precursor, particularly by the bis-benzimidazole salt of the diethylamide bridging N-heterocyclic carbine three core silver complex as precursor.
The hydrogen spectrum and the carbon spectrum that the present invention relates to this type of N-heterocyclic carbine three core argent title complex are demarcated.
The present invention relate to again N-heterocyclic carbine three core argent title complex and preparation method thereof simultaneously.
The present invention propose by the bis-benzimidazole salt of diethylamide bridging as the typical N-heterocyclic carbine three core argent title complex of precursor be a kind of in normal conditions can the senior fluorescent material of stable existence, be expected to be applied in fluorescence chemical field.
For completing above-mentioned every goal of the invention, technical solution of the present invention is as follows:
There is the structure that N-heterocyclic carbine three core silver (I) metal complexes has following formula subrepresentation:
The preparation method of N-heterocyclic carbine three core silver (I) title complex of the present invention, is characterized in that:
Under protection of inert gas, by two [2-(N-ethyl benzo imidazole base) ethyl] amine hexafluorophosphate 1metallizing thing is that the ratio of 0.1-1mol:0.1-1mol joins in reaction vessels with mol ratio, after dissolving, reacts 24 hours at 40 DEG C of temperature, filters, naturally volatilize, obtain carbine metal title complex with the high-purity organic solvent dewatered.
Preparation method of the present invention, the preferred 1-ethyl benzo imidazole of wherein said substituted benzimidazole.
Preparation method of the present invention, wherein said substituted benzimidazole is ethyl benzo imidazole, n-propyl benzoglyoxaline; Described metallic compound is selected from the mixture of one or more of silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide.Be more preferably silver suboxide.
Preparation method of the present invention, wherein said organic solvent is selected from diethanolamine, thionyl chloride tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, N, the mixture of one or more in dinethylformamide, dimethyl sulfoxide (DMSO), be more preferably the mixing solutions of 1,2-ethylene dichloride and acetonitrile.
What be illustrated especially is as follows as the single crystal data of the N-heterocyclic carbine three core argent title complex of precursor by the bis-benzimidazole salt of diethylamide bridging:
The preparation method of the crystal of N-heterocyclic carbine three core argent title complex of the present invention, is characterized in that 0.5 mmol silver suboxide to join 0.3 mmol part 125 mL 1, in 2-ethylene dichloride and acetonitrile (v:v=2:1) solution, stir 24 hours under the condition of 40 DEG C, after reacting completely, solution is carried out suction filtration, then be concentrated to 5ml then to add ether and occur that white powder precipitates, obtain N-heterocyclic carbine three core argent title complex by suction filtration 2.
The present invention's preferred embodiment is example 1
The present invention further discloses the N-heterocyclic carbine three core argent title complex character in fluorescence direction of bis-benzimidazole salt as precursor of diethylamide bridging.
Experiment proves: N-heterocyclic carbine three core argent title complex, at 25 DEG C, prepares 1 × 10 respectively in acetonitrile solution -5mol/L concentration 1and 2measure its fluorescence spectrum after solution, the excitation wavelength of solution is 316nm, and emmission spectrum has emission peak at 397-448nm.See accompanying drawing 2.
The present invention propose by the bis-benzimidazole salt of diethylamide bridging as the N-heterocyclic carbine three core argent title complex of precursor be a kind of in normal conditions can the senior fluorescent material of stable existence, there is adjustable structure, prepare succinct, the obvious advantage of fluorescence photosensitive effect, be expected to be applied in fluorescence chemical field.
Fig. 1 is the crystalline structure figure containing silver complex (embodiment 1);
Fig. 2 is concentration is 1 × 10 -5mol/L 1and 2at 25 DEG C, the fluorescence spectrum figure in acetonitrile solution.
Embodiment
Below in conjunction with preferred embodiment, the present invention will be further described, be illustrated especially, the initial substance diethanolamine, thionyl chloride, halogenated alkane, salt of wormwood, anhydrous magnesium sulfate, ammonium hexafluorophosphate etc. of preparing the compounds of this invention all can commercially or easily be obtained by known method.The reagent prepared used by the compounds of this invention all derives from Tianjin Ke Wei Chemical Co., Ltd., and rank is analytical pure.
Need in addition to be illustrated: all experimental implementation use Schlenk technology, and solvent is through normal process purifying.All for the synthesis of being all analytical pure with the reagent analyzed, not through further process.Fusing point is measured by Boetius block apparatus. 1h and 13c{ 1h}NRM composes by mercury variable V x400 spectrophotometer record, surveying range: 400 MHz and 100 MHz.Chemical shift, δ, the TMS with reference to international standard measures.Fluorescence spectrum is by Cary Eclipse fluorescent spectrophotometer assay.
Embodiment 1
The preparation of two [2-(N-ethyl benzo imidazole base) ethyl] amine hexafluorophosphate ( 1):
In the chloroformic solution of 100 mL, add diethanolamine (5.000 g, 48.1 mmol), be slowly added drop-wise to thionyl chloride (34.334 g, 288.6 mmol) under room temperature, drip off about half an hour, react 6 hours at 60 DEG C.Gained mixture is poured into the NaOH(aqueous solution of 100ml) and stir 1 hour.Chloroform layer to be separated and dry with anhydrous MgSO 4.After removing chloroform, the Dichloroethyl amine obtained is yellow oil.Productive rate: 4.092 g(60%). 1H NMR (400MHz, DMSO-d 6): δ4.22 (t, J= 2.4 Hz, 8H, C H 2), 4.60 (s, 1H, N H). 13C NMR (100 MHz, DMSO-d 6): δ48.4 ( CH 2), 45.0 ( CH 2).
By 1-ethyl benzo imidazole (6.184 g of 100 mL, 42.3 mmol), Dichloroethyl amine (2.000 g, 14.1 mmol) and NaI (6.341 g, 42.3 mmol) THF solution return under stir seven days, there is yellow oil, wash with THF after filtration and product is dissolved in completely 100 mL methyl alcohol afterwards several times, by NH 4pF 6(6.985 g, 42.3 mmol) join in this methanol solution, stirred at ambient temperature three days, and white powder filters also uses a small amount of methanol wash, obtain two [2-(N-ethyl benzo imidazole base) ethyl] amine hexafluorophosphate ( 1).Productive rate: 7.372 g (80%), fusing point: 82-84 C. 1H NMR (400MHz, DMSO- d 6): δ1.55 (t, J= 7.8 Hz, 6H, C H 3), 2.93 (q, J= 6.4 Hz, 4H, C H 2), 3.95 (t, J= 6.4 Hz, 4H, C H 2), 4.55-4.62 (m, 5H, C H 2andN H), 7.72 (t, J= 2.4 Hz, 4H, C H 2), 8.12 (q, J= 1.3 Hz, 4H, C H 2), 9.64 (s, 2H, 2-bimi H). 13C NMR (100 MHz, DMSO- d 6): δ147.2 (Ph C), 146.2 (Ph C), 126.9 (Ph C), 126.4 (Ph C), 123.4 (Ph C), 122.7 (Ph C), 113.6 (Ph C), 46.1 ( CH 2), 44.7 ( CH 2),14.1 ( CH 3) (bimi = benzimidazole).
Embodiment 2
The preparation of N-heterocyclic carbine three core argent title complex:
Silver suboxide (0.116 g, 0.5 mmol) is joined part 1(0.200 g, 0.3 mmol) 1,2-ethylene dichloride/acetonitrile (25 mL, v:v=2:1) in solution, stir 24 hours under the condition of 40 DEG C, after reacting completely, solution is carried out suction filtration, be then concentrated to 5 mL and then add ether and occur that yellow powder precipitates, obtain title complex 1 by suction filtration.Productive rate: 0.146 g (30%), fusing point: 200-202 C.
1H NMR (400MHz, DMSO- d 6): δ1.47 (t, J= 1.0 Hz, 6H, C H 3), 3.19-3.21 (m, 4H, C H 2), 4.58-4.59 (m, 8H, C H 2), 7.50-7.52 (m, 4H, Ph H), 7.87-7.88 (m, 4H, Ph H). 13C NMR (100 MHz, DMSO- d 6): δ124.1 (Ph C), 124.0 (Ph C), 123.9 (Ph C), 111.99 (Ph C), 111.91 (Ph C), 111.8 (Ph C), 45.0 ( CH 2), 43.8 ( CH 2), 15.9 ( CH 3).
Its experiment flow is shown below:
Crystalline structure is shown in Figure of description 1:
The crystal parameters of embodiment 1 silver complex:
Crystal data and structure refinement parameter are included in supportive information.Bruker APEX II CCD diffractometer carries out, and experimental temperature is 296 (2) K, under 50kV and 20mA, with Mo-K α radiation (0.71073) operation, carries out data gathering and reduction with SMART and SAINT software, θscope be 1.8 < θ< 25o.Application SADABS program carries out empirical absorption rectification.Crystalline structure is solved by direct method, carries out complete matrix least-squares refinement with SHELXTL bag to whole non-hydrogen atom coordinate anisotropy thermal parameter.
Application example 1
The fluorescence pattern of N-heterocyclic carbine three core argent title complex is measured by the quartz cell of 1cm path length by Cary Eclipse spectrophotofluorometer.The acetonitrile used in titration be with hydrolith dehydration obtain except water-acetonitrile.The carrying out of titration is cuvette acceptor being put into 4 mL, and prepares 1 × 10 with microsyringe -5mol/L concentration 1and 2solution, at 25 DEG C, measure respectively 1and 2the fluorescence spectrum of solution, the excitation wavelength of solution is 316nm, and emmission spectrum has emission peak at 397-448nm.Data analysis uses Origin 8.0.See accompanying drawing 2.
In sum, content of the present invention is not limited in instances, and the knowledgeable people in same area can propose other example easily within technical director's thought of the present invention, but this example all comprises within the scope of the present invention.

Claims (7)

1. N-heterocyclic carbine three core silver (I) metal complexes has following structure:
2。
2. the preparation method of N-heterocyclic carbine three core silver (I) title complex described in claim 1, is characterized in that:
Under protection of inert gas, by two [2-(N-ethyl benzo imidazole base) ethyl] amine hexafluorophosphate ( 1) metallizing thing is that the ratio of 0.1-1mol:0.1-1mol joins in reaction vessels with mol ratio, after dissolving with the high-purity organic solvent dewatered, react 24 hours at 40 DEG C of temperature, filter, volatilization, obtains carbine metal title complex naturally.
3. preparation method according to claim 2, wherein said substituted benzimidazole is ethyl benzo imidazole, n-propyl benzoglyoxaline; Described metallic compound be selected from silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide, the mixture of one or more.
4. preparation method as claimed in claim 2, wherein said organic solvent is selected from diethanolamine, thionyl chloride tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1, the mixture of one or more in 2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, DMF, dimethyl sulfoxide (DMSO).
5. the crystal of N-heterocyclic carbine three core argent title complex described in claim 1, its crystal parameters is as follows:
。
6. the preparation method of the crystal of N-heterocyclic carbine three core argent title complex described in claim 5, is characterized in that 0.5 mmol silver suboxide to join 0.3 mmol part 125 mL 1, in 2-ethylene dichloride and acetonitrile (v:v=2:1) solution, stir 24 hours under the condition of 40 DEG C, after reacting completely, solution is carried out suction filtration, then be concentrated to 5ml then to add ether and occur that white powder precipitates, obtain N-heterocyclic carbine three core argent title complex by suction filtration.
7. the application of N-heterocyclic carbine three core argent complex crystal described in claim 5 in the senior fluorescent material of preparation.
CN201510239597.XA 2015-05-13 2015-05-13 Azacyclocarbene trinuclear metallic silver complex and preparation method and application thereof Pending CN104926843A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108947907A (en) * 2018-08-14 2018-12-07 天津师范大学 The cyclic annular nitrogen heterocyclic carbene silver complex and the preparation method and application thereof of azobenzene link

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333225A (en) * 2008-07-03 2008-12-31 天津师范大学 Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications
CN104230965A (en) * 2014-09-04 2014-12-24 天津师范大学 Preparation of cyclic silver complex and applications of cyclic silver complex in recognition of objects

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333225A (en) * 2008-07-03 2008-12-31 天津师范大学 Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications
CN104230965A (en) * 2014-09-04 2014-12-24 天津师范大学 Preparation of cyclic silver complex and applications of cyclic silver complex in recognition of objects

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QING WEI. ET AL: ""synthesis and structure of NHC silver(I) complex based on bisbenzimidazolium salt with diethylamine linker"", 《第十八届全国金属有机化学学术讨论会》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108947907A (en) * 2018-08-14 2018-12-07 天津师范大学 The cyclic annular nitrogen heterocyclic carbene silver complex and the preparation method and application thereof of azobenzene link
CN108947907B (en) * 2018-08-14 2021-06-25 天津师范大学 Azobenzene-linked cyclic N-heterocyclic carbene silver complex and preparation method and application thereof

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Application publication date: 20150923