CN116144034A - Metal triangle supermolecule with near infrared fluorescence, preparation method and application thereof - Google Patents
Metal triangle supermolecule with near infrared fluorescence, preparation method and application thereof Download PDFInfo
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- CN116144034A CN116144034A CN202211504266.0A CN202211504266A CN116144034A CN 116144034 A CN116144034 A CN 116144034A CN 202211504266 A CN202211504266 A CN 202211504266A CN 116144034 A CN116144034 A CN 116144034A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 127
- 239000002184 metal Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000013110 organic ligand Substances 0.000 claims abstract description 58
- 238000003384 imaging method Methods 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 190
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 102
- 238000006243 chemical reaction Methods 0.000 claims description 94
- 150000001875 compounds Chemical class 0.000 claims description 77
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 13
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- 239000003054 catalyst Substances 0.000 claims description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 229940125898 compound 5 Drugs 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- AWJPULCSDFBFDR-UHFFFAOYSA-N 5-bromo-2-pyridin-2-ylpyridine Chemical compound N1=CC(Br)=CC=C1C1=CC=CC=N1 AWJPULCSDFBFDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 3
- 239000000110 cooling liquid Substances 0.000 claims description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- UXDYTCZNECXIEG-UHFFFAOYSA-N [N].C(C)N1CCOCC1 Chemical compound [N].C(C)N1CCOCC1 UXDYTCZNECXIEG-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention relates to the field of chemical synthesis, and discloses a metal triangle supermolecule with near infrared fluorescence, a preparation method and application thereof, wherein the supermolecule is a metal triangle supermolecule S1 with near infrared fluorescence and a metal triangle supermolecule S2 with near infrared fluorescence. The metal triangle supermolecule with near infrared fluorescence is formed by coordinating metal organic ligand L1 containing a plurality of terpyridyl, metal organic ligand L2 and transition metal ions according to a proportion, so that the metal triangle supermolecule S1 with near infrared fluorescence is formed, the metal organic ligand L1 and the transition metal ions are coordinated according to a proportion, the metal triangle supermolecule S2 with near infrared fluorescence is formed, the metal triangle supermolecule with near infrared fluorescence has near infrared fluorescence performance, near infrared luminescence is displayed in a biological optical window, and the characteristics of the metal triangle supermolecule with near infrared fluorescence enable the metal triangle supermolecule to be used for near infrared cell imaging probes.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a metal triangle supermolecule with near infrared fluorescence, a preparation method and application thereof.
Background
Supermolecular chemistry is an important area of modern science and is valued by many scientists. The self-assembly of the molecules driven by the metal coordination bonds has the characteristic of directional controllability, so that the self-assembly becomes an important direction of supermolecular chemistry research. Among the many organic ligands, terpyridine ligands are widely used in molecular self-assembly due to their advantage of promoting metal attachment stability. In recent years, through continuous researches of numerous scientists, a series of 2D and 3D supermolecules based on terpyridine ligands and having geometric aesthetic significance are reported successively, however, the simple attractive geometric structure cannot meet the research requirements of the scientists, and the scientists pay more attention to the potential application value. Scientists design and synthesize the supramolecular structure based on terpyridine ligands and explore the application of the supramolecular structure in adsorption, catalysis, degradation, drug transportation and the like, and development of new biological imaging technology and probes is also a research hotspot. In this regard, the photoexcitation states of the designed transition metal complexes are also very useful in optical imaging probes. It has been reported that a large number of Ru (II) complexes can image a variety of organelles and biomolecules. However, the emission wavelength of Ru (II) complexes is typically limited to the range of 600-660nm and will exhibit cytotoxicity, whereas light at wavelengths of 700-1000nm is most penetrating into cells and tissues and this spectral window is also associated with low autofluorescence and minimal phototoxicity. Therefore, how to obtain supermolecules with near infrared fluorescence for cell imaging has become a research hotspot, and we propose a preparation method and application of metal triangle supermolecules with near infrared fluorescence.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a metal triangle supermolecule with near infrared fluorescence, a preparation method and application thereof, so as to solve the problems.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions:
the metal triangle supermolecule with near infrared fluorescence is characterized by comprising a metal organic ligand L1 containing a plurality of terpyridines and a metal triangle supermolecule S1 with near infrared fluorescence, wherein the metal triangle supermolecule S1 with near infrared fluorescence is formed by coordination of a metal organic ligand L2 and an M ion source according to a proportion, and the molar ratio of the metal organic ligand L1 to the metal organic ligand L2 to the M ion source is 3:1:6;
the metal organic ligands L1 of the terpyridyl are coordinated with the M ion source in proportion to form a metal triangle supermolecule S2 with near infrared fluorescence, and the molar ratio of the metal organic ligands L1 to the M ion source is 1:1;
the M ion source is a soluble zinc source;
the structural formula of the metal triangle supermolecule S1 with near infrared fluorescence is shown as formula A:
the structural formula of the metal triangle supermolecule S2 with near infrared fluorescence is shown as a formula B.
The metal organic ligand L1 is shown as a formula 1, and the metal organic ligand L2 is shown as a formula 2;
os is metallic osmium and Ru is metallic ruthenium.
Preferably, the zinc source is at least one of zinc chloride, zinc nitrate, zinc acetate and zinc sulfate, and the zinc source can be provided with or without crystal water.
The preparation method of the metal triangle supermolecule with near infrared fluorescence comprises the following steps:
the first step: the metal organic ligand L1 is obtained by coupling reaction of a compound of a formula 3 and a compound of a formula 4, wherein the compound of the formula 3 is obtained by coordination reaction of a compound of a formula 5 and a compound of a formula 6, and the compound of the formula 5 is obtained by coordination reaction of a compound of a formula 7 and K 2 OsCl 6 The solvent in the coordination reaction process is glycol;
and a second step of: the metal organic ligand L2 is obtained by coupling reaction of a compound of formula 8 and a compound of formula 9, wherein the compound of formula 8 is obtained by coordination reaction of a compound of formula 10 and a compound of formula 11, and the compound of formula 10 and the compound of formula 11 are obtained by coordination reaction of a compound of formula 12 and RuCl 3 Obtained by reaction, the compound of formula 12 is prepared from a compound of formula 13 and Br 2 The compound of the formula 13 is obtained by coupling reaction of a compound of the formula 14 and a compound of the formula 9;
and a third step of: carrying out coordination reaction on an M ion source, a metal organic ligand L1 and a metal organic ligand L2 to obtain a metal triangle supermolecule S1 with a structure of a formula A and near infrared fluorescence;
carrying out coordination reaction on an M ion source and a metal organic ligand L1 to obtain a metal triangle supermolecule S2 with near infrared fluorescence;
the time of the coordination reaction is 10-12 h, the temperature of the coordination reaction is 70+/-5 ℃, the solvent of the coordination reaction is a mixed solvent of chloroform and methanol, and the mixing ratio of the chloroform to the methanol is 1:1.
Preferably, the coupling reaction is obtained by adopting tetra (triphenylphosphine) palladium for catalytic coupling, and the reaction system allows Xu Tianjia acid-binding agent, wherein the acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
Preferably, the solvent for the reaction between the compound of formula 8 and the compound of formula 9 in the second step is at least one of acetonitrile, chloroform, methanol and tetrahydrofuran, and the reaction temperature is reflux;
the solvent in the coordination reaction process of the compound of the formula 10 and the compound of the formula 11 is a mixed solvent of chloroform and methanol, the ratio of the mixed solvent is 1:1, N-ethylmorpholine is added in the reaction process, the temperature in the reaction process is reflux, and the reaction time can be adjusted based on the reaction monitoring result;
12 and RuCl 3 The coordinated reaction solvent is a mixed solvent of methanol and chloroform, the ratio of the mixed solvent is 1:1, N-ethylmorpholine is added in the reaction process, the temperature in the reaction process is reflux, and the reaction time can be adjusted based on the reaction monitoring result;
compounds of formula 13 and Br 2 The solvent for the reaction is 1, 2-dichloroethane, the temperature in the reaction process is reflux, and the reaction time can be adjusted based on the reaction monitoring result.
Preferred preparation method of the metal organic ligand L1 comprises the following steps:
the first step: 2, 2-bipyridine and K 2 OsCl 6 Adding into a stirred glycol solution, N 2 Refluxing overnight under protection, adding an equal volume of saturated sodium dithionite aqueous solution into the cooling liquid after the reaction is finished, and washing with water and diethyl ether after suction filtration to obtain a black solid, namely the compound 1;
and a second step of: adding compound 1 and equivalent 5-bromo-2, 2-bipyridine into a round-bottomed flask, adding ethylene glycol as a reaction solvent into the round-bottomed flask, quickly installing a nitrogen protection device prepared in advance, charging nitrogen, removing air in the device, refluxing overnight, cooling the reaction to room temperature after the reaction is finished, adding water and NH into the flask 4 PF 6 Ultrasonically stirring for 1 hour, then carrying out suction filtration, extracting the obtained solid by using dichloromethane and water, carrying out vacuum spin-drying on the dichloromethane, dissolving a trace amount of methanol, adding diethyl ether to precipitate the solution, and washing the solution by using diethyl ether after suction filtration, wherein the obtained product is black solid, namely the compound 2;
and a third step of: equivalent amounts of the compounds 2, 4'- (4-boronylphenyl) -2,2':6', 2' -terpyridine and 3eqK 2 CO 3 Adding the mixture into a 100mL round-bottom flask, adding a reaction solvent, wherein the reaction solvent is at least one of acetonitrile, chloroform, methanol and tetrahydrofuran, adding a catalyst tetra (triphenylphosphine) palladium, vacuumizing and replacing nitrogen for 2-3 times, carrying out reflux reaction for two days at 90 ℃, cooling the reaction to room temperature after the reaction is finished, dissolving the reaction product by using dichloromethane and methanol, and stirring the reaction product with neutral alumina to obtain black solid, namely the metal-organic ligand L1.
Preferably, the preparation method of the metal organic ligand L2 comprises the following steps:
the first step: sequentially adding a compound 3, 2.6eq of 4'- (4-boric acid phenyl) -2,2':6', 2' -terpyridine and sodium hydroxide into a 250mL single-neck round bottom flask, adding 100mL of tetrahydrofuran as a reaction solution, rapidly adding tetrakis (triphenylphosphine) palladium as a catalyst, repeatedly vacuumizing and introducing nitrogen for 2-3 times, heating to 90 ℃ for two days, cooling to room temperature after the reaction is finished, spinning a solvent, adding methanol, carrying out ultrasonic treatment and suction filtration, purifying the obtained crude product by using a recrystallization method of dichloromethane and methanol, and obtaining a compound 4 which is a white solid;
and a second step of: adding a compound 4 into a 250mL single-neck round-bottom flask, adding 100mL of 1, 2-dichloroethane, carrying out ultrasonic treatment for 10min until the compound is completely dissolved, then adding excessive bromine into a dropper, standing overnight at 90 ℃, cooling the reaction until the solution is dark red after the reaction is finished, quenching the excessive bromine with a saturated sodium hydroxide aqueous solution to make the solution alkaline, adding water for separating, extracting an inorganic phase with dichloromethane for 2-3 times, merging and spin-drying an organic phase, recrystallizing with dichloromethane and methanol, and drying to obtain a compound 5 white solid product;
and a third step of: ruCl of Compound 5 and 0.5eq 3 Adding into 250mL single-port bottle, adding methanol and chloroform at a ratio of 1:1, ultrasonic treating for 10min to dissolve the reactant completely, heating at 75deg.C for two hours, and drippingAdding 10 drops of N-ethylmorpholine, reacting at 75 ℃ overnight, dissolving the crude product by adding dichloromethane and methanol after the reaction is completed, spin-drying the solvent, loading the crude product into a column by adding neutral alumina, eluting by using dichloromethane and methanol as detergents, and obtaining a dark red solid, namely a compound 6;
fourth step: dissolving compound 5 in mixed solvent of chloroform and methanol, and adding 2.4eq RuCl 3 ·3H 2 O, reacting for 24 hours at 80 ℃, cooling to room temperature, collecting solid by pressure filtration, washing with methanol for several times, and drying in a vacuum drying oven to obtain brown solid product 7, namely compound 7;
fifth step: dissolving a compound 6 and a compound 7 of 1eq in a mixed solvent of chloroform and methanol, dropwise adding a plurality of drops of nitrogen ethyl morpholine as a catalyst, heating and refluxing for reacting for 48 hours, cooling to room temperature after the reaction is finished, distilling under reduced pressure to remove the solvent, adding dichloromethane and aluminum powder, mixing the dichloromethane and the methanol as a eluting agent, and distilling under reduced pressure to obtain a red powdery solid, namely a compound 8;
sixth step: adding compound 8 and 12eq of 4'- (4-boracic phenyl) -2,2':6', 2' -terpyridine and 16eq of potassium carbonate into a round bottom flask, adding a mixed solvent which is at least one of acetonitrile, chloroform, methanol and tetrahydrofuran, carrying out ultrasonic treatment until the solid is completely dissolved, adding 0.2eq of catalyst tetra (triphenylphosphine) palladium, heating and stirring under nitrogen protection, carrying out reflux reaction for 6 days, distilling under reduced pressure to remove the solvent after the reaction is finished, adding dichloromethane and aluminum powder into a sample stirring column, taking dichloromethane and methanol as leaching agents, and distilling under reduced pressure to remove the solvent to obtain red solid which is metal organic ligand L2.
Preferably, the time of the complexation reaction is not less than 8 hours.
Preferably, the preparation of the metal triangle supermolecule S1 with near infrared fluorescence comprises the following steps:
dissolving 3eq of metal organic ligand L1 and 1eq of metal organic ligand L2 in a mixed solvent, carrying out ultrasonic treatment for 10min, and dropwise adding Zn (NO 3 ) 2 ·6H 2 O10 mL of methanol solution, then placing the solution on a heating table at 75 ℃ and stirring overnight, and adding excessive NH into a coordination reaction system after the reaction is finished 4 PF 6 Precipitation is carried out on the saturated methanol solution of (2), and after solid-liquid separation, the metal triangle supermolecule S1 with near infrared fluorescence is obtained after washing;
the preparation of the metal triangle supermolecule S2 with near infrared fluorescence comprises the following steps:
dissolving 1eq of metal organic ligand L1 in a mixed solvent, carrying out ultrasonic treatment for 10min, and dropwise adding Zn (NO) into the solution after the metal organic ligand L1 is completely dissolved 3 ) 2 ·6H 2 O10 mL of methanol solution, then placing the solution on a heating table at 75 ℃ and stirring overnight, and adding excessive NH into a coordination reaction system after the reaction is finished 4 PF 6 And (3) precipitating the saturated methanol solution, and washing after solid-liquid separation to obtain the metal triangular supermolecule S2 with near infrared fluorescence.
The metal triangle supermolecule with near infrared fluorescence, specifically the metal triangle supermolecule S1 with near infrared fluorescence and the metal triangle supermolecule S2 with near infrared fluorescence, can be applied to a near infrared cell imaging fluorescent probe.
(III) beneficial effects
Compared with the prior art, the invention provides the metal triangle supermolecule with near infrared fluorescence, the preparation method and the application thereof, and has the following beneficial effects:
1. the preparation method and application of the metal triangle supermolecule with near infrared fluorescence, coordination reaction, control of the coordination ions, proportion, solvent, temperature and other conditions, are helpful for further improving morphology selectivity and further preparing triangle supermolecule with uniformity.
2. The preparation method and the application of the metal triangle supermolecule with near infrared fluorescence provide metal organic ligands L1 and L2 with brand new structures.
3. The preparation method and the application of the metal triangle supermolecule with near infrared fluorescence provide two brand new metal triangle supermolecules S1 and S2 with near infrared fluorescence, and the metal triangle supermolecule with near infrared fluorescence shows excellent fluorescence performance.
Drawings
FIG. 1 is a diagram of Compound 2 prepared in example 1 1 HNMR spectrogram;
FIG. 2 shows the metal-organic ligand L1 prepared in example 1 1 HNMR spectrogram;
FIG. 3 is a diagram of Compound 4 prepared in example 2 1 HNMR spectrogram;
FIG. 4 is a diagram of Compound 5 prepared in example 2 1 HNMR spectrogram;
FIG. 5 is a diagram of compound 6 prepared in example 1 1 HNMR spectrogram;
FIG. 6 is a diagram of compound 8 prepared in example 1 1 HNMR spectrogram;
FIG. 7 is a schematic diagram of the preparation of a metal-organic ligand L2 according to example 2 1 HNMR spectrogram;
FIG. 8 is a triangle-shaped metal organic supermolecule S1 with near infrared fluorescence prepared in example 3 1 HNMR spectrogram;
FIG. 9 is a triangle-shaped metal organic supermolecule S2 with near infrared fluorescence prepared in example 3 1 HNMR spectrogram;
FIG. 10 is an ESI-MS spectrum of a triangular metal-organic supermolecule S1 with near infrared fluorescence prepared in example 3;
FIG. 11 is an ESI-MS spectrum of a triangular metal-organic supermolecule S2 with near infrared fluorescence prepared in example 3;
FIG. 12 is an ESI-MS spectrum of compound 2 prepared in example 1;
FIG. 13 is an ESI-MS spectrum of a metal-organic ligand L1 prepared in example 1;
FIG. 14 is an ESI-MS spectrum of compound 6 prepared in example 2;
FIG. 15 is an ESI-MS spectrum of compound 8 prepared in example 2;
FIG. 16 is an ESI-MS spectrum of example 2 for the preparation of metal-organic ligand L2;
FIG. 17 is an ultraviolet-visible absorption spectrum of the triangular supermolecules S1, S2 prepared in example 4;
FIG. 18 is a graph showing fluorescence emission spectra of triangular supermolecules S1 and S2 prepared in example 5;
FIG. 19 is a near infrared cell imaging of the triangular supramolecules S1 prepared in example 6: (A) treating MDA-231 cells with 10 μg/ml S1; (B) MDA-231 cells were treated with 20. Mu.g/ml of S1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1 to 19, the following embodiments 1 to 6 are used to describe the technical solution of the present invention in detail:
example 1
The preparation method of the metal triangle supermolecule with near infrared fluorescence comprises the following steps:
synthesis of Metal organic ligand L1
S1: synthesis of Compound 1: 2, 2-dipyridine (200.0 mg,0.42 mmol) and K 2 OsCl 6 (129.8 mg,0.83 mmol) was added to a 100mL round bottom flask followed by 10mL ethylene glycol, N 2 Protection, reflux overnight. After the reaction was completed, an equal volume of saturated aqueous sodium dithionite solution was added to the cooling liquid, followed by suction filtration and washing with water and diethyl ether to obtain 173mg of a black solid with a yield of 73%.
S2: synthesis of Compound 2: compound 1 (50 mg,0.087 mmol) and 5-bromo-2, 2-bipyridine (27.4 mg,0.087 mmol) were added to a 100mL round-bottomed flask, 15mL ethylene glycol was added to the round-bottomed flask, a nitrogen blanket was quickly installed, nitrogen was purged from the blanket, and reflux was continued overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and water and NH were added to the flask 4 PF 6 Ultrasonic treatment, stirring for 1 hour, suction filtration, extraction of the obtained solid with dichloromethane and water, repeated extraction of the aqueous phase for 3-4 times, vacuum spin drying of the dichloromethane, dissolution of a trace amount of methanol, addition of diethyl ether to precipitate the solid, suction filtration and diethyl ether washing to obtain 83mg of black solid with a yield of 86%. 1 H NMR(400MHz,Acetonitrile-d3)δ8.70(d,J＝1.8Hz,2H,H a ),8.47(d,J＝8.2Hz,5H,H g ),7.91-7.84(m,6H,H f ),7.64(d,J＝5.7Hz,2H,H c ),7.57(d,J＝5.8Hz,2H,H d ),7.47(d,J＝2.4Hz,5H,H b ),7.35-7.29(m,6H,H e ).ESI-MS(1106.52calcd.For C 30 H 22 Br 2 N 6 Os with PF 6 - ):m/z 408.99[M-2PF 6 ˉ] 2+ (calcd m/z:408.99).
S3: synthesis of metal organic ligand L1: compound 2 (50 mg,0.061 mmol), 4'- (4-boronylphenyl) -2,2':6', 2' -terpyridine (169.8 mg,0.612 mmol) and K 2 CO 3 (50.8 mg,0.367 mmol) was added to a 250mL round bottom flask, to which was added 120mL acetonitrile, 12mL methanol and 12mL water as reaction solvents, and finally tetrakis (triphenylphosphine) palladium (106 mg, 92. Mu. Mol) as catalyst was added. And then repeatedly vacuumizing and replacing nitrogen for 2-3 times, wherein the reaction system is in a nitrogen atmosphere, and carrying out reflux reaction for two days at 90 ℃. After the reaction is completed, the reaction is cooled to room temperature, dissolved by methylene dichloride and methanol, mixed with neutral alumina powder, passed through a column, dissolved by methanol after spin-drying, dissolved by NH 4 PF 6 Suction filtering the precipitate to obtain28mg of red solid was obtained in 33% yield. 1 H NMR(400MHz,Acetonitrile-d3)δ9.23-9.21(m,2H,H a ),8.92(s,4H,Tpy-H 3’,5’ ),8.77-8.73(m,8H,Tpy-H 6,6” ,H g ),8.56(dt,J＝8.1,1.2Hz,4H,Tpy-H 3,3” ),8.03(td,J＝7.7,1.9Hz,5H,Tpy-H 4,4” ),7.97-7.92(m,5H,H f ),7.88(dd,J＝6.0,0.6Hz,2H,H c ),7.83-7.81(m,2H,H d ),7.77(dd,J＝6.0,2.0Hz,2H,H d ),7.73(ddd,J＝5.6,1.4,0.7Hz,2H,H b ),7.51(ddd,J＝7.5,4.7,1.3Hz,4H,Tpy-H 5,5” ),7.42-7.37(m,4H,H e ).ESI-MS(1411.24calcd.For C 60 H 42 N 12 Os with PF 6 - ):m/z 562.16[M–2PF 6 - ] 2+ (calcd m/z:562.16)。
Example 2
The preparation method of the metal triangular supermolecule with near infrared fluorescence provided in the embodiment is basically the same as that in the embodiment 1, except that the preparation method comprises the following steps:
synthesis of Metal organic ligand L2
S1: synthesis of Compound 4: to a 250mL single neck round bottom flask was added, in order, compound 3 (2 g,6.76 mmol), 4'- (4-boronylphenyl) -2,2':6', 2' -terpyridine (5.25 g,14,8 mmol), aqueous sodium hydroxide (1 mol/L,15 mL), and 150mL tetrahydrofuran as a reaction solution. Tetra (triphenylphosphine) palladium (780 mg,0.68 mmol) was rapidly added as catalyst, and the reaction was repeated with repeated vacuum and nitrogen introduction 2-3 times and heating to 90 ℃ for two days. After the reaction is finished, cooling to room temperature, spin-drying the solvent, adding methanol, performing ultrasonic treatment and suction filtration, and purifying the obtained crude product by using dichloromethane and methanol by using a recrystallization method. 3.5g of a white solid was obtained in 68% yield.
S2: synthesis of Compound 5: in a 250mL single neck round bottom flask was added compound 5 (2 g,2.5 mmol), 100mL 1, 2-dichloroethane was added and sonicated for 10 minutes until it was completely dissolved, then excess bromine (10 g,63 mmol) was added dropwise and at 90℃overnight. After the reaction was completed, the reaction was cooled to a dark red color, and the excess bromine was quenched with saturated aqueous sodium hydroxide solution and made alkaline. Then water is added for separating, the inorganic phase is extracted for 2-3 times by using methylene dichloride, the organic phases are combined and dried by spinning, and the mixture is recrystallized by using methylene dichloride and methanol, and 1.8g of white solid product is obtained after drying, and the yield is 75%. 1 H NMR(400MHz,Chloroform-d)δ8.67(s,4H,Tpy-H 3’,5’ ),8.65(d,4H,J＝4.7Hz,Tpy-H 6,6” ),8.60(d,4H,J＝7.9Hz,Tpy-H 3,3” ),7.85-7.80(m,4H,Tpy-H 4,4” ),7.78-7.75(d,4H,PH-H g ),7.31-7.27(m,4H,Tpy-H 5,5” ),7.18(d,4H,J＝8.2Hz,PH-H h ),4.04(s,7H,H -OMe ).
S3: synthesis of Compound 6 (200 mg,0.22 mmol) and RuCl 3 (16.5 mg,0.07 mmol) was added to a 250mL single-necked flask, 75mL of methanol and 75mL of chloroform were added, the reaction was completely dissolved by sonication for 10min, after heating at 75℃for two hours, 10 drops of N-ethylmorpholine were added dropwise, and the reaction was carried out overnight at 75 ℃. After the reaction is completed, the solution is red, after the solvent is dried by spin, dichloromethane and methanol are added to dissolve the crude product, neutral alumina is added for column packing, and dichloromethane and methanol are used as detergents for elution, thus obtaining a dark red product with 60mg and 40% yield. 1 H NMR(400MHz,DMSO-d6)δ9.42(s,4H,TpyA-H 3’,5’ ),9.04(d,4H,J＝8.2Hz,TpyA-H 3,3” ),8.70(d,4H,J＝4.1Hz,TpyB-H 6,6” ),8.67(s,4H,TpyB-H 3’,5’ ),8.63(dt,2H,J＝8.0,1.1Hz,TpyB-H 3,3” ),8.34(d,4H,J＝8.3Hz,PhA-H g ),8.01(td,4H,J＝7.8,1.7Hz,TpyB-H 4,4” ),7.95(t,4H,J＝7.5Hz,TpyB-H 4,4” ),7.87(d,J＝8.3Hz,4H,PhB-H g ),7.55-7.42(m,16H,TpyA-H 6,6” ,TpyB-H 5,5” ,PhA-H h ,PhB-H h ),7.15-7.11(m,4H,TpyA-H 5,5” ),4.01(d,12H,J＝2.8Hz,H a ,H b ).ESI-MS(1993.31calcd.For C 100 H 68 Br 4 C l2 N 12 O 4 Ru):m/z 1957.35[M-Cl - ] 1+ (calcd.m/z:1957.89),959.19[M-2Cl - ] 2+ (calcd.m/z:961.15).
S4: synthesis of Compound 7: in a 100mL single vial was added Compound 5 (200 mg,0.23 mmol), and RuCl 3 ·3H 2 O (125 mg,0.48 mmol), 50mL of ethanol was added as a reaction solvent, and after 10min of sonication, the reaction temperature was raised to 75℃for two days. Cooling to room temperature after the reaction is finished, carrying out suction filtration by using a filter membrane, adding the obtained solid into a single-mouth bottle, adding methanol, carrying out ultrasonic treatment for 10min, and carrying out suction filtration by using the filter membrane for 2-3 times, thus obtaining 115mg of dark brown solid with the yield of 90%.
S5: synthesis of Compound 8: compound 6 (50 mg,0.025 mmol) and compound 7 (34 mg,0.025 mmol) were added to a 250mL single-necked flask, 50mL chloroform and 50mL chloroform were added, after heating at 75deg.C for two hours, 10 drops of N-ethylmorpholine were added dropwise, and reacted at 75deg.C for two days. After the reaction was completed, the solvent was spin-dried and dissolved in dichloromethane and methanol, the mixture was stirred with neutral alumina and passed through a column, dichloromethane and methanol were eluted as a detergent, and after spin-drying the solvent, it was dried to obtain 65mg of a dark red solid with a yield of 75%. 1 H NMR(400MHz,DMSO-d6)δ9.52(s,12H,Tpy-H 3’,5’ ),9.31(d,12H,J＝8.2Hz,Tpy-H 3,3” ),8.24(d,12H,J＝7.9Hz,Ph-H g ),7.99(t,12H,J＝7.8Hz,TpyB-H 4 ,4” ),7.59(d,12H,J＝8.0Hz,Tpy-H h ),7.44(d,12H,J＝5.5Hz,Tpy-H 6,6” ),7.15(t,12H,J＝6.7Hz,Tpy-H 5,5” ),4.04(s,18H,H a ).ESI-MS(3249.92calcd.For C 150 H 102 Br 6 Cl 6 N 18 O 6 Ru 3 ):m/z 1588.66[M-2Cl - ] 2+ (calcd.m/z:1589.46),1047.12[M-3Cl - ] 3+ (calcd.m/z:1047.80)，776.60[M-4Cl - ] 4+ (calcd.m/z:776.98)，606.69[M-5Cl - ] 5+ (calcd.m/z:614.48).，506.08[M-6Cl - ] 6+ (calcd.m/z:506.15).
S6: synthesis of metal organic ligand L2: compound 8 (43.7 mg, 13.4. Mu. Mol), 4' - (4-boronylphenyl) -2,2':6',2 "-terpyridine
(170 mg,0.48 mmol) and K 2 CO 3 (60.0 mg,0.4 mmol) was added to a 250mL round bottom flask, to which was added 100mL acetonitrile, 10mL methanol and 10mL water as reaction solvents, and finally catalyst tetrakis (triphenylphosphine) palladium (40.0 mg, 34.7. Mu. Mol) was added. Then the operation of pumping vacuum and introducing nitrogen is repeated for 2-3 times, and then the reaction is carried out for 6 days at 90 ℃. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product obtained was dissolved with dichloromethane and methanol, and DMF was added thereto, and then water was added thereto to precipitate a solid, which was suction-filtered through a filter membrane, and the red solid obtained after suction-filtration was powdered with neutral alumina and passed through a column to obtain 39mg of red solid L5 in 53% yield. 1 H NMR(400MHz,DMSO-d6)δ9.22(s,12H,TpyA-H 3’,5’ ),8.90(d,12H,J＝8.2Hz,TpyA-H 3,3” ),8.75(s,12H,TpyB-H 3’,5’ ),8.70(d,12H,J＝4.5Hz,TpyB-H 6,6” ),8.65(d,12H,J＝8.0Hz,TpyB-H 3,3” ),8.10(d,12H,J＝7.8Hz,PhA-H g ),8.02(t,12H,J＝7.6Hz,TpyA-H 4,4” ),7.93(d,12H,J＝8.0Hz,PhB-H g ),7.77(d,12H,J＝8.7Hz,TpyB-H 4,4” ),7.56(d,12H,J＝7.8Hz,PhB-H h ),7.50-7.44(m,24H,TpyB-H 5,5” ,TpyA-H 6,6” ),7.31(d,12H,J＝5.3Hz,PhA-H h ),6.98(d,12H,J＝7.1Hz,TpyA-H 5,5” ),3.77(s,18H,H -OMe ).ESI-MS(6086.80calcd.For C 288 H 186 F 36 N 42 O 30 Ru 3 S 12 ):m/z 1748.88[M3NTF - ] 3+ (calcd.m/z:1748.79),1241.67[M-4NTF - ] 4+ (calcd.m/z:1241.56)，937.34[M-5NTF - ] 5+ (calcd.m/z:937.22)，734.46[M-6NTF - ] 6+ (calcd.m/z:734.32).
Example 3
The preparation method of the metal triangle supermolecule with near infrared fluorescence provided by the embodiment is basically the same as that of the embodiment 1 and 2, and is different in that the preparation method comprises the following steps:
synthesis of metal triangle supermolecule S1 with near infrared fluorescence:
synthesis of ruthenium metal triangle supermolecule S1 with near infrared fluorescence: ligand L1 (2.41 mg, 2.14. Mu. Mol) and ligand L2 (4.36 mg, 0.72. Mu. Mol) were added to a 100mL single-necked flask, followed by addition of 15mL of chloroform and 10mL of methanol, heating to completely dissolve the ligand, and then Zn (NO 3 ) 2 ·6H 2 A10 mL solution of O (1.28 mg, 4.28. Mu. Mol) in methanol was then placed on a heated plate and stirred overnight at 75 ℃. After the reaction is finished, NH is added into the mixture after the mixture is cooled to room temperature 4 PF 6 The salt converted anions and stirred for 4h until the exchange was complete. Filtering the solid with a filter membrane, washing with deionized water for 2-3 times, and removing excessive NH 4 PF 6 The salt is then washed with methanol for 2-3 times and dried in an oven to finally obtain a black-red solid. 1 H NMR(400MHz,Acetonitrile-d 3 )δ9.47(s,6H),9.18(s,12H),9.00(s,12H),8.80(d,J＝8.0Hz,14H),8.74(d,J＝6.7Hz,18H),8.61(s,15H),8.51(d,J＝8.5Hz,9H),8.21(d,J＝7.8Hz,15H),8.12(d,J＝7.8Hz,37H),8.05-7.98(m,27H),7.87-7.80(m,40H),7.77(s,18H),7.70(d,J＝8.2Hz,15H),7.54(d,J＝7.4Hz,11H),7.46(s,17H),7.34(d,J＝6.0Hz,31H),7.22(d,J＝.6Hz,8H),6.92(s,12H),3.93(s,18H).ESI-MS(11641.33calcd.For C 456 H 312 Zn 6 F 144 N 72 O 6 P 24 Os 3 Ru 3 with PF 6 - ):m/z 1796.45[M-6PF 6 ˉ] 6+ (calcd m/z:1796.20),m/z1519.38[M-7PF 6 ˉ] 7+ (calcd m/z:1519.03),1311.45[M-8PF 6 ˉ] 8+ (calcd m/z:1311.16),1149.39[M-9PF 6 ˉ] 9+ (calcd m/z:1149.48),1020.13[M-10PF 6 ˉ] 10+ (calcd m/z:1020.13),914.38[M-11PF 6 ˉ] 11+ (calcd m/z:914.30),826.01[M-12PF 6 ˉ] 12+ (calcd m/z:826.12),751.01[M-13PF 6 ˉ] 13+ (calcd m/z:750.50).
Synthesis of metal triangle supermolecule S2 with near infrared fluorescence
Synthesis of ruthenium metal triangle supermolecule S2 with near infrared fluorescence: ligand L1 (4.37 mg, 3.07. Mu. Mol) was added to a single-necked flask, followed by addition of chloroform (10 ml) and methanol (5 ml), ultrasonic dissolution, and dropwise addition of Zn (NO) 3 ) 2 ·6H 2 A solution of O (0.96 mg, 3.07. Mu. Mol) in 5mL of methanol was heated at 70℃overnight. Cooling to room temperature, adding NH 4 PF 6 Stirring for 4h, suction filtration and washing with water and methanol 2-3 times gave a black solid. 1 H NMR(400MHz,Acetonitrile-d3)δ9.39(d,J＝2.1Hz,2H),9.12(s,4H),8.77(d,J＝8.1Hz,4H),8.64(d,J＝8.3Hz,4H),8.19-8.12(m,6H),8.06-8.01(m,4H),7.98(dd,J＝6.1,1.9Hz,2H),7.87(d,J＝4.9Hz,4H),7.80(d,J＝5.8Hz,2H),7.49(ddd,J＝9.5,5.3,2.2Hz,4H),7.40(dd,J＝7.6,5.1Hz,4H).ESI-MS(5299.64calcd.For C 180 H 126 N 36 P 12 F 72 Os 3 Zn 3 with PF 6 - ):m/z 1181.76[M-4PF 6 ˉ] 4+ (calcd m/z:1180.87),m/z 916.38[M-5PF 6 ˉ] 5+ (calcd m/z:915.91),739.29[M-6PF 6 ˉ] 6+ (calcd m/z:739.26),613.08[M-7PF 6 ˉ] 7+ (calcd m/z:613.08),518.18[M-8PF 6 ˉ] 8+ (calcd m/z:518.45),444.59[M-9PF 6 ˉ] 9+ (calcd m/z:444.85).
Example 4
The metal triangle supermolecule with near infrared fluorescence and the application thereof provided by the embodiment comprise the following steps:
dissolving compound 2 (L), ligand L1 and triangular supermolecule in acetonitrile solution to obtain 2×10 -6 The solution of mol/L was subjected to ultraviolet-visible light test. The ultraviolet-visible spectrum is shown in fig. 17.
Example 5
The metal triangle supermolecule with near infrared fluorescence and the application thereof provided by the embodiment comprise the following steps:
dissolving compound 2 (L), ligand L1 and triangular supermolecule in acetonitrile solution to obtain 2×10 -5 And (3) carrying out fluorescence test on the mol/L solution. The fluorescence emission spectrum is shown in FIG. 18.
Example 6
The metal triangle supermolecule with near infrared fluorescence and the application thereof provided by the embodiment comprise the following steps:
MDA-231 cells were seeded into confocal microscope dishes and incubated for 18-24 hours. The medium was removed, fresh medium containing compound 2 (L) was added, and the cells were incubated at 37 ℃ for another 6 hours, and then washed with fresh PBS. The cells were observed with a Zeiss LSM 710NLO confocal microscope (63X oil) and the results are shown in FIG. 19.
The metal triangle supermolecule with near infrared fluorescence provided by the embodiment of the invention is formed by coordinating a metal organic ligand L1 containing a plurality of terpyridyl, a metal organic ligand L2 and transition metal ions in proportion, so that the metal triangle supermolecule S1 with near infrared fluorescence is formed, and the metal organic ligand L2 transition metal ions are coordinated in proportion, so that the metal triangle supermolecule S2 with near infrared fluorescence is formed, the metal triangle supermolecule with near infrared fluorescence has near infrared fluorescence performance, near infrared luminescence is displayed in a biological optical window, and the characteristics of the metal triangle supermolecule with near infrared fluorescence enable the metal triangle supermolecule to be used for a near infrared cell imaging probe.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The metal triangle supermolecule with near infrared fluorescence is characterized by comprising a metal organic ligand L1 containing a plurality of terpyridines and a metal triangle supermolecule S1 with near infrared fluorescence, wherein the metal triangle supermolecule S1 with near infrared fluorescence is formed by coordination of a metal organic ligand L2 and an M ion source according to a proportion, and the molar ratio of the metal organic ligand L1 to the metal organic ligand L2 to the M ion source is 3:1:6;
the metal organic ligand L1 containing a plurality of terpyridyl is coordinated with the M ion source in proportion to form a metal triangle supermolecule S2 with near infrared fluorescence, and the molar ratio of the metal organic ligand L1 to the M ion source is 1:1;
the M ion source is a soluble zinc source;
the structural formula of the metal triangle supermolecule S1 with near infrared fluorescence is shown as formula A:
the structural formula of the metal triangle supermolecule S2 with near infrared fluorescence is shown as a formula B.
The metal organic ligand L1 is shown as a formula 1, and the metal organic ligand L2 is shown as a formula 2;
os is metallic osmium and Ru is metallic ruthenium.
2. The metal triangular supermolecule with near infrared fluorescence according to claim 1, wherein the zinc source is at least one of zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, and the zinc source may be with or without water of crystallization.
3. The preparation method of the metal triangle supermolecule with near infrared fluorescence is characterized by comprising the following steps:
the first step: the metal organic ligand L1 is obtained by coupling reaction of a compound of a formula 3 and a compound of a formula 4, wherein the compound of the formula 3 is obtained by coordination reaction of a compound of a formula 5 and a compound of a formula 6, and the compound of the formula 5 is obtained by coordination reaction of a compound of a formula 7 and K 2 OsCl 6 The solvent in the coordination reaction process is glycol;
and a second step of: the metal organic ligand L2 is obtained by coupling reaction of a compound of formula 8 and a compound of formula 9, wherein the compound of formula 8 is obtained by coordination reaction of a compound of formula 10 and a compound of formula 11, and the compound of formula 10 and the compound of formula 11 are obtained by coordination reaction of a compound of formula 12 and RuCl 3 Obtained by reaction, the compound of formula 12 is prepared from a compound of formula 13 and Br 2 The compound of the formula 13 is obtained by coupling reaction of a compound of the formula 14 and a compound of the formula 9;
and a third step of: carrying out coordination reaction on an M ion source, a metal organic ligand L1 and a metal organic ligand L2 to obtain a metal triangle supermolecule S1 with a structure and near infrared fluorescence;
carrying out coordination reaction on an M ion source and a metal organic ligand L1 in the formula 1 to obtain a metal triangle supermolecule S2 with a structure and near infrared fluorescence;
the time of the coordination reaction is 10-12 h, the temperature of the coordination reaction is 70+/-5 ℃, the solvent of the coordination reaction is a mixed solvent of chloroform and methanol, and the mixing ratio of the chloroform to the methanol is 1:1.
4. The method for preparing a metal triangle supermolecule with near infrared fluorescence according to claim 3, wherein the method comprises the following steps: the coupling reaction is obtained by adopting tetra (triphenylphosphine) palladium for catalytic coupling, and the reaction system allows a Xu Tianjia acid-binding agent which is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
5. The method for preparing a metal triangle supermolecule with near infrared fluorescence according to claim 3, wherein the method comprises the following steps: the preparation method of the metal organic ligand L1 comprises the following steps:
the first step: 2, 2-bipyridine and K 2 OsCl 6 Adding into a stirred glycol solution, N 2 Refluxing overnight under protection, adding an equal volume of saturated sodium dithionite aqueous solution into the cooling liquid after the reaction is finished, and washing with water and diethyl ether after suction filtration to obtain a black solid, namely the compound 1;
and a second step of: adding compound 1 and equivalent 5-bromo-2, 2-bipyridine into a round-bottomed flask, adding ethylene glycol as a reaction solvent into the round-bottomed flask, quickly installing a nitrogen protection device prepared in advance, charging nitrogen, removing air in the device, refluxing overnight, cooling the reaction to room temperature after the reaction is finished, adding water and NH into the flask 4 PF 6 Ultrasonically stirring for 1 hour, then carrying out suction filtration, extracting the obtained solid by using dichloromethane and water, carrying out vacuum spin-drying on the dichloromethane, dissolving a trace amount of methanol, adding diethyl ether to precipitate the solution, and washing the solution by using diethyl ether after suction filtration, wherein the obtained product is black solid, namely the compound 2;
and a third step of: equivalent of Compounds 2, 4' - (4-boronic acid group)Phenyl) -2,2':6', 2' -terpyridine and 3eq K 2 CO 3 Adding the mixture into a 100mL round-bottom flask, adding a reaction solvent, wherein the reaction solvent is at least one of acetonitrile, chloroform, methanol and tetrahydrofuran, adding a catalyst tetra (triphenylphosphine) palladium, vacuumizing and replacing nitrogen for 2-3 times, carrying out reflux reaction for two days at 90 ℃, cooling the reaction to room temperature after the reaction is finished, dissolving the reaction product by using dichloromethane and methanol, and stirring the reaction product with neutral alumina to obtain black solid, namely the metal-organic ligand L1.
6. The method for preparing a metal triangle supermolecule with near infrared fluorescence according to claim 3, wherein the method comprises the following steps: the preparation method of the metal organic ligand L2 comprises the following steps:
the first step: sequentially adding a compound 3, 2.6eq of 4'- (4-boric acid phenyl) -2,2':6', 2' -terpyridine and sodium hydroxide into a 250mL single-neck round bottom flask, adding 100mL of tetrahydrofuran as a reaction solution, rapidly adding tetrakis (triphenylphosphine) palladium as a catalyst, repeatedly vacuumizing and introducing nitrogen for 2-3 times, heating to 90 ℃ for two days, cooling to room temperature after the reaction is finished, spinning a solvent, adding methanol, carrying out ultrasonic treatment and suction filtration, purifying the obtained crude product by using a recrystallization method of dichloromethane and methanol, and obtaining a compound 4 which is a white solid;
and a second step of: adding a compound 4 into a 250mL single-neck round-bottom flask, adding 100mL of 1, 2-dichloroethane, carrying out ultrasonic treatment for 10min until the compound is completely dissolved, then adding excessive bromine into a dropper, standing overnight at 90 ℃, cooling the reaction until the solution is dark red after the reaction is finished, quenching the excessive bromine with a saturated sodium hydroxide aqueous solution to make the solution alkaline, adding water for separating, extracting an inorganic phase with dichloromethane for 2-3 times, merging and spin-drying an organic phase, recrystallizing with dichloromethane and methanol, and drying to obtain a compound 5 white solid product;
and a third step of: ruCl of Compound 5 and 0.5eq 3 Adding into 250mL single-port bottle, adding methanol and chloroform at a ratio of 1:1, ultrasonic treating for 10min to dissolve the reactant completely, heating at 75deg.C for two hours, and dripping10 drops of N-ethylmorpholine and reacting at 75 ℃ overnight, wherein the solution is red after the reaction is completed, spin-drying the solvent, adding dichloromethane and methanol to dissolve the crude product, adding neutral alumina to column, eluting with dichloromethane and methanol as detergents to obtain dark red solid, namely compound 6;
fourth step: dissolving compound 5 in mixed solvent of chloroform and methanol, and adding 2.4eq RuCl 3 ·3H 2 O, reacting for 24 hours at 80 ℃, cooling to room temperature, collecting solid by pressure filtration, washing with methanol for several times, and drying in a vacuum drying oven to obtain brown solid product 7, namely compound 7;
fifth step: dissolving a compound 6 and a compound 7 of 1eq in a mixed solvent of chloroform and methanol, dropwise adding a plurality of drops of nitrogen ethyl morpholine as a catalyst, heating and refluxing for reacting for 48 hours, cooling to room temperature after the reaction is finished, distilling under reduced pressure to remove the solvent, adding dichloromethane and aluminum powder, mixing the dichloromethane and the methanol as a eluting agent, and distilling under reduced pressure to obtain a red powdery solid, namely a compound 8;
sixth step: adding compound 8 and 12eq of 4'- (4-boracic phenyl) -2,2':6', 2' -terpyridine and 16eq of potassium carbonate into a round bottom flask, adding a mixed solvent which is at least one of acetonitrile, chloroform, methanol and tetrahydrofuran, carrying out ultrasonic treatment until the solid is completely dissolved, adding 0.2eq of catalyst tetra (triphenylphosphine) palladium, heating and stirring under nitrogen protection, carrying out reflux reaction for 6 days, distilling under reduced pressure to remove the solvent after the reaction is finished, adding dichloromethane and aluminum powder into a sample stirring column, taking dichloromethane and methanol as leaching agents, and distilling under reduced pressure to remove the solvent to obtain red solid which is metal organic ligand L2.
7. The method for preparing a metal triangle supermolecule with near infrared fluorescence according to claim 3, wherein the method comprises the following steps: the time of the coordination reaction in the third step is not less than 8 hours.
8. The method for preparing a metal triangle supermolecule with near infrared fluorescence according to claim 3, wherein the method comprises the following steps: the preparation of the metal triangle supermolecule S1 with near infrared fluorescence comprises the following steps:
dissolving 3eq of metal organic ligand L1 and 1eq of metal organic ligand L2 in a mixed solvent, carrying out ultrasonic treatment for 10min, and dropwise adding Zn (NO 3 ) 2 ·6H 2 O10 mL of methanol solution, then placing the solution on a heating table at 75 ℃ and stirring overnight, and adding excessive NH into a coordination reaction system after the reaction is finished 4 PF 6 Precipitation is carried out on the saturated methanol solution of (2), and after solid-liquid separation, the metal triangle supermolecule S1 with near infrared fluorescence is obtained after washing;
the preparation of the metal triangle supermolecule S2 with near infrared fluorescence comprises the following steps:
dissolving 1eq of metal organic ligand L1 in a mixed solvent, carrying out ultrasonic treatment for 10min, and dropwise adding Zn (NO) into the solution after the metal organic ligand L1 is completely dissolved 3 ) 2 ·6H 2 O10 mL of methanol solution, then placing the solution on a heating table at 75 ℃ and stirring overnight, and adding excessive NH into a coordination reaction system after the reaction is finished 4 PF 6 And (3) precipitating the saturated methanol solution, and washing after solid-liquid separation to obtain the metal triangular supermolecule S2 with near infrared fluorescence.
9. The application of the metal triangle supermolecule with near infrared fluorescence is characterized in that the metal triangle supermolecule S1 with near infrared fluorescence and the metal triangle supermolecule S2 with near infrared fluorescence are applied to a near infrared cell imaging fluorescent probe.
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