CN109810130B - Rigid linear C60-fluoroboric fluorescent triplet-state photosensitized molecule and preparation method thereof - Google Patents
Rigid linear C60-fluoroboric fluorescent triplet-state photosensitized molecule and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 206010034972 Photosensitivity reaction Diseases 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- -1 fullerene pyrrole ring compound Chemical class 0.000 claims abstract description 13
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 8
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229940126214 compound 3 Drugs 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 6
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 5
- 229940125898 compound 5 Drugs 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000012265 solid product Substances 0.000 claims 1
- 239000003504 photosensitizing agent Substances 0.000 abstract description 17
- 230000002165 photosensitisation Effects 0.000 abstract description 15
- 208000017983 photosensitivity disease Diseases 0.000 abstract description 5
- 231100000434 photosensitization Toxicity 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000006053 organic reaction Methods 0.000 abstract description 3
- 238000002428 photodynamic therapy Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 8
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 125000000168 pyrrolyl group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-M 2-oxobutanoate Chemical compound CCC(=O)C([O-])=O TYEYBOSBBBHJIV-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Abstract
Rigid linear C60A-boron fluoride fluorescence triplet photosensitization molecule and a preparation method thereof, relating to the technical field of functional organic molecule design and synthesis. The fullerene pyrrole ring compound and the fluoroboric fluorescent molecule are connected together through a rigid phenylacetylene bridge group, and one end of the bridge bond is respectively connected with the N atom of the fullerene pyrrole ring structure and the meso position of the fluoroboric fluorescent molecule to form a C2A symmetric rigid linear molecule. Reacting 4-trimethylsilylethynyl aromatic aldehyde with pyrrole to generate 4-trimethylsilylethynyl substituted fluoroboric fluorescent molecule, deprotecting to generate 4-ethynyl substituted fluoroboric fluorescent molecule, coupling with iodoaniline, reacting with bromoacetic acid alkyl ester to generate fluoroboric fluorescent intermediate containing active methylene, and finally reacting with C60And alkyl glyoxylate can be prepared into C which can be applied to the fields of photocatalytic organic reaction, photovoltaic cells, photodynamic therapy and the like through Prato reaction60-fluoroboron fluorescent triplet photosensitizing molecules.
Description
Technical Field
The invention relates to the technical field of functional organic molecule design and synthesis, in particular to a rigid linear C60-fluoroboric fluorescent triplet photosensitized molecules and a preparation method thereof.
Background
Triplet photosensitizers have been recently studied because of their wide application in photovoltaic cells, photocatalytic organic reactions, photopolymerization, photodynamic therapy (PDT), and triplet-triplet annihilation up-conversion. Conventional triplet photosensitizers are primarily compounds containing heavy atoms such as: transition metal complexes, iodine and bromine containing compounds, and the like. Such triplet photosensitizing molecules rely primarily on heavy atoms for intersystem crossing, resulting in photosensitization effects and thus are difficult to further derivatize. The bottleneck in the development of new triplet photosensitizing molecules is the unpredictable nature of the intersystem crossing of organic compounds.
C60Has high intersystem crossing efficiency and high triplet state yield (close to 1), and C60No pollution to the environment, therefore C60Is an ideal spin conversion unit. But due to C60Absorption in the visible region is weak and therefore it is not an ideal triplet photosensitizing molecule by itself.
The fluoboron fluorescent molecule has better solubility, good light and heat stability, higher molar extinction coefficient, fluorescence quantum yield and the like, thereby being a better energy donor.
Researchers have linked BODIPY of different structures to C60The 2-position of pyrrole ring synthesizes triplet photosensitized molecule C1-C8 with strong absorption in visible light region [ Huang, D.; zhao, j.; wu, w.; yi, x; yang, P.; ma, j.asian j.org. chem.2012,1,264; huang, l.; cui, x.; therrien, B.; zhao, j.chem.eur.j.2013,19,17472; huang, l.; zhao, j.chem.commun.2013,49,3751; wu, w.; zhao, j.; sun, j.; gu s.j.org.chem.2012,77, 5305; huang, l.; yu, x.; wu, w.; zhao, j.org.lett.,2012,14,2594]The molecular structure is as follows:
wherein BODIPY is used as a light-capturing antenna and energy donor, spin conversion unit-C60The moiety acts as an energy acceptor. The molecules all show better triplet photosensitization properties, such as: c-1 and C-5 can be applied to energy up-conversion of triplet-triplet forbidden [ Huang, d.; zhao, j.; wu, w.; yi, x; yang, P.; ma, j.asian j.org.chem.2012,1, 264, 30; wu, w.; zhao, j.; sun, j.; gu s.j.org.chem.2012,77,5305](ii) a C-2, C-3 and C-4 can promote photocatalytic organic chemical reaction, and the catalytic efficiency is superior to that of Ru (bpy)3Cl2[Zhao,J.Chem.Eur.J.2013,19,17472；Huang,L.；Zhao,J.Chem.Commun.2013,49,3751；Wu,W.；Zhao,J.；Sun,J.；Guo S.J.Org.Chem. 2012,77,5305](ii) a C-6, C-7 and C-8 are better singlet oxygen sensitizers, wherein the photosensitization efficiency of C-6 is 20 times higher than that of the complex of Ir (III) [ Guo S.J.org.chem.2012,77,5305; huang, l.; yu, x.; wu, w.; zhao, j.org.lett.,2012,14,2594]。
However, in the above molecules, the fluoroboric fluorescent molecule is connected with the '2' position of the fullerene pyrrole ring and C through a specific group60Presenting a certain included angle. In the connection mode, the BODIPY is connected to C through a rigid bridge group60At the "N" position of the pyrrole ring to form C2vSymmetrical rigid line C60-fluoroboron fluorescent triplet photosensitizing molecules. Such BODIPY, carbon bridge and C60On one straight line, the energy or charge transfer is ensured to be completed on one straight line, the photophysical process of the system is simplified, and the influence of other factors on the photosensitization efficiency is also eliminated.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art triplet photosensitizing molecules, it is an object of the present invention to provide a rigid linear C60The preparation method of the-fluoroboron fluorescence triplet photosensitized molecule can overcome the defect of unstable cross-over property between other triplet photosensitized molecules and simplify the photophysical process of the system.
In order to realize the purpose, the invention adopts the following technical scheme:
rigid linear C60-a fluoroboric fluorescent triplet photosensitizing molecule having the general molecular structural formula:
in the general formula, R is selected from alkyl with 1-12 carbon atoms;
in the general formula R1And R2Selected from substituted aryl OR heterocyclic aryl, alkyl with 2-5 carbon atoms, H, Cl, Br, I, -OR3Or SR3Wherein R is3Selected from H, substituted aryl or heterocyclic aryl and alkyl with 2-6 carbon atoms;
in the general formula, Y is
Wherein Z is an alkynyl group having 2 or 4 carbon atoms.
In the above formula, the fluorine boron fluorescent molecule is connected to C through a rigid bridging group60At the "N" position of the pyrrole ring to form a ring having C2vSymmetrical rigid line C60-fluoroboron fluorescent triplet photosensitizing molecules.
Another object of the present invention is to provide a rigid linear C60The invention relates to a preparation method of a fluoroboric fluorescent triplet photosensitized molecule, which adopts the following technical scheme for realizing the purpose:
the preparation route is as follows:
the method sequentially comprises the following steps:
step a: 4-trimethyl silicon (TMS) ethynyl aromatic aldehyde 1 and 2, 4-substituted pyrrole 2 are subjected to condensation reaction under the catalysis of acid, then dichloro dicyano-p-benzoquinone (DDQ) is used as an oxidant, finally alkali is used for neutralization, and boron trifluoride ethyl ether (BF) is used3·OEt2) Fitting for mixingPreparing a TMS-protected fluoroboric fluorescent molecule 3; wherein the molar charge ratio is 1: 2: acid: DDQ: BF (BF) generator3·OEt20.8-1.2: 1.6-2.4: 0.16-0.24: 0.8-1.2: 40-60, the reaction temperature is room temperature, and the reaction time is 36-72 h;
step b: reacting a compound 3 with KOH in a methanol/dichloromethane system, removing TMS to prepare a product 4, wherein the molar ratio of the compound 3 to the KOH is 0.8-1.2: 4-6, the reaction temperature is room temperature, and the reaction time is 0.5-2 h;
step c: under the protection of inert gas, the compound 4 and p-iodoaniline are subjected to coupling reaction in toluene and triethylamine to prepare a product 5, and the catalyst and the ligand are respectively triphenylarsenic and Pd2(dba)3(ii) a Compound 4 and p-iodoaniline, triphenylarsenic and Pd2(dba)3The molar ratio of (a) to (b) is 0.8-1.2: 0.96-1.44: 0.4-0.6: 0.16-0.24, the reaction temperature is 60-120 ℃, and the reaction time is 24-72 hours;
step d: the compound 5 and bromoacetic acid alkyl ester are subjected to substitution reaction under the catalytic action of anhydrous potassium carbonate to prepare a product 6, wherein the molar ratio of the compound 5, the anhydrous potassium carbonate and the bromoacetic acid alkyl ester is 0.8-1.2: 1.2-2.0: 0.96-1.5, the reaction temperature is 100-120 ℃, and the reaction time is 10-24 h;
step e: compound 6, C60Prato reaction with alkyl glyoxylate to produce product C60-B, Compound 6, C60The molar ratio of the alkyl glyoxylate to the alkyl glyoxylate is 1.8-2.2: 0.8-1.2: 16-24 ℃, the reaction temperature is 140-160 ℃, and the reaction time is 3-5 h.
Rigid Linear form C as the invention60-further improvement of the preparation method of the fluoroboric fluorescent triplet photosensitizing molecule:
the step a specifically comprises the following operations: compound 1 was mixed with 1: 180-250 (g: mL) in anhydrous Tetrahydrofuran (THF), and adding compound 2; stirring the mixed solution at room temperature, and adding 2 drops of trifluoroacetic acid dropwise after violently introducing inert gas for 20-40 min; continuously reacting the reaction mixed solution for 12-24 hours at room temperature in an inert gas environment until the TLC plate shows that the compound 1 disappears; adding DDQ to the mixture in a proportion of 1: 14 to 20 (g: m)L) is dissolved in THF, and then is slowly dripped into the reaction mixed liquid; continuously stirring for 4-8 h, and transferring the reaction solution to an ice bath condition; 15-20 mL of triethylamine (Et) were slowly added through a constant pressure dropping funnel3N), stirring for 5-20 min, and slowly adding boron trifluoride diethyl etherate (BF)3·OEt2) (ii) a Continuously stirring the mixture at room temperature for 8-12 h, and stopping the reaction; repeatedly extracting the reaction solution with dichloromethane and water for three times, and drying the reaction solution overnight with anhydrous sodium sulfate; after spin-drying of the solvent, column chromatography was used to obtain product 3 as an orange solid.
The step b specifically comprises the following operations: compound 3 was mixed with 1: dissolving 12-20 (g: mL) in a mixed solution of dichloromethane/methanol (v/v ═ 3), adding KOH, and introducing an inert gas to react; after confirming complete disappearance of compound 3 by dot plate tracing, the solution was extracted with dichloromethane and water, and the organic phase was dried over anhydrous sodium sulfate, dried by spin drying, and separated by column chromatography to obtain product 4.
The step c specifically comprises the following operations: compound 4 was mixed with 1: dissolving 10-20 (g: mL) in a mixed solution of toluene/triethylamine (v/v ═ 3); adding p-iodoaniline, and introducing inert gas for 20-40 min; adding triphenylarsenic and Pd2(dba)3Continuously introducing gas, sealing the bottle mouth, adding a reaction bottle into the oil bath kettle, and continuing to react until the compound 4 basically disappears; after the reaction is finished, the solvent is removed by rotation, and the product 5 is obtained by column separation.
The step d specifically comprises the following operations: taking compound 5 as a mixture of 1: 1.5 to 2.5 (g: mL) in DMF, and then anhydrous K is added2CO3(ii) a Introducing argon gas to protect the reaction mixture for 20-40 min at room temperature, and then rapidly adding bromoacetic acid alkyl ester, namely BrCH2CO2R, continuously introducing argon for 5-10 min, and sealing the reaction bottle; and (3) placing the reaction mixture in an oil bath for reaction, performing thin-layer chromatography tracking until the raw material point basically disappears, removing DMF (dimethyl formamide) under reduced pressure, and then performing column separation on the mixture to obtain the compound 6.
The step e specifically comprises the following operations: c is to be60Mixing the raw materials in a ratio of 1: dissolving 50-55 (g: mL) in o-dichlorobenzene, and adding a compound 6; introducing argon to protect 20-30 percent of the reaction mixture at room temperaturemin, then adding alkyl glyoxylate namely HCOCO2Adding the R, continuously introducing argon for 10-20 min, and putting the reaction mixture into a preheated oil bath for reaction; stopping the reaction when the amount of the fullerene is 30-40 percent; then carrying out reduced pressure distillation to remove the o-dichlorobenzene in the reaction system; dissolving the reaction mixture with carbon disulfide, separating by column chromatography, eluting with carbon disulfide, and removing unreacted C60Then changing to a high-polarity eluting agent to obtain a product C60-B。
The invention provides a rigid linear C60-a fluoroboron fluorescent triplet photosensitizing molecule, wherein the fullerene pyrrole ring compound and the fluoroboron fluorescent molecule in the general structural formula are connected together through a rigid phenylacetylene bridge group, and one end of the bridge bond is respectively connected to the N atom of the fullerene pyrrole ring structure and the meso position of the fluoroboron fluorescent molecule to form a C2A symmetric rigid linear molecule. Compared with the prior art, the invention has the beneficial effects that:
1) the invention reasonably designs the boron fluoride fluorescent light with strong absorption in a visible region to pass through the rigid bridge group and the spin conversion unit C60The N sites of the pyrrole rings are connected together to form a rigid linear triplet photosensitized molecule with stable intersystem crossing property, so that the defect of unstable intersystem crossing property of other triplet photosensitized molecules is overcome, and the photophysical process of the system can be simplified.
2) Rigid linear C prepared by the invention60The fluoroboric fluorescent triplet photosensitizing molecule can produce strong photosensitizing effect.
3) The rigid line type C of the present invention60The-fluoroboric fluorescent triplet photosensitizing molecule can be applied to triplet photosensitizers and can be applied to the fields of photocatalytic organic reaction, photovoltaic cells, photodynamic therapy (PDT), photopolymerization, fluorescent molecular probes, triplet-triplet annihilation up-conversion and the like.
Drawings
FIG. 1 is a rigid line C60-preparation of fluoroboro fluorescent triplet-photosensitized molecules scheme.
FIG. 2 is a rigid line form C prepared in the examples60-fluoroboric fluorescent triplet photosensitized molecule C60of-B11H NMR。
FIG. 3 is a rigid line form C of the embodiment60-fluoroboric fluorescent triplet photosensitized molecule C60of-B113C NMR。
FIG. 4 is a rigid line form C of the embodiment60-fluoroboric fluorescent triplet photosensitized molecule C60Mass spectrum of B1.
Detailed Description
This embodiment uses a rigid linear C60-fluoroboric fluorescent triplet photosensitized molecule C60The structure and the specific preparation method of the compound are described in combination with a preparation scheme (shown in FIG. 1) by taking-B1 as an example.
Step a
3.0mmol of 4-trimethylsilylacetylene benzaldehyde 1-1 and 7.6mmol of 2, 4-dimethylpyrrole 2-1 were dissolved in 90mL of anhydrous Tetrahydrofuran (THF), stirred at room temperature, and vigorously purged with argon for 30min to remove air from the system. 2 drops of trifluoroacetic acid were then added dropwise rapidly and the reaction mixture was stirred at room temperature for 12h in the presence of argon until the TLC plates showed disappearance of 4-trimethylsilylacetylene benzaldehyde. DDQ was dissolved in 10mL of THF in an amount of 1 equivalent, and then slowly added dropwise to the reaction mixture. After stirring for 4h, the reaction was transferred to an ice bath. 18mL of Et were added slowly via a constant pressure dropping funnel3N, after stirring for 5min, 19mL of BF was slowly added3.OEt2. After stirring at room temperature for 12h, the reaction was stopped. The reaction solution was extracted with dichloromethane and water repeatedly three times, and then dried over anhydrous sodium sulfate overnight. After spin-drying of the solvent, separation was performed by column chromatography using dichloromethane and petroleum ether 1: 2 as eluent, 0.82g of the product 3-1 was isolated as an orange solid in 65% yield.
Step b
0.6759g of Compound 3-1 was placed in a 25mL round-bottomed flask, 5mL of dichloromethane was added to completely dissolve Compound 3-1 in the flask, and nitrogen was introduced for 20 min. 0.45g of potassium hydroxide is taken and dissolved by 5mL of methanol, after the solution in the round-bottom flask is completely aerated with nitrogen, the dissolved potassium hydroxide solution is poured into the round-bottom flask, the opening of the round-bottom flask is closed, and the round-bottom flask is stirred for 30min at room temperature. Repeatedly extracting the solution which is completely reacted with dichloromethane and water for three times, finally transferring the organic phase into a conical flask, adding sufficient anhydrous sodium sulfate, drying for 30min, then spin-drying, separating by a column, and selecting eluent petroleum ether with the same proportion as the eluent petroleum ether in the previous step: dichloromethane ═ 2: 1, 0.4536g of product 4-1 are isolated in 81% yield.
Step c
0.5245g of BODIPY alkyne molecules 4-1 and 0.4452g of p-iodoaniline were taken in a 25mL round bottom flask, 6mL of toluene and 2mL of triethylamine were added and the starting materials were completely dissolved by sonication. Introducing argon for 30min, adding 0.2512g of triphenylarsenic into the reaction solution, introducing argon for 20min, and adding 0.2758g of Pd2(dba)3Adding the reaction solution, continuously introducing argon for 20min, plugging the bottle mouth with a rubber plug, sealing with a preservative film and a rubber band, adding into an oil bath pot, carrying out oil bath stirring at 60 ℃ for 72h, and stopping the reaction until the plate is dotted to confirm that the compound 4-1 is completely consumed. After spin-drying the solvent, 0.4433 g of product 5-1 was isolated by column chromatography in 67% yield.
Step d
0.6232g of compound 5-1 and 0.3006g of anhydrous potassium carbonate are dissolved in 2mL of N, N-dimethylformamide, argon is introduced for 20min, 190 mu L of ethyl bromoacetate is added by a micro-syringe, argon is introduced for 10min, the bottle mouth is sealed by a rubber stopper and a preservative film, and oil bath stirring is carried out at 120 ℃ until the compound 5-1 is basically completely converted. And distilling the mixed solution under reduced pressure by using an oil pump, ultrasonically dissolving a small amount of dichloromethane, wherein a target product 6-1 is very easily adsorbed by silica gel, adding 5-10 mL of triethylamine before adding the mixed solution into a chromatographic column to saturate the adsorption of the silica gel, and then adding petroleum ether: 1-dichloromethane: 2 as eluent, 0.2354g of the target product 6-1 was isolated, with a yield of 31%.
Step e
0.2310g of Compound 6-1 and 0.1584mg of C60Dissolved in 6mL of o-dichlorobenzene. Introducing argon gas to the reaction mixture at room temperature for 30min, and adding ethyl glyoxylate (HCOCO)2Et was added and argon was passed in for a further 10min and the reaction mixture was placed in an oil bath which had been previously heated to 170 ℃. When 35% of fullerene remained after 4 hours, the reaction was stopped. Then, o-dichlorobenzene in the reaction system was removed by distillation under reduced pressure. Dissolving the reaction mixture with carbon disulfide, separating by column chromatography, eluting with carbon disulfide, and removing unreacted C60Then the eluent with high polarity is used to obtain 73.1 mg of the target product C60-B1, yield 25%.
The target product C prepared in the above example60of-B11H NMR，13C NMR is shown in fig. 2, 3, respectively, and the mass spectral data of the molecule was experimentally tested: 1329.2601(C95H34BF2N3O4, M)+) (as shown in fig. 4).
Target product C prepared as described above60The structural formula of-B1 is shown below:
for the person skilled in the art, with the target product C60-B (structural formula shown below) formula RDifferent choices of Y can prepare a plurality of rigid linear C with different structures60-a fluoroboron fluorescent triplet photosensitizing molecule having the general molecular structure:
example 1 (rigid Linear type C60-fluoroboric fluorescent triplet photosensitized molecule C60-B2)：
In the general formula, R is methyl and Y is
R1Is methyl, R2Is ethyl.
Example 2 (rigid Linear type C60-fluoroboric fluorescent triplet photosensitized molecule C60-B3)：
In the general formula, R is isopropyl, Y is
R1Is methoxy, R2Is ethyl.
Example 3 (rigid Linear C)60-fluoroboric fluorescent triplet photosensitized molecule C60-B4)：
In the general formula, R is dodecyl and Y is
R1Is ethyl, R2Is Cl.
Example 4 (rigid Linear type C60-fluoroboric fluorescent triplet photosensitized molecule C60-B5)：
In the general formula, R is n-butyl, Y is
R1Is ethyl, R2Is H.
Example 5 (rigid Linear C)60-fluoroboric fluorescent triplet photosensitized molecule C60-B6)：
In the general formula, R is n-propyl and Y is
R1Is toluene, R2Is methyl.
The above-mentioned different rigid line type C60Fluoroboric fluorescent triplet photosensitizing molecule (C)60-B2～C60-B6), preparation method and reaction mechanism thereof and C60The same applies to-B1, and is not described in detail here.
Claims (1)
1. Rigid linear C60The preparation method of the fluoroboric fluorescent triplet photosensitized molecule is characterized by comprising the following preparation routes:
in the preparation route, R is selected from alkyl with 1-12 carbon atoms;
R1and R2Selected from alkyl with 2-5 carbon atoms, H, Cl, Br, I, -OR3Or SR3Wherein R is3Selected from H and alkyl with 2-6 carbon atoms;
y is
；
The preparation method sequentially comprises the following steps:
step a: compound 1 was dosed at 1 g: dissolving 180-250 mL of the compound in anhydrous tetrahydrofuran, and adding a compound 2; stirring the mixed solution at room temperature, and adding inert gas violently for 20-40 min, and then dropwise adding trifluoroacetic acid; continuously reacting the reaction mixed solution for 12-24 hours at room temperature in an inert gas environment until the TLC plate shows that the compound 1 disappears; adding DDQ at a ratio of 1 g: dissolving 14-20 mL of the solution in THF, and slowly dropwise adding the solution into the reaction mixed solution; continuously stirring for 4-8 h, and transferring the reaction solution to an ice bath condition; slowly adding 15-20 mL of triethylamine Et by using a constant-pressure dropping funnel3N, stirring for 5-20 min, and slowly adding boron trifluoride diethyl etherate BF3·OEt2(ii) a Continuously stirring the mixture at room temperature for 8-12 h, and stopping the reaction; repeatedly extracting the reaction solution with dichloromethane and water for three times, and drying the reaction solution overnight with anhydrous sodium sulfate; after the solvent is dried by spinning, separating by using column chromatography to obtain an orange solid product 3; wherein the molar charge ratio is 1: 2: acid: DDQ: BF (BF) generator3·OEt2=0.8～1.2：1.6～2.4：0.16～0.24：0.8～1.2：40～60；
Step b: compound 3 was mixed at 1 g: 12-20 mL of the composition is dissolved in a solvent with a volume ratio of 3: 1, adding KOH into a dichloromethane/methanol mixed solution, and introducing inert gas for reaction; after the plate counting tracking confirms that the compound 3 completely disappears, extracting the solution by using dichloromethane and water, drying an organic phase by using anhydrous sodium sulfate, then carrying out spin drying, and carrying out column separation to obtain a product 4; the molar ratio of the compound 3 to KOH is 0.8-1.2: 4-6, the reaction temperature is room temperature, and the reaction time is 0.5-2 h;
step c: compound 4 was dosed at 1 g: dissolving 10-20 mL of the composition in a solvent with a volume ratio of 3: 1 in a mixed solution of toluene/triethylamine; adding p-iodoaniline, and introducing inert gas for 20-40 min; adding triphenylarsenic and Pd2(dba)3Continuously introducing gas, sealing the bottle mouth, adding a reaction bottle into the oil bath kettle, and continuing to react until the compound 4 basically disappears; after the reaction is finished, removing the solvent by spinning, and separating by passing through a column to obtain a product 5; compound 4 and p-iodoaniline, triphenylarsenic and Pd2(dba)3The molar ratio of (a) to (b) is 0.8-1.2: 0.96-1.44: 0.4-0.6: 0.16-0.24, the reaction temperature is 60-120 ℃, and the reaction time is 24-72 hours;
step d: compound 5 was taken as 1 g: dissolving 1.5-2.5 mL of the aqueous solution in DMF, and adding anhydrous K2CO3(ii) a Introducing argon gas to protect the reaction mixture for 20-40 min at room temperature, and then rapidly adding bromoacetic acid alkyl ester, namely BrCH2CO2R, wherein R is selected from alkyl with 1-12 carbon atoms, argon is continuously introduced for 5-10 min, and the reaction bottle is sealed; placing the reaction mixture in an oil bath for reaction, performing thin-layer chromatography tracking, removing DMF under reduced pressure when the raw material point basically disappears, and separating the mixture by a column to obtain a compound 6; the molar ratio of the compound 5, anhydrous potassium carbonate and bromoacetic acid alkyl ester is 0.8 ℃ -1.2: 1.2-2.0: 0.96-1.5, the reaction temperature is 100-120 ℃, and the reaction time is 10-24 h;
step e: c is to be60Mixing the raw materials in a ratio of 1 g: dissolving 50-55 mL of the compound in o-dichlorobenzene, and adding a compound 6; introducing argon to protect the reaction mixture for 20-30 min at room temperature, and then introducing alkyl glyoxylate, namely HCOCO2Adding R, wherein R is selected from alkyl with 1-12 carbon atoms, continuously introducing argon for 10-20 min, and putting the reaction mixture into a preheated oil bath for reaction; stopping the reaction when the amount of the fullerene is 30-40 percent; then carrying out reduced pressure distillation to remove the o-dichlorobenzene in the reaction system; dissolving the reaction mixture with carbon disulfide, separating by column chromatography, eluting with carbon disulfide, and removing unreacted C60Then, changing to a high-polarity eluting agent to obtain a target product; compound 6, C60The molar ratio of the alkyl glyoxylate to the alkyl glyoxylate is 1.8-2.2: 0.8-1.2: 16-24 ℃, the reaction temperature is 140-160 ℃, and the reaction time is 3-5 h.
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