CN115232161B - Trimerdanyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof - Google Patents
Trimerdanyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract description 33
- -1 monobromoperylene diimide derivative Chemical class 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 8
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004327 boric acid Substances 0.000 claims abstract 2
- 238000005886 esterification reaction Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 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 2
- 238000012546 transfer Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
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- 238000000746 purification Methods 0.000 abstract 1
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 102100027340 Slit homolog 2 protein Human genes 0.000 description 1
- 101710133576 Slit homolog 2 protein Proteins 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- YGPLLMPPZRUGTJ-UHFFFAOYSA-N truxene Chemical compound C1C2=CC=CC=C2C(C2=C3C4=CC=CC=C4C2)=C1C1=C3CC2=CC=CC=C21 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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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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Abstract
The invention discloses a trimeric indenyl-BODIPY-perylene diimide ternary system molecular structure shown in a formula (V) and a preparation method thereof. The method is realized by the following steps: the meso-bromo-trimeric indenyl BODIPY shown in the formula (I) and p-methoxybenzaldehyde are reacted through Knoevenagel to generate a meso-bromo-trimeric indenyl BODIPY derivative shown in the formula (II), then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) is obtained through Miyaura boric acid esterification, and then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) and the bay-position monobromoperylene diimide derivative shown in the formula (IV) are subjected to Suzuki coupling reaction to obtain the trimeric indenyl-BODIPY-perylene diimide ternary system molecule shown in the formula (V). The synthesis method is simple, the reaction condition is mild, and the separation and purification are simple. Different groups in the ternary system can perform intermolecular high-energy transfer after being excited by light, and can be applied to the fields of light molecular absorption antennas, artificial simulated photosynthesis and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and the field of molecular-based photoelectric materials, and relates to a trimeric indenyl-BODIPY-perylene diimide ternary system molecule and a preparation method thereof.
Background
Application research of a molecular model based on photoinduction energy/electron transfer mechanism in aspects of optical molecular devices, solar cells, artificial light synthesis and the like has become an active research field at home and abroad. Dye molecules with electron/energy donor-acceptor properties have shown broad application prospects in the field of organic photoelectric functional materials. In the molecular models of different structure types, the unique three-dimensional star-shaped structure of the ternary system molecule is beneficial to regulating and controlling the photoelectric property and morphological characteristics of the molecule, and a plurality of outward extending support arms can improve the charge transfer and energy transfer efficiency, so that the ternary system molecule has been widely focused. However, the ternary system molecule with the donor-acceptor structure still has the defects of more synthesis steps, complex reaction, low yield and the like, so that the design and synthesis of the ternary system molecule easy to synthesize with high-efficiency energy/electron transfer process have important significance.
The perylene diimide derivative has excellent light, heat and chemical stability, has strong absorption and emission in a visible light region, and has higher fluorescence quantum yield; because the perylene has a larger conjugated plane in the molecule, the perylene diimide derivative generally has pi-pi stacking effect between molecules, which promotes the formation of two-dimensional structures between molecules and molecules, and has good conductivity and proper electron affinity, and the perylene diimide molecule has wide application in the fields of organic field effect transistors, organic light emitting diodes, solar cells and the like. The trimeric indene (truxene) has a large rigid conjugated structure, is a triple symmetry plane rigid polycyclic aromatic hydrocarbon, is favorable for intramolecular charge transfer, and has three end groups 2, 7 and 12 which are easy to carry out functional design and modification, and has proved to be one of ideal compounds for preparing ternary system molecules. In addition, the BODIPY is also a fluorescent dye with excellent performance, and has the advantages of higher photo-thermal stability, molar absorptivity, fluorescence quantum yield, long fluorescence life, moderate oxidation-reduction potential, negligible triplet state and the like; and the fluorescence molecular parent nucleus of the fluoboric dipyrrole is relatively stable and has certain chemical activity, the structure is easy to modify, the absorption and emission wavelength can be adjusted to a near infrared region, and the fluorescence molecular parent nucleus can be applied to the fields of photoelectric materials, fluorescence imaging and the like. Based on excellent properties and structural diversification of perylene diimide, trimeric indene and fluoroborodipyrrole molecules, the trimeric indene-BODIPY-perylene diimide ternary system molecule with high-efficiency charge transfer or energy transfer is synthesized by a simple chemical synthesis method, has very important significance, and is beneficial to promoting application in aspects of organic field effect transistors, light molecular absorption antennas, artificial simulated photosynthesis and the like.
Disclosure of Invention
The invention aims to: aiming at the defects existing in the prior art, the invention aims to provide a trimeric indenyl-BODIPY-perylene diimide ternary system molecule and a preparation method thereof.
The technical scheme is as follows: in order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention relates to a trimeric indenyl-BODIPY-perylene diimide ternary system molecule, which has the following structure:
the invention relates to a synthetic route of a trimeric indenyl-BODIPY-perylene diimide ternary system molecule, which comprises the following steps:
The preparation process of the trimeric indenyl-BODIPY-perylene diimide ternary system molecule includes the following steps:
Step 1: dissolving bromotrimeric indenyl BODIPY (I), p-methoxybenzaldehyde and p-toluenesulfonic acid (PTSA) in dry toluene, adding piperidine, reacting for 5 hours at 140 ℃, diluting with dichloromethane after the reaction, washing an organic phase with distilled water, separating the organic phase, drying the organic phase by anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain a bromotrimeric indenyl BODIPY derivative (II);
Step 2: mixing and dissolving bromotrimeric indenyl BODIPY derivative (II), potassium acetate, bisboronic acid pinacol ester, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride (Pd (dPPf) Cl 2) in dry toluene under the protection of argon, stirring and reacting for 4 hours at 100 ℃, diluting with dichloromethane after the reaction is finished, washing an organic phase with distilled water, separating the organic phase, drying the organic phase with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the meso-phenylboronic acid ester trimeric indenyl BODIPY derivative (III);
step 3: dissolving a meso-phenylborate trimerization indenyl BODIPY derivative (III) and a bay monobromoperylene diimide derivative (IV), potassium carbonate and tetraphenylphosphine palladium in tetrahydrofuran, distilled water and methanol, reacting for 12 hours at 65 ℃ under the protection of argon, diluting with methylene dichloride after the reaction is finished, washing an organic phase with distilled water, combining organic layers and drying with anhydrous sodium sulfate, separating out an organic phase, drying with anhydrous sodium sulfate, evaporating a solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the trimerization indenyl-BODIPY-perylene diimide ternary system molecule shown in the formula (V).
In the reaction step, the catalyst of the tetraphenylphosphine palladium is 10 percent of the mass of the meso-phenylborate trimeric indenyl BODIPY derivative (III);
In the above reaction step, the ratio of the mass of the meso-phenylboronate trimeric indenyl BODIPY derivative represented by the formula (III) to the mass of the bay-site monobromoperylene diimide derivative represented by the formula (IV) was 1:3.
The beneficial effects of the invention are that
Compared with the prior art, the trimeric indenyl-BODIPY-perylene diimide ternary system molecule and the preparation method thereof have the advantages that: (1) The same molecule has BODIPY group and perylene diimide group, has strong electron absorption in ultraviolet region, visible light region and near infrared region, has wide light absorption range, has high fluorescence emission intensity in near infrared region, and is near infrared fluorescent dye with excellent performance. (2) The compound is in a three-arm star shape, can effectively weaken pi-pi interaction among molecules, forms a ternary system molecule of a plurality of energy donors and energy acceptors, can generate an energy transfer process in the same molecular system, is beneficial to improving photoelectric conversion efficiency, has high photoinduced energy transfer efficiency, and can be used for light absorption antennas, artificial simulated biological photosynthesis, field effect transistors and the like. (3) The synthesis route is simple, the reaction condition is mild, the reaction selectivity is good, the universality is realized, and the synthesis of the ternary system-like molecules can be popularized and applied.
Drawings
FIG. 1 is an ultraviolet-visible absorption spectrum of meso-bromotrimeric indenyl BODIPY derivative (II), bay-position monobromoperylene diimide derivative (IV) and trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) in methylene chloride;
FIG. 2 is the fluorescence emission spectra of meso-bromotrimeric indenyl BODIPY derivative (II), bay-position monobromoperylene diimide derivative (IV) and trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) in methylene chloride.
Detailed Description
The invention will be further explained with reference to specific examples, which are not intended to limit the invention in any way.
The structure of the compound was characterized by 1 H-NMR, UV-visible and fluorescence spectra and the photophysical properties of the compound were studied. The detection instrument comprises: bruker ARX500 nuclear magnetic resonance (TMS is an internal standard, deuterated chloroform is a solvent), shimadzu UV-3100 ultraviolet-visible spectrophotometer (scanning range 400-800 nm, light path slit 2 nm), PE LS-55 fluorescence spectrophotometer (wavelength range: excitation light 200-800nm, emission light 200-900nm, slit variable: excitation light path 2.5-15nm, emission light path 2.5-20nm, step distance: 0.1 nm).
Example 1
Bromotrimeric indenyl BODIPY (I) (100 mg,0.11 mmol), p-methoxybenzaldehyde (45 mg,0.33 mmol) and p-toluenesulfonic acid (PTSA) (20 mg,0.1 mmol) were dissolved in 20mL of dry toluene, 0.2mL of piperidine was added, the reaction was monitored by thin layer chromatography using a Dean-stark apparatus under reflux stirring at 140℃and after the reaction of the starting materials was completed, toluene in the reaction was distilled off by a water separator, the reaction was cooled to room temperature, 100mL of methylene chloride was added, and the organic phase was washed with distilled water, the solvent was distilled off under reduced pressure after drying over anhydrous sodium sulfate, and 80mg of bromotrimeric indenyl BODIPY derivative (II) was obtained by chromatography on a silica gel column using methylene chloride-petroleum ether (V: V=1:1) as an eluent, yield 64％;1H NMR(600MHz,CDCl3)：δ＝8.43(d,J＝7.8Hz,1H),8.19(d,J＝8.4Hz,2H),7.67-7.58(m,8H),7.55-7.51(m,2H),7.48-7.47(m,1H),7.37-7.36(m,1H),7.25-7.23(m,2H),6.95-6.94(m,4H),6.65(s,2H),3.87(s,6H),3.03-2.92(m,6H),2.17-2.13(m,6H),1.55(s,6H),0.28-0.22(m,18H).
Example 2
The trimeric indenyl bromo BODIPY derivative (II) (80 mg,0.07 mmol), potassium acetate (52 mg,0.53 mmol), pinacol biborate (81 mg,0.31 mmol), [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride (Pd (dPPf) Cl 2) (6 mg,0.01 mmol) was dissolved in dry toluene (Toluene) (4 mL) under the protection of argon, stirred, heated to 100deg.C for reaction, after TLC monitoring no starting material in the reaction, the reaction flask was cooled to room temperature, 100mL of dichloromethane was added, and the organic phase was washed with distilled water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the meso-phenyl borate trimeric indenyl BODIPY derivative (III) was obtained (65 mg, yield) by silica gel column chromatography using dichloromethane-petroleum ether (V: V=4:1) as eluent 75％;1H-NMR(600MHz,CDCl3)：δ＝8.48(d,J＝8.4Hz,1H),8.40(d,J＝8.4Hz,1H),8.34(d,J＝7.8Hz,1H),7.91-7.87(m,4H),7.64(d,J＝16.8Hz,2H),7.60(d,J＝8.4Hz,4H),7.47-7.46(m,1H),7.36-7.35(m,1H),7.25-7.22(m,2H),6.95-6.94(m,4H),6.95-6.94(m,4H),6.65(s,2H),3.87(s,6H),3.03-3.0(m,6H),2.31-2.13(m,6H),1.55(s,6H),1.41(s,12H),1.40(s,12H),0.26-0.17(m,18H).
Example 3
Dissolving meso-phenylboronate BODIPY derivative (III) (65 mg,0.05 mmol), bay monobromoperylene diimide derivative (IV) (130 mg,0.16 mmol), potassium carbonate (55 mg,0.39 mmol), tetrakis triphenylphosphine palladium (7 mg,0.01 mmol) in dry tetrahydrofuran (20 mL), distilled water (2 mL) and methanol (MeOH) (2 mL) mixed solvent under the protection of argon, heating to 65 ℃ and stirring for 12-14 hours, cooling the reaction flask to room temperature after the reaction, adding 100mL of dichloromethane, washing the organic phase with distilled water, drying the organic phase with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, separating by silica gel column chromatography with dichloromethane-petroleum ether (V: V=4:1) as eluent to obtain the trimeric indenyl-perylene diimide ternary system molecule (V) 76mg, yield 58％;1H-NMR(400MHz,CDCl3)：δ＝8.69-8.67(m,10H),8.55-8.43(m,3H),8.20-8.10(m,4H),7.68-7.51(m,11H),7.37-7.35(m,1H),7.23-7.22(m,2H),6.96-6.94(m,4H),6.66-6.64(m,2H),5.22-5.12(m,4H),3.87(s,6H),3.14-2.96(m,6H),2.27-1.83(m,22H),1.55(s,6H),1.31-1.19(m,64H),0.83-0.79(m,24H),0.43-0.28(m,18H).
Example 4
Ultraviolet-visible absorption spectra of meso-bromotrimeric indenyl BODIPY derivative (II), bay-position monobromoperylene diimide derivative (IV) and trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) solutions
The meso-bromotrimeric indenyl BODIPY derivative (II), the bay monobromoperylene diimide derivative (IV) and the trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) are respectively dissolved in methylene dichloride to prepare a solution with the concentration of 1X 10 -5 mol/L, and the ultraviolet-visible absorption spectrum is measured. FIG. 1 is the UV-visible absorption spectrum of a solution of meso-bromotrimeric indenyl BODIPY derivative (II), bay-position monobromoperylene diimide derivative (IV) and trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) in the present invention.
Example 5
Fluorescence emission spectra of meso-bromotrimeric indenyl BODIPY derivative (II), bay-position monobromoperylene diimide derivative (IV) and trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) solutions
The meso-bromotrimeric indenyl BODIPY derivative (II), the bay mono-bromoperylene diimide derivative (IV) and the trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) are respectively dissolved in methylene dichloride to prepare a solution with the concentration of 1X 10 -5 mol/L, the meso-bromotrimeric indenyl BODIPY derivative (II) is excited by using the wavelength of 644nm, and the bay mono-bromoperylene diimide derivative (IV) is excited by using the wavelength of 500nm to determine the fluorescence emission spectrum; the trimeric indenyl-BODIPY-perylene diimide ternary system molecules (V) are excited by using wavelengths of 500nm and 644nm respectively, and characteristic emission peaks of BODIPY groups are emitted, so that efficient energy transfer can occur from the perylene diimide groups to the BODIPY groups; FIG. 2 shows the fluorescence emission spectra of the meso-bromotrimeric indenyl BODIPY derivative (II), the bay-position monobromoperylene diimide derivative (IV) and the trimeric indenyl-BODIPY-perylene diimide ternary system molecule (V) solution according to the present invention.
Claims (5)
1. A trimeric indenyl-BODIPY-perylene diimide ternary system molecule of formula (V):
2. A process for the preparation of a trimeric indenyl-BODIPY-perylene diimide ternary system molecule of formula (V) as defined in claim 1, characterized in that said process comprises: the meso-bromo-trimeric indenyl BODIPY shown in the formula (I) and p-methoxybenzaldehyde are reacted through Knoevenagel to generate a meso-bromo-trimeric indenyl BODIPY derivative shown in the formula (II), then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) is obtained through Miyaura boric acid esterification reaction, and then the meso-borate trimeric indenyl BODIPY derivative and the bay-position monobromoperylene diimide derivative shown in the formula (IV) are subjected to Suzuki coupling reaction to obtain the trimeric indene-BODIPY-perylene diimide ternary system molecule shown in the formula (V);
3. the preparation method according to claim 2, characterized in that the preparation method comprises the following experimental steps:
Step 1: dissolving bromotrimeric indenyl BODIPY (I), p-methoxybenzaldehyde and p-toluenesulfonic acid (PTSA) in dry toluene, adding piperidine, reacting for 5 hours at 140 ℃, diluting with dichloromethane after the reaction, washing an organic phase with distilled water, separating the organic phase, drying the organic phase by anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain a bromotrimeric indenyl BODIPY derivative (II);
Step 2: mixing and dissolving bromotrimeric indenyl BODIPY derivative (II), potassium acetate, bisboronic acid pinacol ester, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride (Pd (dPPf) Cl 2) in dry toluene under the protection of argon, stirring, reacting for 4 hours at 100 ℃, diluting with dichloromethane after the reaction, washing an organic phase with distilled water, separating the organic phase, drying the organic phase by anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the meso-borate trimeric indenyl BODIPY derivative (III);
Step 3: dissolving a meso-borate trimeric indene BODIPY derivative (III) and a bay monobromoperylene diimide derivative (IV), potassium carbonate and tetraphenylphosphine palladium in tetrahydrofuran, distilled water and methanol, reacting for 12 hours at 65 ℃ under the protection of argon, diluting with methylene dichloride after the reaction is finished, washing an organic phase with distilled water, combining organic layers and drying with anhydrous sodium sulfate, separating the organic phase, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove a solvent, and separating and purifying by silica gel column chromatography to obtain the trimeric indene-BODIPY-perylene diimide ternary system molecule shown in the formula (V).
4. A process according to claim 3, characterized in that in the experimental step the catalyst tetrakis triphenylphosphine palladium is used in an amount of 10% of the mass of the meso-borate trimeric indenyl BODIPY derivative (III).
5. The process according to claim 3, wherein the ratio of the amount of the meso-borate trimeric indenyl BODIPY derivative represented by the formula (III) to the amount of the substance of the bay-position monobromoperylene diimide derivative represented by the formula (IV) in the experimental step is 1:3.
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