CN101265261B - Porphyrin-fullerene assembling body and its preparation and use as functional material - Google Patents
Porphyrin-fullerene assembling body and its preparation and use as functional material Download PDFInfo
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- CN101265261B CN101265261B CN2008100365151A CN200810036515A CN101265261B CN 101265261 B CN101265261 B CN 101265261B CN 2008100365151 A CN2008100365151 A CN 2008100365151A CN 200810036515 A CN200810036515 A CN 200810036515A CN 101265261 B CN101265261 B CN 101265261B
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Abstract
The invention relates to a preparation method of a U-shaped porphyrin dimmer and a fullerene derivative, and application in organic small molecule gel thereof. The two series of monomer molecules can not form gel structure, the two component mixed system can form self-assembly body by performing complexing of porphyrin dimmers and fullerene derivatives to form gel phase in solvent such as decahydronaphthalene, etc. The gels contain porphyrin and fullerene as the main body, and are combined with cholesterol segment, which represents a new gel assembly method. As the macrocyclic conjugated structure of the porphyrin and the fullerene has characteristic absorption, the gel materials can be used in the fields of photoelectron material, liquid crystal, etc. The synthetic method has simple operation and mild condition. The obtained gel has wide application range.
Description
Technical field
The present invention relates to porphyrin-fullerene assembling body, its preparation and as purposes such as novel materials.
Background technology
(low molecular organic gelator LMOG) is a research field of rising in recent years to Low Molecular-Weight Gel.On macroscopic aspect, the Low Molecular-Weight Gel agent is meant in specific solvent and adds a certain amount of gelifying agent, can make solvent liquid present gel and solidifies, handstand container and system can not flow.[Lin, Y. such as Weiss; Kachar, B.; Weiss, RG.J.Am.Chem.Soc.1989,111,5542.] at first this class phenomenon is concluded out, and it is carried out deep research.The development of technology also makes the means of research become diversified, and in recent years, more research began to lay particular emphasis on the microtexture of this class phenomenon.A large amount of SEM, TEM, AFM research has disclosed the reason that this class phenomenon produces, and promptly the crosslinked solvent that makes of filamentary structure can not flow.This filamentary structure itself is exactly a class nano wire or a micro wire, the introducing of π system can so that this class formation as microtronics material [Terech, P.; Weiss, R.G.Chem.Rev.1997,97,3133.].
Because electronics and energy can transmit by the ordered arrangement of pi-pi accumulation, the assembly that structure contains big π system is at photoelectric material, and also there is great role in fields such as semi-conductor.
Porphyrin and soccerballene all have unique big ring conjugated structure, are respectively that good electron is given body and acceptor, have in the ultraviolet-visible light district very widely to absorb.Therefore, the assembling physical efficiency of their derivative makes up different organic functional materials, is the focus of investigation of materials always.
Aspect the Low Molecular-Weight Gel research of porphyrin, Shinkai etc. have reported some results.Calendar year 2001, Shinkai has reported that a class is connected Low Molecular-Weight Gel agent [Ishi-I, the Y. of porphyrin and cholesterol by diamines; Iguchi, R.; Snip, E.; Ikeda, M.; Shinkai, S.Langmuir.2001,17,5825.].By the pi-pi accumulation of porphyrin, on the nitrogen-atoms between the hydrogen bond of reactive hydrogen and the cholesterol relatively stronger Van der Waals force can make this quasi-molecule form filamentary structure, some solvents are formed gel.Shinkai etc. also find, add the gel-formation power that soccerballene can strengthen this organic micromolecule gel.
Aspect the Low Molecular-Weight Gel research of soccerballene, [Ishi-i, T. such as Shinkai; Ono, Y.; Shinkai, S.Chem.Lett.2000,29,808] synthesized the segmental fullerene derivate of introducing cholesterol, find that this compound can form gel in methylene dichloride, destroy this gelling system but add tetraphenylporphyrin.
Single porphyrin compound or single fullerene derivate generally can not form gel, and the research that the mixture that does not possess the porphyrin of gel ability and fullerene molecule forms gel does not have bibliographical information.
[Wu, Z. in the work before the contriver; Shao, X.; Li, C.; Hou, J.; Wang, K.; Jiang, X.; Li, Z.J.Am.Chem.Soc.2005,127,17460], the contriver had once prepared the biporphin compound of a class " U " shape, and with this compound soccerballene was carried out Study of recognition.The present invention has developed " U " shape biporphin compound and fullerene derivate, and constructs gelling system with their assembly.This system is expected to be applied to develop functional materialss such as photoelectric material and liquid crystal.
Summary of the invention
The problem that will solve of the present invention provides the assembly of biporphin compound and fullerene derivate and the biporphin compound and a fullerene derivative of intermediate one class " U " shape thereof.
The problem that also will solve of the present invention provides the preparation method of above-claimed cpd.
The problem that the present invention also will solve provides the purposes of above-mentioned assembly, comprises Low Molecular-Weight Gel system that the assembly by above-mentioned biporphin compound and fullerene derivate the forms purposes as functional materials.
The invention provides porphyrin-fullerene assembling body, have following structure:
R in the formula
1, R
2Be identical or different group, be respectively C
8～C
16Alkyl, (CH
2CH
2O)
3CH
3Or (CH
2CH
2O)
4CH
3, M=Zn or Cu, Ph represent phenyl or substituted-phenyl, and the substituting group of described substituted-phenyl is C
1～C
6Alkyl or alkoxyl group,
R
3, R
4Be identical or different group, be respectively C
8～C
16Alkyl or
Dotted line is represented the junction.
Recommend: R
1, R
2Be respectively n-C
12H
25, (CH
2CH
2O)
3CH
3, (CH
2CH
2O)
4CH
3Or n-C
16H
33, M=2H, Zn or Cu, Ph represents phenyl, R
3, R
4Be respectively n-C
16H
33Or
Further recommend: R
1Be n-C
12H
25And R
2Be n-C
16H
33, perhaps R
1Be (CH
2CH
2O)
3CH
3And R
2Be (CH
2CH
2O)
4CH
3, M=2H, Zn or Cu, Ph represents phenyl, R
3Be n-C
16H
33Or
Biporphin compound provided by the present invention and fullerene derivate structure are as follows:
R wherein
1, R
2, R
3, R
4, M and Ph as previously mentioned, recommend following compound:
Porphyrin provided by the invention-fullerene assembling body is recommended and can be prepared by above-mentioned biporphin compound and fullerene derivate: biporphin compound and fullerene derivate are mixed in organic solvent, mol ratio is recommended as 1: 1, recommends reaction preparation in 1 minute～5 hours under the room temperature.Described organic solvent is recommended perhydronaphthalene.The preparation method of described biporphin compound recommends at first under the condition that propionic acid refluxes, obtain a porphyrin compound, this porphyrin compound is through hydrolysis, obtain another porphyrin acid, this porphyrin acid compound and diamine compound generation condensation reaction obtain the biporphin compound, the mole dosage of condensing agent is recommended as 1.2～10 times of porphyrin acid mole dosage, and the structural formula of described porphyrin acid compound and diamine compound is as follows:
R in the formula
1, R
2, Ph as previously mentioned.Further recommend R
1, R
2Be identical or different group, be respectively C
12H
25, (CH
2CH
2O)
3CH
3, (CH
2CH
2O)
4CH
3Or C
16H
33Ph represents phenyl.
Above-mentioned biporphin compound also can be again and the hydrate of Zn salt, mantoquita, Zn salt, hydrate such as Zn (OAc), the Zn (OAc) of mantoquita
22H
2O or Cu (OAc) react in organic solvent, and the mol ratio of described biporphin compound and aforementioned metal salt is recommended as 1: 2～and 100, obtaining M is the biporphin compound of Zn or Cu, described organic solvent is recommended methylene dichloride and methyl alcohol etc.
The reaction conditions of recommending is as follows: porphyrin acid compound and diamine compound materials mol ratio are (1～4): 1, temperature of reaction is a room temperature, reaction times is 10～60 hours, condensing agent is recommended EDCI (carbodiimide hydrochloride) or HATU (2-(7-azo benzotriazole)-N, N, N ', N '-tetramethyl-urea phosphofluoric acid ester), reaction solvent is recommended methylene dichloride or chloroform. Further the reaction conditions of recommending is as follows: the materials mol ratio is 2: 1, and temperature of reaction is a room temperature, and the reaction times is 30 hours.
The preparation method of described fullerene derivate recommends, at first obtain the compound of malonic ester, this malonic ester compound and soccerballene C60 at organic bases as 1, react under 8-diazacyclo ring-7-hendecene and iodine (DBU), 4-Dimethylamino pyridine (DMAP) or the carbon tetrabromide condition, obtain the fullerene derivate of target, the structural formula of the compound of described malonic ester is as follows:
R in the formula
3Be recommended as n-C
16H
33Or
The reaction conditions of recommending is as follows: malonic ester compound and soccerballene C
60The materials mol ratio is 0.5～3: 1, and temperature of reaction is a room temperature, and the reaction times is 1～10 hour, and reaction solvent is recommended as toluene or benzene etc.Further recommend malonic ester compound and soccerballene C
60The materials mol ratio is 1: 1, and temperature of reaction is a room temperature, and the reaction times is 3 hours.
The preparation method of compound and reaction formula are exemplified below among the present invention:
Wherein DMAP represents the 4-Dimethylamino pyridine, and Ac represents ethanoyl, and Ta represents p-toluenesulfonyl, and HOBt represents I-hydroxybenzotriazole.
Other two fullerene derivates 23 and 24 involved in the present invention utilize the described method preparation of document [Camps, et al.J.Chem.Soc.Perkin Trans.1.1997,11,1595.].They are used to produce new biporphin-fullerene assembling body and gelifying agent, do not describe in the discovery document of their this performances.
Compound among the present invention can be used as the Low Molecular-Weight Gel agent.
In order to help the structure of clearer understanding above-claimed cpd, illustrate below.
Table 1 is the test result of biporphin compound, fullerene derivate and their the assembly formation gel in different solvents.
Table 1. biporphin compound, fullerene derivate and their assembly produce the gel phase The performance test results.
| Perhydronaphthalene (Decalin) | Chloroform (chlorofor m) | Toluene (Toluene) | Hexanaphthene (cyclohexa ne) | Normal hexane (n-hexane) | |
| 1a 1b 1b·23 1b·24 1b·3 1b·4 | S pG pG pG pG pG | S S S S S S | S S S S S S | S pG pG pG pG pG | S P pG pG pG pG |
| Perhydronaphthalene (Decalin) | Chloroform (chlorofor m) | Toluene (Toluene) | Hexanaphthene (cyclohexa ne) | Normal hexane (n-hexane) | |
| 1c 1c·23 1c·24 1c·3 1c·4 2 2·23 2·24 2·3 2·4 3 4 23 24 | pG pG pG G pG S S S S S S S S S | S S S S S S S S S S S S S S | S S S S S S S S S S S S S S | pG pG pG pG pG S S S S S S S S S | pG pG P P P P P P P P S S S P |
In the table, S represents solution, and pG represents that part becomes gel, G to represent to form gel.The concentration of being tested all is 35mM.
Wherein 1c24,1c3,1c4,223,224,23,24 represent the assembly of corresponding biporphin compound and fullerene derivate respectively, its preparation method is that biporphin compound and fullerene derivate are dissolved in organic solvent such as the toluene solvant, stirring at room 5 minutes removes solvent under reduced pressure then and obtains.
The titrating result of ultraviolet shows that the binding constant of this two compounds is 10
4M
-1About, the Job-plot experimental result shows that this two compounds is the pattern bonded by 1: 1.
By table 1 as seen, the one-tenth gel effect of assembly 1c3 in perhydronaphthalene solution is best.
The Low Molecular-Weight Gel that assembly of the present invention forms in some organic solvents such as perhydronaphthalene, the gel that obtains can be as novel material especially functional materials such as photoelectron material and liquid crystal (seeing Table 2).
The liquid crystal property research of table 2 biporphin compound and fullerene derivate.
| Compound number | Mesomorphic phase changes |
| 3 1a 1a·3 1b 1b·3 1c 1c·3 | Solid ca.70 I Solid 45 Sc ca.140 I Solid 40 Sx ca.130 I Solid 64 Sc 164 I Solid 51 SG 140 I Solid 54 SC 102 Sx 163 I Solid 47 SG 95 Sx 153 I |
Wherein, Solid represents solid glassy state, Sc, and SG, Sx represent to have formed smectic liquid crystal, and I represents molten state.
Description of drawings
The gel test result of fullerene derivate 3 in the perhydronaphthalene solvent among Fig. 1: the embodiment 15.
The gel test result of biporphin compound 1c in the perhydronaphthalene solvent among Fig. 2: the embodiment 15.
The gel test result of assembly 1c3 in perhydronaphthalene solution among Fig. 3: the embodiment 15.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
The preparation of biporphin compound
Embodiment 1
With compound 5 (6.96g, 20.0mmol), phenyl aldehyde 6 (6.36g 60.0mmol) refluxes in propionic acid (300mL), add pyrroles 7 (5.5mL, 80.0mmol).Continue to reflux the pressure reducing and steaming solvent 3 hours.Column chromatography (CS
2/ toluene 1: 1) obtain thick product, the methylene chloride reprecipitation gets purple product 8 (910mg, 5%).
1H NMR (300MHz, CDCl
3): δ 8.85 (m, 8H), 8.63 (d, J=2.4Hz, 1H), 8.20-8.23 (m, 7H), 7.71-7.80 (m, 9H), 7.24 (d, J=5.7Hz, 1H), 4.28 (t, J=6.3Hz, 2H), 3.91 (s, 3H), 2.00 (m, 2H), 1.61 (m, 2H), 1.26-1.53 (m, 16H), 0.90 (t, J=6.9Hz, 2H).
13C NMR (CDCl
3): δ 167.0,158.5, and 142.2,138.8,136.8,134.6,133.9,131.2,127.7,126.7,120.2,118.9,118.6,111.5,69.4,32.0,29.8,29.7,29.5,29.4,26.1,22.7,14.1.MS (MALDI-TOF): m/z 858[M+H]
+.C
58H
56N
4O
3The ultimate analysis calculated value: C, 81.28; H, 6.59; N, 6.54. measured value: C, 81.38; H, 6.48, N, 6.38.
Embodiment 2
Compound 8 (428mg 0.50mmol) is dissolved in pyridine, and adding NaOH (1.00g, the 25.0mmol) aqueous solution (20mL), stirring and refluxing 12 hours, decompression steams solvent.Add 10mL water, add 3N hydrochloric acid to pH=3.Chloroform (80mL * 2) extraction.Organic phase is washed to pH=7, and anhydrous sodium sulfate drying is spin-dried for and obtains purple product 9 (420mg, 100%).
1H NMR (300MHz, CDCl
3): δ 11.29 (br, 1H), 9.05 (s, 1H), 8.85 (m, 6H), 8.76 (d, J=3.9Hz, 2H), 8.32 (d, J=8.7Hz, 1H), 8.20 (br, 6H), 7.76 (br, 9H), 7.37 (d, J=8.7Hz, 1H), 4.50 (2H), 2.09 (m, 2H), 1.63 (m, 2H), 1.26-1.45 (m, 16H), 0.90 (3H) ,-2.80 (s, 2H) .MS (MALDI-TOF): m/z 844.7[M+H]
+
Embodiment 3
(421mg, 0.50mmol), (147mg, 0.25mmol), DMAP (20mg, 0.16mmol catalytic amount cat.amount) uses CH to compound 10 to compound 9
2Cl
2(100mL) dissolving, and adding EDCI (250mg, 1.30mmol), stirring at room 30 hours.Water (80mL * 4) is washed anhydrous sodium sulfate drying.Be spin-dried for column chromatography (sherwood oil/CH behind the solvent
2Cl
21: 1), obtain purple product 1a (273mg, 29%).IR (KBr): v 3444,2923,2852,1659,1537,1469,970,800cm
-1.UV-Vis (decalin): 419,514,550,591,649nm.
1H NMR (400MHz, CDCl
3): δ 10.21 (s, 2H), 9.48 (s, 1H), 9.17 (d, J=2.4Hz, 2H), and 8.75-8.85 (m, 16H), 8.16-8.21 (m, 14H), 7.59-7.76 (m, 18H), 7.35 (d, J=8.7Hz, 2H), 6.68 (s, 1H), 4.46 (t, J=6.6Hz, 4H), 4.16 (t, J=6.9Hz, 4H), 2.11 (m, 4H), 1.96 (m, 4H), 1.14-1.60 (m, 88H), 0.78-0.88 (m, 12H) ,-2.80 (s, 4H).
13C NMR (CDCl
3): δ 162.9,156.7, and 146.1,142.3,142.2,138.4,135.2,134.6,127.6,127.5,126.6,126.5,121.7,121.3,120.1,119.9,119.2,111.2,70.1,69.8,32.0,31.9,29.8,29.7,29.6,29.5,29.4,29.3,26.1,26.0,22.7,22.6.14.1,14.0..MS (MALDI-TOF): m/z 2238[M+H]
+.HRMS (MALDI-TOF): C
152H
177N
10O
6The ultimate analysis calculated value: 2238.3928. measured value: 2238.3847.
Embodiment 4
Compound 1a (56mg, 0.025mmol) and Zn (OAc)
22H
2(38mg 0.17mmol) is dissolved in methylene dichloride (15mL) and methyl alcohol (5mL), stirring at room 20 hours to O.Add chloroform behind the pressure reducing and steaming solvent, wash with water, anhydrous sodium sulfate drying.Be spin-dried for solvent, column chromatography (sherwood oil/CH
2Cl
21: 1) obtain purple product 1b (47mg, 80%).IR (KBr): 3386,2923,2852,1658,1535,1486,1467,1003,796cm
-1.UV-Vis (perhydronaphthalene): 428,562,602nm.
1H NMR (300MHz, CDCl
3): δ 10.25 (s, 2H), 9.48 (s, 1H), 9.10 (2H), 8.83-8.94 (m, 16H), 8.10-8.21 (m, 14H), 7.60-7.73 (m, 18H), 7.28 (d, J=8.1Hz, 2H), 6.67 (s, 1H), 4.46 (t, J=6.6Hz, 4H), 4.16 (t, J=6.9Hz, 4H), 2.11 (m, 4H), 1.96 (m, 4H), 1.14-1.60 (m, 88H), 0.78-0.88 (m, 12H).
13C NMR (CDCl
3): δ 163.0,156.5, and 150.4,150.3,150.2,150.1,150.0,146.1,143.0,142.9,135.9,134.6,134.5,134.4,134.3,132.0,131.8,127.4,127.3,126.5,126.3,121.7,121.1,121.0,120.9,120.0,111.0,70.1,69.8,32.0,31.9,29.7,29.6,29.5,29.4,29.3,29.2,26.1,26.0,22.7,22.6,14.1,14.0.MS (MALDI-TOF): m/z 2367.2,2302.3, and 2240.2.
Embodiment 5
Compound 1a (56mg, 0.025mmol) and Cu (OAc)
22H
2(38mg 0.17mmol) is dissolved in methylene dichloride (15mL) and methyl alcohol (5mL), stirring at room 20 hours to O.Add chloroform behind the pressure reducing and steaming solvent, wash with water, anhydrous sodium sulfate drying.Be spin-dried for solvent, column chromatography (sherwood oil/CH
2Cl
21: 1) obtain purple product 1c (53mg, 91%).IR (KBr): 3389,2924,2853,1658,1537,1490,1468,1004,796cm
-1.UV-Vis (perhydronaphthalene): 415,538nm.MS (MALDI-TOF): m/z 2362.3,2240.4.C
152H
172Cu
2N
10O
6The ultimate analysis calculated value: C, 77.29; H, 7.34; N, 5.93. measured value: C, 77.22; H, 6.67; N, 5.82.
Embodiment 6
(4.51g, 13.8mmol), (6.36g 60.0mmol), is heated to backflow to phenyl aldehyde 6 to compound 11 in propionic acid (300mL).(5.36g 80.0mmol) continued stirring and refluxing 3 hours to add pyrroles 7.After the cooling, remove solvent under reduced pressure, add methylene dichloride (200mL) dissolving, water successively, saturated sodium bicarbonate, washing.Anhydrous sodium sulfate drying is spin-dried for solvent, column chromatography (CH
2Cl
2/ ethanol 50: 1) obtain purple solid phase prod 12 (1.01g, 9%).
1H NMR (300MHz, CDCl
3): δ 8.80-8.85 (m, 8H), 8.63 (d, J=2.4Hz, 1H), 8.20-8.22 (m, 7H), 7.71-7.80 (m, 9H), 7.32 (d, J=5.7Hz, 1H), 4.47 (t, J=6.3Hz, 2H), 4.08 (t, J=6.3Hz, 2H), 3.90-3.93 (m, 5H), 3.70-3.78 (m, 4H), (t, J=1.8Hz, 2H), 3.40 (s, 3H) ,-2.78 (s, 2H).
13C NMR (CDCl
3): δ 166.6,158.1,142.0,138.6,136.7,134.4,131.0128.9,128.4,127.9,127.6,126.6,120.1,119.0,118.3,111.9,71.9,71.8,71.0,70.7,70.5,69.6,69.2,58.9,51.9.MS (MALDI-TOF): m/z 835.6[M+H]
+.C
53H
46N
4O
6The ultimate analysis calculated value: C, 76.24; H, 5.55; N, 6.71. measured value: C, 76.68; H, 5.61; N, 6.35.
Embodiment 7
(420mg 0.50mmol) is dissolved in the 60mL pyridine compound 12, adds sodium hydroxide (2.00g, water 50mm0l) (30mL) solution then.16 hours postcooling of stirring and refluxing are to room temperature, and the hydrochloric acid that the drips 3N pH=3 that neutralizes uses methylene dichloride (100mL * 3) extraction then.Organic phase merges back contact water (100mL * 2) and saturated common salt water washing (100mL), after use anhydrous sodium sulfate drying.Be spin-dried for solvent, crude product column chromatography (CH
2Cl
2/ ethanol 20: 1) separate, obtain purple solid phase prod 13 (337mg, 82%).
1H NMR (300MHz, CDCl
3): δ 9.00 (d, J=1.8Hz, 1H), 8.80-8.92 (m, 5H), 8.76 (d, J=4.8Hz, 2H), 8.20-8.24 (m, 8H), 7.78 (m, 9H), 7.34 (d, J=5.7Hz, 1H), 4.59 (m, 2H), 4.09 (m, 2H), 3.87 (m, 2H), 3.81 (m, 2H), 3.73 (m, 2H), 3.62 (m, 2H), 3.42 (s, 3H) ,-2.78 (s, 2H).
13C NMR (CDCl
3): δ 165.7,157.2, and 147.2,142.1,139.9,138.5,136.6,134.6,131.4,129.0,127.8,126.7,120.5,120.4,117.6,117.1,111.8,72.0,70.9,70.7,69.5,68.8,59.1.MS (MALDI-TOF): m/z 821.1[M+H]
+.C
52H
44N
4O
6The ultimate analysis calculated value: C, 76.08; H, 5.40; N, 6.82. measured value: C, 75.46; H, 5.49; N, 6.34.
Embodiment 8
Compound 13 (420mg, 0.51mmol) and 2-(7-azo benzotriazole)-N, N, N ', (800mg 2.10mmol), uses 30mLN to N '-tetramethyl-urea phosphofluoric acid ester (HATU), dinethylformamide (DMF) dissolving, stirring at room 1 hour.Diamine compound 14 (0.25mmol) joins in the above-mentioned reaction solution then with 10mL DMF dissolving.Continue stirring at room 24 hours, and added the 100mL methylene dichloride again.Anhydrous sodium sulfate drying is used in mixing solutions water (100mL * 3) and saturated common salt water washing (100mL) then.After underpressure distillation removes and desolvates, gained crude product column chromatography (CH
2Cl
2/ methyl alcohol 20: 1) separate, obtain purple solid phase prod 15 (103mg, 19%).
1H NMR (300MHz, CDCl
3): δ 10.27 (s, 2H), 9.32 (s, 1H), 9.10 (d, J=2.4Hz, 2H), 8.75-8.85 (m, 16H), 8.16-8.21 (m, 14H), 7.59-7.76 (m, 18H), 7.35 (d, J=8.4Hz, 2H), 6.81 (s, 1H), 4.68 (t, J=4.8Hz, 4H), 4.34 (t, J=4.8Hz, 4H), 4.13 (t, J=4.8Hz, 4H), 3.92 (t, J=4.8Hz, 4H), 3.78 (t, J=4.8Hz, 4H), 3.35-3.65 (m, 36H), 3.32 (s, 6H), 3.26 (s, 6H) ,-2.83 (s, 2H).
13C NMR (CDCl
3): δ 163.0,156.6, and 146.4,142.1,138.0,134.6,130.8,129.1,127.6,126.7,122.6,121.5,120.1,118.9,111.9,71.8,70.9,71.8,70.9,70.8,70.7,70.5,70.4,69.8,69.6,69.5,59.1,59.0.MS (MALDI-TOF): m/z 2127.1[M+H]
+.HRMS (MALDI-TOF): C
128H
129N
10O
20Calculated value: 2125.9379. measured value: 2125.9365.
Embodiment 9
Compound 15 (30mg, 0.014mmol), Zn (OAc)
22H
2(100mg 0.45mmol), is dissolved in 30mL methylene dichloride and the 10mL methyl alcohol stirring at room 20 hours to O.Remove solvent under reduced pressure, add the chloroform dissolving, water (40mL * 3) and saturated aqueous common salt (40mL) washing, anhydrous sodium sulfate drying.Be spin-dried for solvent, column chromatography (CH
2Cl
2/ methyl alcohol 20: 1) obtain purple solid phase prod 2 (28mg, 89%).
1H NMR(300MHz，CDCl
3)：δ9.94(s，2H)，9.13(s，1H)，8.80-8.95(m，18H)，8.16-8.22(m，14H)，7.65-7.76(m，18H)，7.35(d，J＝8.4Hz，2H)，6.66(s，1H)，4.52(t，J＝4.2Hz，4H)，4.15(t，J＝4.5Hz，4H)，3.98(t，J＝4.5Hz，4H)，3.71(t，J＝4.5Hz，4H)，3.62(t，J＝4.5Hz，4H)，3.33-3.43(m，12H)，3.13-3.17(m，6H)，3.04(t，J＝4.2Hz，4H)，2.91-2.97(m，6H)，2.79(t，J＝1.8Hz，4H)，2.70(t，J＝4.2Hz，4H)，2.65(s，6H)，2.54(s，6H).
13C NMR(CDCl
3)：δ163.3，156.2，150.1，146.9，143.1，137.6，137.5，136.4，134.5，132.0，131.8，128.5，127.3，126.4，122.1，121.4，120.9，119.5，118.4，111.6，100.5，71.8，71.1，70.8，70.4，70.1，69.9，69.8，69.6，69.4，69.3，58.9，58.3，58.2.MS(MALDI-TOF)：m/z 2127.1[M-2Zn+5H]
+。
The preparation of fullerene derivate
Embodiment 10
Compound 18 (111mg, 0.25mmol), acid 19 (164mg, 0.50mmol), DMAP (10mg) is dissolved in the 30mL methylene dichloride, add under the stirring at room EDCI (250mg, 1.30mmol).Continue reaction 12 hours.Water (20mL * 4) is washed anhydrous sodium sulfate drying then.Be spin-dried for solvent, column chromatography (sherwood oil/EtOAc 20: 1) obtains white solid product 20 (92mg, 49%).IR (KBr): v 2920,2851,1749,1468,1203,1140,1062,873cm
-1.
1H NMR (300MHz, CDCl
3): δ 5.38 (d, J=3.6Hz, 1H), 4.69 (m, 1H), 4.64 (s, 2H), 4.15 (t, J=6.9Hz, 2H), 3.49 (s, 2H), 2.34 (d, J=7.8Hz, 2H), 0.84-2.05 (m, 69H), 0.68 (s, 3H).
13C NMR (CDCl
3): δ 166.6,166.1, and 166.0,139.2,123.0,75.5,65.9,61.6,56.7,56.2,50.0,42.3,41.1,39.5,36.6,36.2,35.8,31.9,31.8,29.7,29.6,29.5,29.4,29.2,28.5,25.8,22.8,22.7,19.3,18.7,14.1.C
48H
82O
6The ultimate analysis calculated value: C, 76.34; H, 10.94. measured value: C, 76.24; H, 11.16.
Embodiment 11
C
60(144mg, 0.20mmol), CBr
4(66mg, 0.20mmol), compound 20 (150mg 0.20mmol) is dissolved in (150mL) toluene, and dropping DBU (68 μ L, 0.20mmol).Stirring at room reaction 4 hours.Remove solvent under reduced pressure, column chromatography (is used CS earlier
2Toluene then) obtain brown solid product 3 (92mg, 31%).IR(KBr)：v 2920，2850，1747，1464，1262，1197，1096，801，526cm
-1.
1H NMR(300MHz，CDCl
3)：δ5.39(1H)，4.95(s，2H)，4.75(m，1H)，4.54(t，J＝6.0Hz，2H)，2.38(d，J＝7.8Hz，2H)，0.84-2.05(m，69H)，0.68(s，3H).
13CNMR(CDCl
3)：δ165.8，163.2，163.1，145.4，145.3，145.2，145.1，144.9，144.7，144.6，143.9，143.0，142.9，142.2，141.9，141.0，139.4，139.2，138.8，123.2，77.3，77.0，76.8，75.8，71.4，67.7，62.8，56.7，56.2，50.0，42.3，39.5，36.2，35.8，31.9，31.8，29.8，29.7，29.4，29.3，28.2，28.0，23.8，22.8，22.7，22.6，19.4，18.7，14.1，11.9。
Embodiment 12
Compound 21 (0.82g, 3.7mmol), cholesterol 16 (3.00g, 7.7mmol), DMAP (0.30g), HOBt (0.10g) with methylene dichloride (100mL) dissolving, add then EDCI (3.50g, 18mmol).Stirring at room reaction 3 days.Water (100mL * 5) and saturated common salt water washing (100mL) then, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, column chromatography (CH
2Cl
2) obtain white solid product 22 (1.53g, 43%).IR(KBr)：v 2938，2868，1782，1755，1468，1224，1140，1070cm
-1.
1H NMR(300MHz，CDCl
3)：δ5.39(d，J＝3.6Hz，2H)，4.70(m，2H)，4.65(s，4H)，3.62(s，2H)，2.39(d，J＝7.8Hz，4H)，0.84-2.05(m，76H)，0.68(s，6H).
13C NMR(CDCl
3)：δ166.5，165.4，139.2，123.1，75.6，61.7，56.7，56.1，50.0，42.3，39.7，39.5，37.9，36.9，36.6，36.2，35.8，31.9，31.8，28.2，28.0，27.6，24.3，23.8，22.8，22.6，21.0，19.3，18.7，11.9.Anal.Calcd.for C
61H
96O
8：C，76.52；H，10.11.Found：C，76.21；H，9.78。
Embodiment 13
C
60(144mg, 0.20mmol), CBr
4(66mg, 0.20mmol), compound 22 (190mg 0.20mmol) is dissolved in toluene (150mL), and adding DBU (100 μ L, 0.30mmol).Stirring at room reaction 4 hours.After removing solvent under reduced pressure, column chromatography (is used CS earlier
2Toluene then) obtain brown solid product 4 (77mg, 23%).IR(KBr)：v 2961，2866，1747，1465，1262，1197，1096，1025，803，527cm
-1.
1H NMR(300MHz，CDCl
3)：δ5.39(d，J＝2.7Hz，2H)，4.97(s，4H)，4.76(m，2H)，2.37(d，J＝9.6Hz，4H)，0.85-2.03(m，76H)，0.67(s，6H).
13C NMR(CDCl
3)：δ165.9，162.7，145.2，144.7，143.9，143.0，142.2，141.9，141.0，139.3，123.2，76.6，75.8，56.7，56.1，50.0，42.3，39.7，39.5，38.0，36.6，36.2，35.8，31.9，31.8，29.7，28.2，28.0，27.7，24.3，23.8，22.8，22.6，21.0，19.4，18.7，11.9。
Embodiment 14
The preparation of assembly
The biporphin compound and the fullerene derivate of equimolar amount are dissolved in toluene, and stirring at room 5 minutes removes solvent under reduced pressure, obtains assembly.
Embodiment 15
The gel test
Use the inverted method of test tube (test-tube-tilting).In the test tube about internal diameter 6mm, add a certain amount of gumforming compound and perhydronaphthalene solvent (concentration is 35mM).System is heated to 70 ℃, and it is dissolved fully.Slowly cooling (average 1.5 ℃/min) to room temperature (23 ℃).System can not flow if test tube is inverted, and then is defined as gel.If system has tangible viscosity to increase phenomenon, but still can flow, then be defined as semi-gelled.
Claims (12)
1. porphyrin-fullerene assembling body is characterized in that having following structure:
R in the formula
1, R
2Be identical or different group, be respectively C
8～C
16Alkyl, (CH
2CH
2O)
3CH
3Or (CH
2CH
2O)
4CH
3, M=Zn or Cu, Ph represent phenyl or substituted-phenyl, and the substituting group of described substituted-phenyl is C
1～C
6Alkyl or alkoxyl group,
R
3, R
4Be identical or different group, be respectively C
8～C
16Alkyl or
2. porphyrin-fullerene assembling body as claimed in claim 1 is characterized in that described R
1Be n-C
12H
25And R
2Be n-C
16H
33, perhaps R
1Be (CH
2CH
2O)
3CH
3And R
2Be (CH
2CH
2O)
4CH
3, M=Zn or Cu,
Described R
3Be n-C
16H
33Or
, R
4For
3. biporphin compound is characterized in that having following structural formula:
R in the formula
1, R
2Be identical or different group, be respectively C
8～C
16Alkyl, (CH
2CH
2O)
3CH
3Or (CH
2CH
2O)
4CH
3, M=Zn or Cu, Ph represents phenyl.
4. biporphin compound as claimed in claim 3 is characterized in that described R
1, R
2Be identical or different group, be respectively C
12H
25, (CH
2CH
2O)
3CH
3, (CH
2CH
2O)
4CH
3Or C
16H
33, M=Zn or Cu, Ph represents phenyl.
5. fullerene derivate is characterized in that having following structural formula:
R
3, R
4Be identical or different group, be respectively C
8～C
16Alkyl or
6. fullerene derivate as claimed in claim 5 is characterized in that described R
3, R
4Be identical or different group, be respectively n-C
16H
33Or
7. the preparation method of assembly as claimed in claim 1, it is characterized in that by biporphin compound and fullerene derivate in organic solvent, reaction preparation in 1 minute～5 hours under the room temperature, described biporphin compound and fullerene derivate have following structure respectively:
R wherein
1, R
2, R
3, R
4With M according to claim 1.
8. preparation method as claimed in claim 7 is characterized in that described organic solvent is a toluene, and described biporphin compound and fullerene derivate mol ratio are 1: 1,1 minute～5 hours reaction times.
9. preparation method as claimed in claim 7, the preparation method who it is characterized in that described biporphin compound is, condensation reaction takes place and obtains the biporphin compound in porphyrin acid compound and diamine compound in organic solvent, perhaps the above-mentioned biporphin compound that obtains is reacted in organic solvent with the hydrate of the hydrate of Zn salt, Cu salt, Zn salt or mantoquita again to obtain the biporphin compound that M is Zn or Cu; The condensing agent of described condensation reaction is carbodiimide hydrochloride or 2-(7-azo benzotriazole)-N, N, N ', N '-tetramethyl-urea phosphofluoric acid ester; Reaction times is 10～60 hours, and temperature of reaction is a room temperature, and the structural formula of described porphyrin acid compound and diamine compound is as follows:
R in the formula
1, R
2As described in claim 7.
10. preparation method as claimed in claim 7 is characterized in that the preparation method of described fullerene derivate is, in organic solvent, and malonic ester compound and soccerballene C
60React under organic bases and iodine or carbon tetrabromide condition, the reaction times is 1～10 hour, and temperature of reaction is a room temperature, and the structural formula of the compound of described malonic ester is as follows:
R in the formula
3Be C
8～C
16Alkyl or
11. the purposes of the described porphyrin-fullerene assembling body of claim 1 is characterized in that being used to prepare liquid crystal material and photoelectric material.
12. the purposes of the described porphyrin-fullerene assembling body of claim 1 is characterized in that as the Low Molecular-Weight Gel agent.
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