CN101210024A - Synthesis of middle position-tetraaryldiphenanthrene diselenoporphyrin derivative and application thereof - Google Patents
Synthesis of middle position-tetraaryldiphenanthrene diselenoporphyrin derivative and application thereof Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000003786 synthesis reaction Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 porphyrin compound Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 150000004032 porphyrins Chemical class 0.000 claims description 49
- 238000002360 preparation method Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LGYRSBHBVKFZGX-UHFFFAOYSA-N phenyl(selenophen-2-yl)methanol Chemical compound C1(=CC=CC=C1)C(O)C=1[Se]C=CC=1 LGYRSBHBVKFZGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004847 absorption spectroscopy Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 8
- 239000003814 drug Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002070 nanowire Substances 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000002560 therapeutic procedure Methods 0.000 abstract description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 230000005669 field effect Effects 0.000 abstract 1
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 241000272165 Charadriidae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PNNXBWWSFIVKQW-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCC PNNXBWWSFIVKQW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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Abstract
The invention discloses a 5,10,15,20-tetra-aryl diphenanthrene (9,10-b:9,10-1)-22,24-diseleno porphyrin compound which is obtained by the reaction of phenanthro-pyrrole and 2,5-di(aryl hydroxyl methyl) selenophen under low temperature and catalysis of BF3 Et2O in anaerobic atmosphere. The Soret spectral bands of the compound appear in 521nm, compared with tetraphenyl diseleno porphyrin without conjugated aromatic ring at beta-site, the Soret spectral bands are red shifted by 52nm and enter a green light zone above 500nm. The compound has wide application prospects in such areas as photodynamics therapy photosensitizer, OFETs (organic field effect tubes), molecular antenna, light energy converter, optical conversion material, molecular switch, molecular logic gate, molecular wire, organic solar battery, organic electroluminescence, non-linear optical material, optical storage, molecular identification and medicine and so on.
Description
One, technical field
The present invention relates to 5,10,15,20-four aryl two phenanthro-s [9,10-b:9,10-l]-22,24-two seleno derivatives of porphyrin and preparation method thereof.
Two, background technology
Porphyrins has the photoelectric properties of many uniquenesses, good light and thermally stable, bigger molar absorptivity is arranged in visible-range, thereby obtained paying close attention to widely and using in fields such as biological chemistry, medicine and pharmacology, analytical chemistry, photochemical catalysis and Materials science.In recent years, utilize the electronic structure and the photoelectric properties of porphyrin molecule uniqueness, the aspects such as development of design and synthetic photoelectric functional material and photoelectric device have become domestic and international ten minutes active research field, for example aspect the quantity of photogenerated charge and energy transfer of the biological photosynthetic reaction centre of simulation, the porphyrin molecule is as the light absorption units in the model compound, can realize that the photoinduction charge separation is [referring to (a) Gust D.Moore T.A.Science, 1989,244,35; (b) Wasielewski M.R.Chem.Review, 1992,92,435; (c) Moore T.A.Gust D.et al.Nature, 1984,307,630; (d) Liddell P.A.Kuciauskas D.Sumida J.P.et al.J.Am Chem.Soc .1997,119,1400; (e) Kuciauskas D.Liddell P.A.Moore A.L.et al J.Am.Chem.Soc.1998,120,10880; (f) Yfroah G.S.Liddell P.A.Nature, 1997,385,239; (g) Yfroah G.S.Liddell P.A.et al.Nature, 1998,392,497.]; In addition, porphyrin compound at organic effect electron tube (OFETs) [referring to Aramaki S.Sakai Y.Ono N.Appl.Phy.Let.2004,84,2085.], divide sub antenna [referring to (a) Li J.Ambroise A.Yang S.I.Diers J.R.Seth J.Wack C.R.Bocian D.F.Holten D.Lindsey J.S.J.Am.Chem.Soc.1999,121,8927; (b) Choi M.S.Aida T.Yamazaki T.et al.Angew.Chem.Int.Ed.2001,40,3194.], light-energy transmodulator [referring to: Gust D.Moore T.A.Moore A.L.Acc.Chem.Res.2001,34,40.], photoelectric conversion material [referring to: Crossley M.J.burn P.L.Chem.Commun.1991,21,1569.], molecular switch [referring to: Wasielewiski M.R.Goszrola D.Z.Science, 1992,257,63.], the molecule logical gate [referring to: Wagner R.W.Lindsey J.S.J.Am.Chem.Soc.1996,119,3996.], molecular wire [referring to: Richard W.Wagner R.W.Lindsey J.S.J.Am.Chem.Soc.1994,116,9759.], organic solar batteries [referring to: (a) Antohe S.Tugulea L.Phys.Stat.Sol (A), 1996,1153,581; (b) Takahashi K.Kuraya N.et al.Solar Enegy Materials ﹠amp; Solar Cell, 2000,61,403.], organic electroluminescent is [referring to Baldo M.A.O ' Bren D.F.et al.Nature, 1998,395,151.], nonlinear optical material is [referring to LidzeyD.G.Bradley D.C.et al.Nature, 1998,395,53.], optical storage [referring to: (a) Tyler B.N.Neil R.B.Adv.Mater, 2001,13 (5), 347; (b) Liu Z.M.Amir A.Yasseri J.Lindsey J.S.et al Science 2003,302 (28), 1543.], aspect such as molecular recognition and medicine [referring to Yang Jizhang, Chinese Journal of New Drugs, 1995,4 (3), 59] has a wide range of applications.
In four nitrogen-atoms in porphyrin center one or several replaced by other atoms (as O, S, Se, Te etc.), is called the porphyrin modified at the center, heterocycle porphyrin or for porphyrin.Just become meta-tetraphenyl two seleno porphyrin (Se after for example two nitrogen-atoms are replaced by two selenium atoms in meta-tetraphenylporphyrin
2TPP) [referring to Ulman, A.Manassen, J.Frolow, F.et al.Tetrahedron Letters 1978,2,167-170].The seleno porphyrin is except the extensive use that possesses above-mentioned general porphyrin, the photosensitizers that also can be used as photodynamic therapy is [referring to Lash T.D.in The Porphyrin Handbook, ed.Kadish, K.M.Smith, K.M.Guilard, R.Academic Press, San Diego, 2000, vol.2,125].
Research for meta-tetraphenyl two seleno porphyrins, the protoporphyrin compound that compares is wanted much less, at present international monopoly also have only one [referring to Detty, M.R.Gollnick, S.O.Davies, S.et al.PCT Int.Appl. (2003), 64, PatentNo.WO 2003011286, Application No.WO 2002-US24010], two seleno porphyrin compounds of bibliographical information all are the molecule that meta contains different aryl substituents in addition, and the Se that the β position replaces
2The report of TPP yet there are no bibliographical information.Wherein great majority be to its character research [referring to You, Y.Gibson, S.L.Hilf, R.Davies, S.R.et al.Journal ofMedicinal Chemistry 2003,46,3734-3747; Hilmey, D.G.Abe, M.Nelen, M.I.et al.Journal ofMedicinal Chemistry 2002,45,449-461.Stilts, C.E.Nelen, M.I.Hilmey, D.G.et al.Journal ofMedicinal Chemistry 2000,43,2403-2410; Stein, P.Ulman, A.Spiro, T.G.Journal of PhysicalChemistry 1984,88 (3), 369-374; Hill, R.L.Gouterman, M.Ulman, A.Inorganic Chemistry (1982), 21 (4), 1450-1455; Ulman, A.Manassen, J.Frolow, F.Rabinovich, D.InorganicChemistry 1981,20 (7), 1987-1990; Ulman, A.Manassen, J.Frolow, F.Rabinovich, D.Journal ofthe American Chemical Society 1979,101 (23), 7055-7059.].Seleno porphyrin molecule is normally by pyrroles and 2, and 5-two (phenyl hydroxymethyl) selenophen obtains [referring to Latos-Grazynski, L.The porphyrin handbook by condensation, oxidizing reaction under acidic conditions; Kadish, K.M.Smith, K.M.Guilard, T.Eds.Academic:New York, 2000; Vol.2, pp 361-416; Ulman, A.Manassen, J.Frolow, F.Rabinovich, D.Tetrahedron Letters1978, (2), 167-70.].Because ring-opening polymerization and oxidizing reaction easily take place in the pyrroles under catalyst action, cause by product many, purification difficult, productive rate is lower, is generally 10%, even lower.
The characteristic spectrum of porphyrin generally is to be absorbed in Soret bands of a spectrum very strong about 400nm or to claim B peak (S by one
0→ S
2Transition) and four be absorbed in Q bands of a spectrum (S more weak more than the 500nm
0→ S
1Transition) constitutes.Except the porphyrin system of ring expansion, the feature electron absorption band of porphyrin molecule seldom has above more than the 500nm.But no matter be to be applied in optical dynamic therapy and near infrared sensor, still be applied in fields such as nonmetal electronic conductor, catalysis and solar energy converting material, all need to have strong absorption at the long visible light wave range (more than the 500nm) of wavelength as the porphyrin compound of photosensitizers.The synthetic electron absorption of design as seen/porphyrins of near infrared region is the field, forward position of current international research.People have carried out a lot of effort aspect the longer porphyrin compound of absorb light wavelength exploring.Know that the ultraviolet-visible absorption peak of porphyrin quasi-molecule mainly is subjected to the influence of its molecule parent planarity, planarity is poorer, absorption spectrum λ
MaxRed shift further [referring to Haddad, R.E.Gazeau, S.Pecaut, J.J.Am.Chem.Soc.2003,125,1253].In addition, and usefulness Se atom replacement center nitrogen-atoms [referring to Ulman, A.Manassen, J.Frolow, F.Rabinovich, D.Tetrahedron Letters 1978,2,167-170], the substituted radical that perhaps changes porphyrin molecule meta or β position is [referring to Lash T.D.in The Porphyrin Handbook, ed.Kadish, K.M.Smith, K.M.Guilard, R.Academic Press, San Diego, 2000, vol.2,125], can make spectral red shift, for example Se
2The λ of TPP
Max(469nm) just there is not meta-tetraphenylporphyrin H of modifying than the center
2TPP (419nm) red shift 40nm, but also far from 500nm.
Three, summary of the invention
The purpose of this invention is to provide meta-tetraphenyl two phenanthro-s two seleno derivatives of porphyrin and preparation method thereof.
Technical scheme of the present invention is as follows:
Meta-tetraphenyl two phenanthro-s two seleno porphyrins, its general structure is seen accompanying drawing 1.Wherein, the R group can be hydrogen, chlorine, methoxyl group, n-Hexadecane oxygen base etc.
A kind of method for preparing above-mentioned meta-tetraphenyl two phenanthro-s two seleno derivatives of porphyrin, chemical equation is seen accompanying drawing 2:
The BF that in reaction vessel, adds selenophen derivative, phenanthro-pyrroles and catalytic amount
3Et
2O makes solvent with anhydrous methylene chloride, and reaction is 48 hours under oxygen free condition.Product carries out column chromatography for separation, obtains meta-four aryl two phenanthro-s two seleno derivatives of porphyrin behind methyl alcohol and chloroform recrystallization.
With
1H-NMR, IR, UV-Vis, ESI MASS and MALDI-TOF MASS characterize and have confirmed the structure (seeing accompanying drawing and subordinate list) of derivatives of porphyrin.Detecting used instrument is: (TMS is interior mark to BrukerARX500 type nuclear magnetic resonance analyser, deuterium is a solvent for DMSO), Tianjin, island UV-3100 type ultraviolet-visible spectrophotometer (sweep limit 400～1000nm, light path slit 2nm), the micro-fusing point instrument of X-4 digital display, U.S. Thermo ELECTRON CORPORATION mass spectrum workstation, American AB I MALDI-TOF mass spectrum Voyager System.
Beneficial effect of the present invention
The present invention compared with prior art, its remarkable advantage is: having synthesized meta first is that phenyl replaces, the β position is the heterocycle derivatives of porphyrin of phenanthrene ring conjugation, the Soret bands of a spectrum of this class conjugation porphyrin compound appear at 521nm, the tetraphenyl two seleno porphyrins that do not have a kinds of aromatic ring conjugation with the β position relatively its Soret bands of a spectrum red shift 52nm, enter the above green glow zone of 500nm.This is the center modified porphyrin compound of absorbing wavelength maximum up to now, can improve the assimilated efficiency to visible light greatly, improves the efficiency of conversion of solar cell.This compounds has a wide range of applications at aspects such as organic effect electron tube (OFETs), branch sub antenna, light-energy transmodulator, photoelectric conversion material, molecular switch, molecule logical gate, molecular wire, organic solar batteries, organic electroluminescent, nonlinear optical material, optical storage, molecular recognition and medicine.
Four, description of drawings
Fig. 1 is meta-tetraphenyl two phenanthro-s two seleno derivatives of porphyrin structural formulas;
Fig. 2 is the chemical equation of preparation meta-tetraphenyl two phenanthro-s two seleno derivatives of porphyrin;
Fig. 3 is the MALDI-TOFMS spectrum of embodiment of the invention 1a;
Fig. 4 is the ultra-violet absorption spectrum of embodiment of the invention 1a;
Fig. 5 is the MALDI-TOF MS spectrum of embodiment of the invention 1b;
Fig. 6 is the ultra-violet absorption spectrum of embodiment of the invention 1b;
Fig. 7 is the MALDI-TOF MS spectrum of embodiment of the invention 1c;
Fig. 8 is the ultra-violet absorption spectrum of embodiment of the invention 1c;
Fig. 9 is the MALDI-TOFMS spectrum of embodiment of the invention 1d;
Figure 10 is the ultra-violet absorption spectrum of embodiment of the invention 1d;
Five, embodiment
Embodiment 1:5; 10,15,20-tetraphenyl-two phenanthro-[9; 10-b:9; 10-l]-22, synthesizing of 24-two seleno porphyrins (1a) adds 1mmol (278mg) 2 in the 250ml round-bottomed flask, 5-two (phenyl hydroxymethyl) selenophen, 1mmol (217mg) phenanthro-pyrroles and 60ml anhydrous methylene chloride; putting into magneton begins to stir; under the argon shield reaction flask is put into cryogenic unit and lucifuge, control reaction temperature is at-50 ± 5 ℃, and adding total amount is the BF of 80 μ l
3Et
2O, make it react 2 hours at low temperatures after, allow it be warming up to room temperature naturally again and continue reaction 48 hours.1.0mmol DDQ (227mg) joins in the reaction soln, reacts 1 hour.The pressure reducing and steaming solvent carries out chromatographic separation, obtains green crystals behind methyl alcohol and chloroform recrystallization.Productive rate: 19.7%; Molten point:＞250 ℃; MALDI-TOFMS:calcd for C
68H
40N
2Se
21042.98, found:1044.47 (M
+) (Fig. 3);
1H-NMR (500MHz, CDCl
3) δ 8.71 (4H, s), 8.63-8.65 (4H, m), 8.50 (8H, m), 8.26-8.27 (4H, m), 7.71 (8H, m), 7.61 (4H, m), 7.44 (4H, m), 7.10 (4H, m); UV-vis:505nm, 580nm, 810nm (Fig. 4).
Embodiment 2:5,10,15,20-four (4-chloro-phenyl-)-two phenanthro-s [9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1b) are with embodiment 1, productive rate: 29.4%.Molten point:＞250 ℃; MALDI-TOFMS:calcd for C
68H
36Cl
4N
2Se
21180.76, found:1182.45 (M
+) (Fig. 5);
1H-NMR (500MHz, CDCl
3) δ 8.67-8.69 (4H, m), 8.64 (4H, m), 8.40-8.42 (8H, m), 8.20-8.21 (4H, m), 7.69-7.70 (8H, m), 7.50-7.53 (4H, m), 7.17-7.20 (4H, m); UV-vis:524nm, 598nm, 820nm (Fig. 6).
Embodiment 3:5,10,15,20-four (4-methoxyphenyl)-two phenanthro-s [9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1c) are with embodiment 1, productive rate: 43.9%.Molten point:＞250 ℃; MALDI-TOFMS:calcd for C
72H
48N
2O
4Se
21163.08, found:1162.80 (M
+) (Fig. 7);
1H-NMR (500MHz, CDCl
3) δ 8.62-8.65 (8H, m), 8.42-8.43 (8H, m), 8.27-8.29 (4H, m), 7.42-7.45 (4H, m), 7.22-7.26 (8H, m), 7.12-7.15 (4H, m), 3.99 (12H, s); UV-vis:526nm, 605nm, 844nm (Fig. 8).
Embodiment 4:5,10,15,20-four (4-n-Hexadecane oxygen phenyl)-two phenanthro-s [9,10-b:9,10-l]-22,24-two seleno porphyrins (1d) synthetic
The preparation method is with embodiment 1, productive rate: 41.3%; Molten point: 151 ℃; MALDI-TOF MS:calcd for C
132H
168N
2O
4Se
2, 2004.68, found:2006.88 (M
+) (Fig. 9);
1H-NMR (500MHz, CDCl
3) δ 8.68 (4H, s), 8.62-8.64 (4H, d), 8.41-8.42 (8H, m), 8.27-8.29 (4H, m), 7.41-7.44 (4H, m), 7.22-7.24 (8H, m), 7.11-7.14 (4H, m), 4.12-4.14 (8H, t), 1.99-1.94 (8H, m), 1.33 (104, s), and 0.93-0.94 (12H, m); UV-vis:530nm, 606nm, 849nm (Figure 10).
Embodiment 5:5,10,15,20-tetraphenyl-two phenanthro-[9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1a) is with embodiment 1, but control reaction temperature is at-40 ℃.Productive rate: 11.3%.
Embodiment 6:5,10,15,20-tetraphenyl-two phenanthro-[9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1a) is with embodiment 1, but oxygenant is p-Chloranil.Productive rate: 9.3%.
Embodiment 7:5,10,15,20-tetraphenyl-two phenanthro-[9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1a) be with embodiment 1, but 2,5-two (phenyl hydroxymethyl) selenophen and phenanthro-pyrroles mol ratio are 1.2: 1.Productive rate: 14%.
Embodiment 8:5,10,15,20-tetraphenyl-two phenanthro-[9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1a) be with embodiment 1, but 2,5-two (phenyl hydroxymethyl) selenophen and phenanthro-pyrroles mol ratio are 1.1: 1.Productive rate: 16%.
Embodiment 9:5,10,15,20-tetraphenyl-two phenanthro-[9,10-b:9,10-l]-22, the synthesis preparation method of 24-two seleno porphyrins (1a) be with embodiment 1, but 2,5-two (phenyl hydroxymethyl) selenophen and phenanthro-pyrroles mol ratio are 0.8: 1.Productive rate: 8%.
Claims (6)
1. meta-four aryl two phenanthro-s two seleno porphyrin compounds, its structural formula is as follows:
R is H, Cl, OCH
3Or OC
16H
33
2. the preparation method of the compound of claim 1, concrete steps are as follows:
(1) in reaction vessel, adds 2,5-two (aryl hydroxymethyl) selenophen, phenanthro-pyrroles and anhydrous methylene chloride, wherein 2,5-two (phenyl hydroxymethyl) selenophen and phenanthro-pyrroles mol ratio are 1.2: 1 to 0.8: 1, under oxygen free condition, reaction flask put into cryogenic unit and lucifuge, control reaction temperature adds the BF of catalytic amount then below-40 ℃
3Et
2O, make it react 2 hours at low temperatures after, allow it be warming up to room temperature naturally again and continue reaction 48 hours;
(2) will join in the reaction soln of step (1) with the oxygenant of mole number with the phenanthro-pyrroles, react 1 hour, the pressure reducing and steaming solvent gets meta-tetraphenyl two phenanthro-s two seleno porphyrins.
3. preparation method according to claim 2 is characterized in that control reaction temperature is between-50 ± 5 ℃ in the step (1).
4. preparation method according to claim 2 is characterized in that oxygenant is DDQ in the step (2).
5. preparation method according to claim 2 is characterized in that the reaction mol ratio of middle pyrroles of step (1) and selenophen is (1: 1).
6. the purposes of the compound of claim 1 is characterized in that: the significant red shift of the ultraviolet-visible absorption spectroscopy of the compound of claim 1.
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