CN104761578B - Based on rhodium tetraphenylporphyrin azepine fluorine boron two pyrroles's near infrared absorption phosphor material and its preparation method and purposes - Google Patents
Based on rhodium tetraphenylporphyrin azepine fluorine boron two pyrroles's near infrared absorption phosphor material and its preparation method and purposes Download PDFInfo
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- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims description 22
- 238000010521 absorption reaction Methods 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 13
- -1 rhodium tetraphenylporphyrin azepine fluorine boron Chemical compound 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000010948 rhodium Substances 0.000 claims abstract description 16
- AMZABBNNBJXIGP-UHFFFAOYSA-N [B].[F].N1C=CC=CC=C1.C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] Chemical compound [B].[F].N1C=CC=CC=C1.C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] AMZABBNNBJXIGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 claims description 8
- YBCUEJCLNHHXBS-UHFFFAOYSA-K [Rh](Cl)(Cl)Cl.C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2 Chemical compound [Rh](Cl)(Cl)Cl.C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2 YBCUEJCLNHHXBS-UHFFFAOYSA-K 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 206010028980 Neoplasm Diseases 0.000 claims description 4
- DTKVAHYKYRDBSY-UHFFFAOYSA-N [B].[F].N1C=CC=CC=C1 Chemical compound [B].[F].N1C=CC=CC=C1 DTKVAHYKYRDBSY-UHFFFAOYSA-N 0.000 claims description 4
- 201000011510 cancer Diseases 0.000 claims description 4
- 238000002560 therapeutic procedure Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 125000001475 halogen functional group Chemical group 0.000 claims 2
- WDFMGHVUOCNRLB-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin hydrochloride Chemical compound Cl.c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 WDFMGHVUOCNRLB-UHFFFAOYSA-N 0.000 claims 1
- 206010011224 Cough Diseases 0.000 claims 1
- 239000012267 brine Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 4
- JZMMZXDSJLGJFD-UHFFFAOYSA-N 2-bromo-1h-azepine Chemical compound BrC1=CC=CC=CN1 JZMMZXDSJLGJFD-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- SBHDJEBOAUTUSH-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] SBHDJEBOAUTUSH-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 231100000002 MTT assay Toxicity 0.000 description 2
- 238000000134 MTT assay Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 208000007578 phototoxic dermatitis Diseases 0.000 description 2
- 231100000018 phototoxicity Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- HMKMKLAEOLHRDT-UHFFFAOYSA-N N1C(C=C2C3=C4C=CC=CC4=CC=C3C(C=C3NC(=C4)C=C3)=N2)=CC=C1C=C1C=CC4=N1 Chemical class N1C(C=C2C3=C4C=CC=CC4=CC=C3C(C=C3NC(=C4)C=C3)=N2)=CC=C1C=C1C=CC4=N1 HMKMKLAEOLHRDT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- NPRDEIDCAUHOJU-UHFFFAOYSA-N [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NPRDEIDCAUHOJU-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002165 resonance energy transfer Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0076—PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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Abstract
The near-infrared compound based on rhodium porphyrin azepine fluorine boron two pyrroles for one class, they have following structure：Compared with prior art, its remarkable advantage is the present invention：First passage Rh C key axial direction connected mode has synthesized rhodium porphyrin azepine fluorine boron two pyrroles { Rh (ttp) aza BODIPY } compound.Such compound is with the optical property of transition metal rhodium and aza BODIPY.On the one hand, due to central metal RhШUnique d6Electronic configuration, so that this compound has very effective intersystem crossing coefficient, produces long-life phosphorescent emissions and singlet oxygen.On the other hand, aza BODIPY has very strong absorption near infrared region, can successfully by the absorbing wavelength red shift of this compound near infrared region, be more beneficial for being widely applied.The invention discloses its preparation method.
Description
Technical field
The present invention relates near infrared absorption phosphor material, specifically, it is related to rhodium tetraphenylporphyrin-azepine fluorine boron two pyrroles
{ Rh (ttp)-aza-BODIPY } near infrared absorption phosphor material and its preparation method and purposes.
Background technology
Near infrared absorption fluorescent dye becomes the focus of Recent study due to its unique performance, widely applies
In various fields.In near infrared region, biological tissue absorbs and scattering is minimum, [referring to：(a)Aubin,
J.E.Autofluorescence of viable cultured mammalian
cells.J.Histochem.Cytochem.,1979,27,36–43.12.(b)Weisleder,R.A clearer vision
For in vivo imaging.Nat.biothchnol., 2001,19,316-317.] therefore can be greatly enhanced the group of photon
The impact knitted penetration capacity and avoid autofluorescence interference, reduces the light injury to organism.[referring to：(a)Wu,X.M.,et
al.In vivo and in situ tracking cancer chemotherapy by highly photostable NIR
fluorescent theranostic prodrug.J.Am.Chem.Soc.,2014,136,3579-3588.(b)Wu,X.M.；
Chang S.；Sun X.R.,et al.Constructing NIR silica-cyanine hybrid nanocomposite
for bioimaging in vivo:a breakthrough in photo-stability and bright
Fluorescence with large Stokes shift.Chem.Sci., 2013,4,1221 1228.] phosphorescent compound quilt
It is considered the material of a class great potential, be widely used in the fields such as OLED, solaode.[referring to：(a)Li,
L.L.；Diau,E.W-G.Porphyrin-sensitized solar cells.Chem.Soc.Rev.,2013,42,291-
304.] compared with conventional fluorescent material, phosphorescent compound has luminescent lifetime length and big Stokes shift advantage.Other one
Individual important advantage is that phosphor material shows the advantage of uniqueness in OLED application aspect, and such as fluorescent material can only pass through substance
State-singlet energy branch mode forms singlet excitons, and phosphor material turns not only by singlet state-singlet energy
Move, simultaneously again can be by triplet-triplet energies branch mode formation exciton, therefore phosphor material quantum in highest in theory
Yield can reach 100%, can overcome the restriction of quantum yield in fluorescent material 25%.[referring to：(a)Tao,Y.T.；
Yang,C.H.；Qin,J.G.Organic host materials for phosphorescent organic light-
emitting diodes.Chem.Soc.Rev.,2011,40,2943-2970.(b)Baldo,M.A.；O’Brien,B.F.；
You,Y.,et al.Highly efficient phosphorescent emission from organic
Electroluminescent devices.Nature, 1998,395,151-154.] therefore, based near infrared absorption and phosphorescence
The advantage of transmitting, near infrared absorption phosphor material has wide application at aspects such as following military affairs, the energy, biology and environment
Prospect.
Transient metal complex is the phosphor material of a class excellent performance, and its remarkable advantage is that luminescent lifetime is long, but by
In metal to ligand charge transfer (MLCT) and part to metal electric charge transfer (LMCT) near infrared region electron transition taboo
Resistive matter, the absorption near infrared region for such material very overly soft pulse to no any absorption, this property seriously limits this kind of compound
Application.Nir dye the most frequently used at present is organic fluorescence small molecule, is typically reached by organic compound structure method of modifying
To the purpose of red-shifted absorption wavelength, but its luminescent lifetime is typically very short, generally can extend its life-span by introducing heavy atom,
But organic molecule typically understands the red shift with absorbing wavelength and stability is gradually lowered.As business-like nir dye at present
The less stable of middle Cy5, Cy7, this greatly limits it and extensively applies.[referring to：(a)Benson,R.C.；Kues,
H.A.Absorption and fluorescence properties of cyanine dyes.Chem.Eng.Data,
1977,22,379-383.(b)Zhang X.F.；Xiao,Y.；Qi,J.,et al.Long-wavelength,
photostable,two-photon excitable BODIPY fluorephores readily modifiable for
Molecular probes.J.Org.Chem., 2013,78,9153-9160.] porphyrin is as the natural photosensitizer of a class, widely
It is present in nature, and play important role.It is the part that a class has extremely strong coordination ability, the periodic table of elements
In most elements include metal and nonmetallic can with porphyrin be coordinated generate various property compound, but its
Significantly shortcoming is that near infrared absorption is weaker.The method of porphyrin absorbing wavelength red shift near infrared region is logical by one of which
Cross thick on porphyrin ring and aromatic rings, profit has designed and synthesized the phosphorescence of Pd and Pt porphyrin near infrared absorption in this way
Compound, but this method can only obtain a class compound.[referring to：(a)Niedermair,F.；Borisov,S.M.；Zenkl,
G.,et al.Tunable phosphorescent NIR oxygen indicators based on mixed benzo-
and naphthoporphyrin complexes.Inorg.Chem.,2010,49,9333-9342.(b)Sommer,J.R.；
Shelton,A.H.；Parthasarathy,A.,et al.Photophysical properties of near-infrared
phosphorescentπ-extended platinum porphyrins.Chem.Mater.,2011,23,5296-5304.
(c).Lebedev,A.Y.；Cheprakov,A.V.；Sakadzìc,S.,et al.Densritic phosphorescent
probes for oxygen imaging in biological systems.ACS Appl.Mater.Interfaces,
2009,1,1292-1304.] azepine fluorine boron two pyrroles (aza-BODIPY) is the nir dye of a quasi-representative, is nearly ten years
The new fluorescent chemicalses of the class that grows up, are increasingly favored by scientists.This kind of compound is near infrared region
There is stronger molar absorption coefficient, but its luminescent lifetime is shorter.[referring to：(a)Loudet,A.；Burgess,K.BODIPY
dyes and their derivatives:syntheses and spectroscopic
properties.Chem.Rev.2007,107,4891–4932.(b)Kiloran,J.,Allen,L.,Gallagher,J.F.,
Gallagher,W.M.；O’Shea,D.F.Synthesis of BF2chelates of
tetraarylazadipyrromethenes and evidence for their photodynamic therapeutic
behavior.Chem.Commun.,2002,17,1862-1863.(c)Pierre,A.B.,et al.Two-photo
absorption-related properties of functionalized BODIPY dyes in the infrared
Range up to telecommunication wavelengths.Adv.Mater.2009,21,1151-1154.] except this it
Outward, aza-BODIPY also has relatively more negative reduction potential energy, such as its S1Excited energy is less than common BODIPY, this property
Make it can be used as preferable intramolecular energy acceptor.[referring to：(a)Guo,S.；Ma,L.H.；Zhao,J.,et
al.BODIPY triads triplet photosensitizers enhanced with intramolecular
resonance energy transfer(RET):broadband visible light absorption and
application in photooxidation.Chem.Sci.,2014,5,489–500.(b)Bandi,V.；El-Khouly,
M.E.；Nesterov,V.N.,et al.Self-assembled via metal-ligand coordination aza
BODIPY-zinc phthalocyanine and azabodipy-zinc naphthalocyanine conjugates:
synthesis,structure,and photoinduced electron transfer.J.Phys.Chem.C,2013,
117,5638-5649.] therefore, aza-BODIPY be a kind of more satisfactory strengthen rhodium porphyrin near infrared region absorb glimmering
Optical molecule.
Content of the invention
In the present invention, rhodium porphyrin and aza-BODIPY are dexterously directly connected by first by metal-carbon key
Come.In this connected mode, transition metal d track and aza-BODIPY directly participate in frontier molecular orbitals bonding, due to weight
The participation of metal d track, intersystem crossing coefficient dramatically increases, thus effectively improving luminescent lifetime.Meanwhile, aza-BODIPY is also
Can make the absorption of transient metal complex successfully red shift near infrared region.We have designed and have closed in this way
Become a series of rhodium tetraphenylporphyrins-azepine fluorine boron two pyrroles { Rh (ttp)-aza-BODIPY } near infrared absorption phosphor material.
This is a kind of method of very simple and flexible, can as desired by change transient metal complex or change its with closely red
The connected mode of outer dyestuff obtains a series of near infrared absorption phosphor materials, and this provides a kind of novel easy synthesis side for us
Method.
Present invention is to design and provide a class rhodium porphyrin-azepine fluorine boron two pyrroles { Rh (ttp)-aza-BODIPY }
Near infrared absorption phosphor material and preparation method thereof and property research.
The present invention relates to technical scheme is as follows：
The near-infrared compound based on rhodium porphyrin-azepine fluorine boron two pyrroles for one class, they have following structure：
The preparation method of above-claimed cpd is as follows：
A kind of method preparing the above-mentioned near-infrared compound based on rhodium porphyrin-azepine fluorine boron two pyrroles, it includes following
Step：
Add rhodium tetraphenylporphyrin chloride (Rh (ttp) Cl) (1eq), halo azepine fluorine boron two pyrroles in the reactor
(halo aza-BODIPY) (1.1eq), K2CO3(20eq) and benzene solvent, reactant mixture freezing degassing three times, in nitrogen protection
Lower 150 DEG C of reactions, question response terminates, and decompression is spin-dried for solvent, uses CH2Cl2The developing solvent of/hexane carries out silica gel column chromatography and separates,
Obtain the near infrared absorption phosphorescent compound based on rhodium porphyrin-azepine fluorine boron two pyrroles.
Characterized with 1H-NMR, UV-Vis, Fluorescence spectral, MALDI-TOF MASS and confirm this light
Quick dose of structure.
Beneficial effects of the present invention
Compared with prior art, its remarkable advantage is the present invention：First passage Rh-C key axial direction connected mode has synthesized rhodium
Porphyrin-azepine fluorine boron two pyrroles { Rh (ttp)-aza-BODIPY } compound.Such compound with transition metal rhodium and
The optical property of aza-BODIPY.On the one hand, due to central metal RhШUnique d6Electronic configuration is so that this compound has
Very effective intersystem crossing coefficient, produces long-life phosphorescent emissions and singlet oxygen.On the other hand, aza-BODIPY is near
There is very strong absorption ultrared, successfully this compound of red can be moved on near infrared region, be more beneficial for being widely applied.
These achievements in research provide a kind of method of easier flexible synthesis near infrared absorption phosphor material for us.Due to such chemical combination
The advantages of thing possesses near infrared absorption, long lifetime phosphorescent, can produce the singlet oxygen killing cancerous cell simultaneously, has phosphorescence
Picture and optical dynamic therapy property, therefore can be used for the real-time diagnosis treatment of cancer.2nd, due to heavy atoms effect, produce effectively
Intersystem crossing coefficient, can as triplet state photosensitizer be used for light-catalyzed reaction.3rd, can be used for photoelectric material.With traditional
Fluorescent material is compared, and phosphorescent compound has the long phosphor-decay life-span, and the important feature of another one is that it can catch simultaneously
Obtain singletstate and triplet excitons, reach internal quantum efficiency theoretical value 100% utilization ratio, can be used for OLED.
Brief description
Fig. 1 is the ultra-violet absorption spectrum of photosensitizer A in the present invention；
Fig. 2 is the ultra-violet absorption spectrum of photosensitizer B in the present invention；
Fig. 3 is the ultra-violet absorption spectrum of photosensitizer C in the present invention；
Fig. 4 is the emission spectrum of photosensitizer A in the present invention；
Fig. 5 is the emission spectrum of photosensitizer B in the present invention；
Fig. 6 is the emission spectrum of photosensitizer C in the present invention；
Fig. 7 is photosensitizer A in the present invention, B and C stability；
Fig. 8 is photosensitizer A in the present invention, and B is contrasted with methylene blue singlet oxygen generation efficiency；
Fig. 9 is that in the present invention, photosensitizer C and methylene blue singlet oxygen generation efficiency contrast；
Figure 10 is the MTT assay test result of photosensitizer C in the present invention.
Specific embodiment
Detect that instrument is：(TMS is internal standard to BrukerARX500 type nuclear magnetic resonance analyser, deuterated C6D6For solvent), Shimadzu
UV-4500 type ultraviolet-visible spectrophotometer (sweep limitss 300-900nm, slit width 2.0nm), the F-4600 U.S. of Hitachi
BrukerDaltonicsautoflexII mass spectrum work station.
The synthesis of embodiment 1. compound A：
Add rhodium tetraphenylporphyrin chloride Rh (ttp) Cl (15.8mg, 0.019mmol), bromo azepine in the reactor
Fluorine boron two pyrroles aza-BODIPY-a (13.7mg, 0.021mmol), K2CO3(53.9mg, 0.39mmol) and 1.0mL benzene, reaction
Mixture freezing degassing three times, 150 DEG C are reacted 28 hours under nitrogen protection.Question response terminates, and decompression is spin-dried for solvent, uses
CH2Cl2/hexane(1:1) developing solvent carries out silica gel column chromatography and separates, and obtains 17.1mg compound A. yield：61%.Rf=
0.61(CH2Cl2/ hexane=1:1).1H NMR(400MHz,CDCl3):δ 0.44 (d, J=8.5Hz, 2H), 2.69 (s,
12H), 5.45 (d, J=8.4Hz, 2H), 5.98 (s, 1H), 6.75 (s, 1H), 7.30-7.36 (m, 6H), 7.45 (d, J=
8.0Hz, 2H), 7.51-7.52 (m, 9H), 7.56-7.63 (m, 3H), 7.80 (d, J=3.3Hz, 2H), 8.04 (d, J=
7.7Hz, 4H), 8.09 (d, J=7.8Hz, 4H), 8.87 (s, 8H).；HRMS(FABMS):Calcd for
[C80H56BBrF2RhN7]+([M]+):m/z 1347.2903.Found:m/z.1347.2906.Its ultra-violet absorption spectrum is shown in Fig. 1,
Emission spectrum is shown in Fig. 4, and stability is shown in Fig. 7, sees Fig. 8 with the contrast of methylene blue singlet oxygen generation efficiency.
The synthesis of embodiment 2. compound B：
Add rhodium tetraphenylporphyrin chloride Rh (ttp) Cl (15.8mg, 0.019mmol), bromo azepine in the reactor
Fluorine boron two pyrroles aza-BODIPY-b (13.7mg, 0.021mmol), K2CO3(53.9mg, 0.39mmol) and 1.0mL benzene, reaction
Mixture freezing degassing three times, 150 DEG C are reacted 30 hours under nitrogen protection.Question response terminates, and decompression is spin-dried for solvent, uses
CH2Cl2/hexane(1:1) developing solvent carries out silica gel column chromatography and separates, and obtains 11.4mg compound B. yield：66%.Rf=
0.57(CH2Cl2/ hexane=1:1).1H NMR(400MHz,CDCl3):δ 0.52 (d, J=8.6Hz, 2H), 2.71 (s,
12H), 5.57 (d, J=9.0Hz, 2H), 6.22 (s, 1H), 6.71 (s, 1H), 7.25-7.30 (m, 3H), 7.48 (d, J=
7.8Hz, 2H), 7.51-7.58 (m, 9H), 7.60-7.67 (m, 6H), 7.82 (d, J=7.2Hz, 2H), 8.06 (d, J=
7.6Hz,8H),8.83(s,8H).HRMS(FABMS):Calcd for[C80H56BBrF2RhN7]+([M]+):m/z
1347.2903.Found:m/z.1347.2908.
Its ultra-violet absorption spectrum is shown in Fig. 2, and emission spectrum is shown in Fig. 5, and stability is shown in Fig. 7, produces with methylene blue singlet oxygen
Efficiency comparative sees Fig. 8.
The synthesis of embodiment 3. compound C：
Add rhodium tetraphenylporphyrin chloride Rh (ttp) Cl (15.8mg, 0.019mmol), bromo azepine in the reactor
Fluorine boron two pyrroles aza-BODIPY-c (13.7mg, 0.021mmol), K2CO3(53.9mg, 0.39mmol) and 1.0mL benzene, reaction
Mixture freezing degassing three times, 150 DEG C are reacted 32 hours under nitrogen protection.Question response terminates, and decompression is spin-dried for solvent, uses
CH2Cl2/hexane(1:1) developing solvent carries out silica gel column chromatography and separates, and obtains 6.74mg compound B. yield：39%.1H
NMR(400MHz,CDCl3):δ 0.40 (d, J=8.4Hz, 1H), 0.44 (s, 1H), 2.67 (s, 12H), 5.00 (t, J1=
4.0Hz,J2=7.8Hz, 1H), 5.51 (s, 1H), 6.33 (d, J=7.4Hz, 1H), 6.69 (s, 1H), 6.88 (t, J1=
7.8Hz,J2=7.8Hz, 1H), 7.17 (d, J=7.8Hz, 1H), 7.37-7.39 (m, 8H), 7.47-7.50 (m, 2H), 7.53-
7.55 (m, 5H), 7.71 (s, 1H), 7.81-7.82 (m, 4H), 7.84 (d, J=8.0Hz, 4H), 7.99 (d, J=7.4Hz,
4H),8.08(s,8H).HRMS(FABMS):Calcd for[C80H56BBrF2RhN7]+([M]+):m/z
1347.2903.Found:m/z.1347.2906.
Its ultra-violet absorption spectrum is shown in Fig. 3, and emission spectrum is shown in Fig. 6, and stability is shown in Fig. 7, produces with methylene blue singlet oxygen
Efficiency comparative sees Fig. 9.
Embodiment 4. is applied
We adopt ultraviolet spectroscopy, do reference with methylene blue, the mono-colour laser of the wavelength 671nm mesh that has been test of light source
The mark stability of compound and the efficiency value of singlet oxygen.Test result indicate that synthesized target compound have good steady
Qualitative, higher singlet oxygen generation efficiency, can be applied successfully to optical dynamic therapy.We are under having light and no light condition
Carry out MTT assay test in HeLa cell for the photosensitizer C respectively, detect its cytotoxicity.Test result indicate that no
Under the conditions of light source irradiates, with the increase of photosensitizer concentration, the activity of cell is not changed in substantially, maintains 100% about, knot
Fruit shows that in dark, cell does not have death in the presence of photosensitizer.By contrast, the LASER Light Source in 671nm irradiates
Under, the activity of cell drastically declines with the increase of photosensitizer concentration, shows that photosensitizer C has very strong phototoxicity.Therefore target
Compound does not have dark toxicity, has very strong phototoxicity, can be used successfully to the medicine preparing optical dynamic therapy cancer cell.Its
MTTassay test result is shown in Figure 10.
Claims (3)
1. the near-infrared compound based on rhodium porphyrin-azepine fluorine boron two pyrroles for the class, is characterized in that they have following structure：
2. a kind of method of the near-infrared compound based on rhodium porphyrin-azepine fluorine boron two pyrroles prepared described in claim 1, its
Feature is that it comprises the following steps：
Add rhodium tetraphenylporphyrin chloride, halo azepine fluorine boron two pyrroles (halo aza-BODIPY), K in the reactor2CO3
And benzene solvent, the ratio of the amount of their material is：Rhodium tetraphenylporphyrin chloride brine is for azepine fluorine boron two pyrroles K2CO3=1
1.1 20, reactant mixture freezing degassing three times, 150 DEG C of reactions under nitrogen protection, question response terminates, and decompression is spin-dried for solvent,
With volume ratio 1:1 CH2Cl2The developing solvent of/hexane carries out silica gel column chromatography and separates, and obtains based on rhodium porphyrin-azepine fluorine boron two pyrrole
Cough up compound.
3. described in claim 1, optical dynamic therapy is being prepared based on the near-infrared compound of rhodium porphyrin-azepine fluorine boron two pyrroles
Application in the medicine of cancer cell.
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| Control over Photoinduced Energy and Electron Transfer in Supramolecular Polyads of Covalently linked azaBODIPY Bisporphyrin‘Molecular Clip’ Hosting Fullerene;Francis D’Souza et al.;《J. Am. Chem.Soc.》;20111224;第134卷;第654-664页 * |
| Synthesis of One-Dimensional Metal-Containing Insulated Molecular Wire with Versatile Properties Directed toward Molecular Electronics Materials;Yasushi Tsuji et al.;《J. Am. Chem. Soc.》;20140115;第36卷;第1742-1745页 * |
| 一个不常见的溶剂效应-Rh(ttp)Cl的31P NMR研究;许肖龙 等;《波谱学杂志》;19910930;第8卷(第3期);第322页 * |
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