CN103666461B - Iridium complex organic fluorescent nanoparticles and preparation method thereof - Google Patents

Iridium complex organic fluorescent nanoparticles and preparation method thereof Download PDF

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CN103666461B
CN103666461B CN201410005612.XA CN201410005612A CN103666461B CN 103666461 B CN103666461 B CN 103666461B CN 201410005612 A CN201410005612 A CN 201410005612A CN 103666461 B CN103666461 B CN 103666461B
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complex
iridium
preparation
organic fluorescence
p4vp
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CN103666461A (en
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周治国
秦丽洁
卢阳
薛峰峰
杨红
杨仕平
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Shanghai Normal University
University of Shanghai for Science and Technology
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Shanghai Normal University
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Abstract

The invention discloses a kind of iridium complex organic fluorescent nanoparticles and a preparation method thereof. The structural formula of the iridium complex organic fluorescent nanoparticles is R2Ir(Mu-Cl)2R2@PEO-b-P4VP, wherein R2Ir(Mu-Cl)2R2 is dichloro-bridged, R is dfppy, ppy or pq, PEO-b-P4VP is polyglycol-b-poly(4-vinylpyridine), the iridium complex organic fluorescent nanoparticles have a spherical morphology, and the grain size is 50nm to 150nm. The nanoparticles have excellent luminescent properties, can emit fluorescent light from blue light to red light and have significant potential application value in the field of luminescent organic nanomaterials; the preparation method of the iridium complex organic fluorescent nanoparticles has the advantages of simpleness in operation, mild conditions, low equipment requirement, no pollution and the like.

Description

One class complex of iridium organic fluorescence nanoparticle and preparation method thereof
Technical field
The present invention relates to organic nano material field, be specifically related to class complex of iridium organic fluorescence nanoparticle and preparation method thereof.
Background technology
Small-sized due to nanoparticle, suitable with biomacromolecule, such as enzyme, polynucleotide, antibody etc.And compared to cell, size then reduces 100 to 10000 times, therefore these nano particles can enter cell, and with cell surface or inner and bio-molecular interaction, this is the early detection of study of disease, Precise Diagnosis and particular treatment provide potential application platform.At present, nanoparticle is mainly used in medicine and gene delivery, bio-sensing, bio-imaging etc. in biological field.
At title complexs such as photochemistry field phosphorescence heavy metal complex such as iridium, platinum, rhenium, ruthenium and osmiums, due to optical physics and the spectrochemical property of its brilliance, it has had lot of documents to report in photocatalyst, Optochemical sensor, photochemistry biomarker etc.But as the phosphor material of superior performance, the research of phosphorescence heavy metal complex in organic fluorescence nano material is relatively less.The present invention has not only synthesized three kinds of phosphorescent metal complex of iridium, and conventional amphiphilic block copolymer is incorporated into the preparation system of fluorescent nano particles in being prepared by medicament, obtain the good organic nano material of this biocompatibility, add the stability of fluorescent material in aqueous phase on the one hand, contribute to the stable transfer in its organism in addition on the one hand.
Summary of the invention
The object of the invention is to preparation one class complex of iridium organic fluorescence nanoparticle.
Present invention also offers the preparation method of above-mentioned nanoparticle.
One class complex of iridium organic fluorescence nanoparticle, it is characterized in that, its structural formula is:
R 2ir (μ-Cl) 2r 2@PEO-b-P4VP, wherein R 2ir (μ-Cl) 2r 2for dichloro bridge, R is dfppy(2-fluorophenyl pyridine), ppy(2-phenylpyridine) or pq(2-phenylquinoline), PEO-b-P4VP is polyoxyethylene glycol-b-poly 4 vinyl pyridine, and described complex of iridium organic fluorescence nanoparticle has spherical morphology, and particle diameter is at 50 ~ 150nm.
That is, the concrete structure formula of three kinds of dichloro bridges is respectively:
The preparation method of above-mentioned complex of iridium organic fluorescence nanoparticle comprises the following steps:
In molar ratio for 1:1 ~ 3:1 takes the dichloro bridge R of complex of iridium 2ir (μ-Cl) 2r 2be dissolved in DMF with PEO-b-P4VP, stir after spending the night and to dialyse with deionized water; The concentration of dichloro bridge in DMF of complex of iridium is 3 ~ 10mmol/L.
Described R 2ir (μ-Cl) 2r 2preparation method comprise the steps:
Under nitrogen protection, the IrCl that mol ratio is 1:2 ~ 1:5 is got 33H 2o and R, adding volume ratio is the cellosolvo of 1:1 ~ 5:1 and the mixed solvent of water, above-mentioned mixing solutions is heated to 60 DEG C ~ 135 DEG C, stirs after 1 ~ 45 hour, and preferably after 10 ~ 20 hours, cooling, filters, and washing, R is dfppy, ppy or pq.
The present invention relates to organic nano science and technology field, disclose three kinds of complex of iridium organic fluorescence nanoparticles and preparation method thereof, and water-solublely can be improved it by single stage method, its structure is such as formula shown in I, there is remarkable optical property, the fluorescence between 550 ~ 650nm can be sent, in light function organic nano material field, there is great potential using value.This nano material is formed by chemically crosslinked effect by the dichloro bridge of three kinds of complex of iridium and a kind of diblock copolymer PEO-b-P4VP.Have simple to operate, mild condition, low for equipment requirements, the advantage such as not pollute.
Accompanying drawing explanation
Fig. 1 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 1.
Fig. 2 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 1.
Fig. 3 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 2.
Fig. 4 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 2.
Fig. 5 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 3.
Fig. 6 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 3.
Fig. 7 is the fluorescence spectrum figure of the complex of iridium organic fluorescence nanoparticle in embodiment 1,2,3.
Specific embodiment
Just the present invention will be further described for embodiment, is not used for limiting the present invention.
Embodiment 1
(1) dichloro bridge (dfppy) is prepared 2ir (μ-Cl) 2(dfppy) 2: under nitrogen protection, get the IrCl that mol ratio is 2:5 33H 2o and dfppy, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 DEG C, stirs after 24 hours, cooling, filters, washing.
(2) (dfppy) is prepared 2ir (μ-Cl) 2(dfppy) 2@PEO-b-P4VP: the dichloro bridge (dfppy) of complex of iridium 2ir (μ-Cl) 2(dfppy) 2be 12:1 with the mol ratio of PEO-b-P4VP; The concentration of dichloro bridge in DMF of complex of iridium is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
The result of the present embodiment, as shown in the FESEM Electronic Speculum of Fig. 1, is all spherical morphology, and size is 50 ~ 100nm.
Fig. 2 is the TEM Electronic Speculum result of the present embodiment.
Embodiment 2
(1) dichloro bridge (ppy) is prepared 2ir (μ-Cl) 2(ppy) 2: under nitrogen protection, get the IrCl that mol ratio is 1:3 33H 2o and polypyrrole, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 DEG C, stirs after 24 hours, cooling, filters, washing.
(2) (ppy) is prepared 2ir (μ-Cl) 2(ppy) 2@PEO-b-P4VP:
The dichloro bridge (ppy) of complex of iridium 2ir (μ-Cl) 2(ppy) 2be 12:1 with the mol ratio of PEO-b-P4VP; The concentration of dichloro bridge in DMF of complex of iridium is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
As shown in Figure 3, major part is spherical morphology to the FESEM Electronic Speculum figure of the present embodiment products obtained therefrom, size 50 ~ 100nm.
Fig. 4 is the TEM Electronic Speculum result of the present embodiment.
Embodiment 3
(1) dichloro bridge (pq) is prepared 2ir (μ-Cl) 2(pq) 2: under nitrogen protection, get the IrCl that mol ratio is 1:3 33H 2o and pq, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 DEG C, stirs after 24 hours, cooling, filters, washing.
(2) (pq) is prepared 2ir (μ-Cl) 2(pq) 2@PEO-b-P4VP: the dichloro bridge (pq) of complex of iridium 2ir (μ-Cl) 2(pq) 2be 12:1 with the mol ratio of PEO-b-P4VP; The concentration of dichloro bridge in DMSO of complex of iridium is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
As shown in Figure 5, major part is spherical morphology to the FESEM Electronic Speculum figure of the present embodiment products obtained therefrom, size 100 ~ 150nm.
Fig. 6 is the TEM Electronic Speculum result of the present embodiment.
As shown in Figure 7, embodiment 1, under 360nm exciting light, sends 627nm red fluorescence to the complex of iridium organic fluorescence nanoparticle fluorescence spectrogram of embodiment 1 ~ 3.Embodiment 2, under 360nm exciting light, sends 565nm fluorescent orange.Embodiment 3, under 360nm exciting light, sends 582nm light green fluorescence.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment.The equivalence completed under not departing from principles of this disclosure so every or amendment, all fall into the scope of protection of the invention.

Claims (5)

1. a class complex of iridium organic fluorescence nanoparticle, it is characterized in that, its structural formula is: R 2ir (μ-Cl) 2irR 2@PEO-b-P4VP, wherein R 2ir (μ-Cl) 2irR 2for dichloro bridge, R is 2-fluorophenyl pyridine, 2-phenylpyridine or 2-phenylquinoline, and PEO-b-P4VP is polyoxyethylene glycol-b-poly 4 vinyl pyridine, and described complex of iridium organic fluorescence nanoparticle has spherical morphology, and particle diameter is at 50 ~ 150nm.
2. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 1, is characterized in that, comprise the following steps:
In molar ratio for 1:1 ~ 3:1 takes the dichloro bridge R of complex of iridium 2ir (μ-Cl) 2irR 2be dissolved in DMF with PEO-b-P4VP, stir after spending the night and to dialyse with deionized water.
3. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 2, is characterized in that, the concentration of dichloro bridge in DMF of complex of iridium is 3 ~ 10mmol/L.
4. the preparation method of the complex of iridium organic fluorescence nanoparticle according to Claims 2 or 3, is characterized in that, described R 2ir (μ-Cl) 2irR 2preparation method comprise the steps:
Under nitrogen protection, the IrCl that mol ratio is 1:2 ~ 1:5 is got 33H 2o and R, adding volume ratio is the cellosolvo of 1:1 ~ 5:1 and the mixed solvent of water, above-mentioned mixing solutions is heated to 60 DEG C ~ 135 DEG C, stirs after 1 ~ 45 hour, cooling, filters, and washing, R is 2-fluorophenyl pyridine, 2-phenylpyridine or 2-phenylquinoline.
5. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 4, is characterized in that, churning time is 1 ~ 30 hour.
CN201410005612.XA 2014-01-06 2014-01-06 Iridium complex organic fluorescent nanoparticles and preparation method thereof Expired - Fee Related CN103666461B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591358A (en) * 2009-06-30 2009-12-02 上海师范大学 A kind of phosphorescent iridium complex that contains isosulfocyanate radical and its production and application
WO2012105753A2 (en) * 2011-02-01 2012-08-09 부산대학교 산학협력단 Deep-blue phosphorescent iridium complex using an n-methylimidazolyl triazole ancillary ligand
CN102942920A (en) * 2012-11-15 2013-02-27 安徽工业大学 Iridium complex phosphorescence material with trifluoroacetyl phenyl substituent quinolone as ligand and preparation method thereof
WO2013165118A1 (en) * 2012-04-30 2013-11-07 율촌화학주식회사 Novel intermetallic compound, and blue phosphorescent organic light-emitting diode including same

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Publication number Priority date Publication date Assignee Title
US8445577B2 (en) * 2011-07-25 2013-05-21 Iowa State University Research Foundation, Inc. Amphiphilic multi-arm copolymers and nanomaterials derived therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591358A (en) * 2009-06-30 2009-12-02 上海师范大学 A kind of phosphorescent iridium complex that contains isosulfocyanate radical and its production and application
WO2012105753A2 (en) * 2011-02-01 2012-08-09 부산대학교 산학협력단 Deep-blue phosphorescent iridium complex using an n-methylimidazolyl triazole ancillary ligand
WO2013165118A1 (en) * 2012-04-30 2013-11-07 율촌화학주식회사 Novel intermetallic compound, and blue phosphorescent organic light-emitting diode including same
CN102942920A (en) * 2012-11-15 2013-02-27 安徽工业大学 Iridium complex phosphorescence material with trifluoroacetyl phenyl substituent quinolone as ligand and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Complex coacervate core micelles;Ilja K. Voets et al.;《Advances in Colloid and Interface Science》;20081017;300-318 *
Influence of Metalation on the Morphologies of Poly(ethylene oxide)-block-poly(4-vinylpyridine) Block Copolymer Micelles;Stanislav N. Sidorov et al.;《Langmuir》;20040324;3543-3550 *

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