CN1651444A - Ruthenium (II) compounding material used for pH sensing and its preparation method - Google Patents
Ruthenium (II) compounding material used for pH sensing and its preparation method Download PDFInfo
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- CN1651444A CN1651444A CN 200410001166 CN200410001166A CN1651444A CN 1651444 A CN1651444 A CN 1651444A CN 200410001166 CN200410001166 CN 200410001166 CN 200410001166 A CN200410001166 A CN 200410001166A CN 1651444 A CN1651444 A CN 1651444A
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- carzphen
- ruthenium
- title complex
- phen
- bpy
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Abstract
A ruthenium (Ru) matched used for pH value sensor is prepared through condensating reaction between 1,10-O-phenanthroline-5,6-dione and proper aldehyde under existance of acetic acid and ammonium acetate to obtain ligands R-carzphen and R'-carzphen, and reflux reaction between R-carzphen or R'-carzphen and bis(2,2'-dipyridine)-dichloro-ruthenium bihydrate or bis (1,10-o-phenanthroline)-dichloro-ruthenium bihydrate to obtain the mononuclear or binuclear match of Ru.
Description
Technical field
The present invention relates to pH luminescence sensor technical field.
Background technology
Have can protonated/deprotonation group replacement inert ruthenium (II) multi-pyridine ligand, be the simplest class pH sensor molecules device [1].By protonated/deprotonation effect, but the electron-transfer reaction in the switch molecule, thus the fluorescent switch of realization pH inductive ruthenium (II) multi-pyridine ligand.Nitrogenous heterocyclic ruthenium (II) multi-pyridine ligand is the maximum fluorescent pH sensing title complex of research.Nitrogen heterocyclic has pyridine, pyrazine, pyrimidine, carbazole and imidazole group.Pyridine, pyrazine and pyrimidine have lower antibonding π track, are good π acceptors, and imidazoles then is that the π that the π acceptor of difference is become reconciled gives body [1].Another advantage of imidazole ring-containing is to control orbital energies by prototropy.Usually imidazole ring and ruthenium (II) coordinate metal complexes does not have fluorescence usually or fluorescence is very weak, and imidazole ring does not show hyperfluorescence [2,3] with ruthenium (II) coordinate metal complexes, but very low fluorescence on/off is than [4].The present invention contains ruthenium (II) multi-pyridine ligand of carbazole and imidazole group simultaneously, and the title complex preparation method is simple, and good stability has high fluorescence on/off ratio.
Reference:
[1]Scandola，F.；Bignozzi，C.A.；Chiorboli，C.；Indelli，M.T.；Rampi，M.A.Coord.Chem.Rev.1990，97，299.
[2]Kaim，W.；Kohlmann，S.Inorg.Chem.1990，29，1898.
[3](a)Haga，M.A.Inorg.Chim.Acta?1983，75，29.(b)Haga，M.A.；Tsunemitu，A.Inorg.Chim.?Acta?1989，164，137.
[4](a)Jing，B.W.；Wu，T.；Tai，C.H.；Zhang，M.H.；Shen，T.Bull.Chem.?Soc.Jpn.2000，73，1749.(b)Cao，H.；Ye，B.H.；Li，H.；Li，R.H.；Zhou，J.Y.；Ji，L.N.Polyhedron?2000，19，1975.(c)Cao，H.；Ye，B.H.；Zhang，Q.L.；Ji，L.N.Inorg.Chem.Commun.1999，2，338.(d)Wang，K.Z.；Gao，L.H.；Bai，G.Y.；Jin，L.P.Inorg.Chem.Commun.2002，5，841.
Summary of the invention
In order to seek good stability, raw material is easy to get inexpensive and the preparation method is simple and the novel material of the responsive response of fluorescence intensity pH variation, and the present invention has ruthenium (II) multi-pyridine ligand that above-mentioned advantage contains carbazole and imidazole group simultaneously.This title complex has highly sensitive pH sensing character, and maximum fluorescence on/off is better than similar ruthenium (II) multi-pyridine ligand than up to nearly 120.
Embodiment
The technical solution used in the present invention is: design the new ruthenium complexe of a class.The key ingredient of this title complex is a kind of phenanthroline derivative ligand R-carzPhen or a kind of phenanthroline derivative ligand R '-carzPhen (molecular structure is seen Fig. 1) that contains the alkyl chain bilateral replacement of carbazole and imidazole group simultaneously that contains the one-sided replacement of alkyl chain of carbazole and imidazole group simultaneously, it is with 2,2 '-dipyridyl (bpy) or 1, a kind of mixed ligand mononuclear coordination compound [RuL that 10-phenanthroline (Phen) and Ru (II) form
2(R-carzPhen)]
2+(L=bpy or Phen) and dinuclear complex [(L)
2Ru (R '-carzPhen) Ru (L)
2]
4+(molecular structure is seen Fig. 2).Route of synthesis as shown in Figure 3.Concrete method for making is as follows:
1. the method for making of part R-carzPhen or R '-carzPhen: will measure 1 of mol ratio, the heated and stirred reaction 4 hours in the presence of acetic acid and ammonium acetate of 10-phenanthroline-5,6-diketone and suitable aldehyde.After the cooling, solution transfers pH to be bordering on 7 with strong aqua.The solid that suction filtration goes out to separate out, after the hot ethanol washing, vacuum-drying gets faint yellow solid, productive rate 80%.
2. title complex [RuL
2(R-carzPhen)]
2+[(L)
2Ru (R '-carzPhen) Ru (L)
2]
4+The method for making of (L=bpy or Phen): will measure two (2 of mol ratio, 2 '-dipyridyl)-two chloro-two hydration rutheniums (II) or two (1, the 10-phenanthroline)-two chloro-two hydration rutheniums (II) and R-carzPhen or R '-carzPhen back flow reaction after 10 hours in the solution of ethylene glycol adds for example NaClO of saturated inorganic or organic salt
4The aqueous solution is separated out red solid.The dried thick product of suction filtration obtains target product after recrystallization from suitable solvent or column chromatography separation.
3.Ru (II) the pH method for sensing of title complex: mix in suitable medium such title complex for example in homogeneous phase solution or the film, change environment PH, can be observed fluorescence (for example the visible monochromatic ray of 450nm excites) intensity considerable change with the variation of environment PH, its emissive porwer presents the difference response ([(Phen) at low value and high value pH zone
2Ru (R '-carzPhen) Ru (Phen)
2]
4+Aqueous solution fluorescence sense characteristic be illustrated in Fig. 4, maximum fluorescence on/off ratio can surpass similar Ru (II) title complex up to 120.
Fig. 1. the molecular structure of part of the present invention (R=C wherein
nH
2n+1And R=(CH
2)
n, n is the positive integer more than or equal to 1).
Fig. 2. the molecular structure of the Ru of pH sensing of the present invention (II) coordination ion (R=C wherein
nH
2n+1And R '=(CH
2)
n, n is the positive integer more than or equal to 1).
Fig. 3. the route of synthesis (R=C of part and title complex
nH
2n+1R '=(CH
2)
n).
Fig. 4. title complex is [(Phen)
2Ru (C
6H
12-carzPhen) Ru (phen)
2]
4+Fluorescence spectrum with the variation of pH value of solution (pH=0.68～12.0).
Claims (3)
1. the monokaryon or double-core ruthenium (II) title complex that form of phenanthroline derivative ligand R '-carzPhen of replacing of the phenanthroline derivative ligand R-carzPhen of the one-sided replacement of alkyl chain that contains carbazole and imidazole group simultaneously or a kind of alkyl chain bilateral that contains carbazole and imidazole group simultaneously.Title complex is characterised in that forming general formula by R-carzPhen and R '-carzPhen and bpy (2,2 '-dipyridyl) or phen (1, the 10-phenanthroline) is [(L)
2Ru (R-carzPhen)] X
mS
n(wherein L=bpy or phen; Inorganic or the organic counter anion of X=, m=1-2; S=solvent molecule, n=arithmetic number) monokaryon ruthenium (II) title complex or general formula are [(L)
2Ru (R '-carzPhen) Ru (L)
2] X
xS
n(x=1-4; L=bpy or phen) double-core ruthenium (II) title complex.
2. part R-carzPhen and R '-carzPhen, title complex are [(L)
2Ru (R-carzPhen)] X
mS
n(wherein L=bpy or phen; Inorganic or the organic counter anion of X=, m=1-2; The S=solvent molecule, the n=arithmetic number) and [(L)
2Ru (R '-carzPhen) Ru (L)
2] X
xS
n(x=1-4; L=bpy or phen) synthetic method.
3. be dispersed in the pH transmitter of some medium (for example in homogeneous phase solution and the film) based on Ru (II) title complex of invention.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344464A (en) * | 2011-07-20 | 2012-02-08 | 北京师范大学 | High water-solubility ruthenium metal complex singlet oxygen fluorescent probe, preparation method thereof, and application thereof |
| CN104225595A (en) * | 2013-06-06 | 2014-12-24 | 南京大学 | Nanoparticle for integration of breast cancer diagnosis and treatment and preparation method thereof |
| CN104838254A (en) * | 2012-11-30 | 2015-08-12 | 锡克拜控股有限公司 | Marking of material, marked material and process of authentication or dilution determination |
| CN106366131A (en) * | 2016-08-29 | 2017-02-01 | 北京师范大学 | Preparation method and application of physiological pH (potential of hydrogen) sensing dinuclear ruthenium complex |
| CN105062463B (en) * | 2015-07-23 | 2017-11-03 | 北京师范大学 | The binuclear ruthenium of different alkyl chain lengths is used as the lysosome probe in cell |
| CN107561026A (en) * | 2017-09-11 | 2018-01-09 | 北京师范大学 | Ruthenium complex for super acids, strong acid and alkaline environment optical sensing |
| CN111735781A (en) * | 2017-11-14 | 2020-10-02 | 北京师范大学 | Triphenylamine grafted ruthenium complex ratio luminescence pH sensor |
-
2004
- 2004-02-03 CN CN 200410001166 patent/CN1651444A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344464A (en) * | 2011-07-20 | 2012-02-08 | 北京师范大学 | High water-solubility ruthenium metal complex singlet oxygen fluorescent probe, preparation method thereof, and application thereof |
| CN102344464B (en) * | 2011-07-20 | 2014-03-26 | 北京师范大学 | High water-solubility ruthenium metal complex singlet oxygen fluorescent probe, preparation method thereof, and application thereof |
| CN104838254A (en) * | 2012-11-30 | 2015-08-12 | 锡克拜控股有限公司 | Marking of material, marked material and process of authentication or dilution determination |
| CN104225595A (en) * | 2013-06-06 | 2014-12-24 | 南京大学 | Nanoparticle for integration of breast cancer diagnosis and treatment and preparation method thereof |
| CN104225595B (en) * | 2013-06-06 | 2018-12-21 | 南京大学 | A kind of breast cancer diagnosis and treatment Integral rice corpuscles and preparation method thereof |
| CN105062463B (en) * | 2015-07-23 | 2017-11-03 | 北京师范大学 | The binuclear ruthenium of different alkyl chain lengths is used as the lysosome probe in cell |
| CN106366131A (en) * | 2016-08-29 | 2017-02-01 | 北京师范大学 | Preparation method and application of physiological pH (potential of hydrogen) sensing dinuclear ruthenium complex |
| CN106366131B (en) * | 2016-08-29 | 2018-10-23 | 北京师范大学 | Physiological pH senses the preparation method and application of binuclear ruthenium |
| CN107561026A (en) * | 2017-09-11 | 2018-01-09 | 北京师范大学 | Ruthenium complex for super acids, strong acid and alkaline environment optical sensing |
| CN107561026B (en) * | 2017-09-11 | 2020-07-31 | 北京师范大学 | Ruthenium complex for optical sensing of super acid, strong acid and alkaline environment |
| CN111735781A (en) * | 2017-11-14 | 2020-10-02 | 北京师范大学 | Triphenylamine grafted ruthenium complex ratio luminescence pH sensor |
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