CN107163084B - A kind of amine-ruthenium conjugation metal complex and its application in near-infrared electrochomeric films - Google Patents
A kind of amine-ruthenium conjugation metal complex and its application in near-infrared electrochomeric films Download PDFInfo
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Abstract
The invention discloses a kind of amine-ruthenium conjugation metal complex and its applications in near-infrared electrochomeric films.The amine-ruthenium conjugation metal complex structural formula has the characteristics that tri-state electrochromism, is connected and composed by the three ring gear ruthenium complexes that triaryl amine group and terminal carboxyl group are modified by covalent bond as shown in formula I.The present invention tests the performance of the near-infrared electrochromic device assembled by the amine-ruthenium conjugation metal complex single thin film as working electrode: there are two reversible redox peaks between 0.1V and 1.1V, it is with good stability in 1,2- dichloroethanes；Lower input voltage is, it can be achieved that the bifurcation of significant tri-state electrochromism behavior and near-infrared absorbs.Amine of the present invention-ruthenium conjugation metal complex has potential application value in the fields such as optical-fibre communications and electronic device.
Description
Technical field
The present invention relates to a kind of amine-ruthenium conjugation metal complex and its applications in near-infrared electrochomeric films, belong to
In near-infrared electrochromism field.
Background technique
Electrochromism refers to that showing for reversible, stable color change occurs under external electric field action for the optical properties of material
As.Electrochomeric films are widely used, such as applied to necks such as intelligent window, electronic console, dynamic camouflage and information storages
Domain.Common electrochromic material includes organic nothing of inorganic, metal oxide, organic conductive polymer and redox active
Machine material.However there are the electrochomeric films of obvious spectrogram variation to be seldom found in the near infrared region.Near-infrared electrochromism
Film has good application on the active material especially in energy-saving window and optical attenuator.Near-infrared electrochomeric films
Using can be to avoid common silica gel optical fiber biggish energy loss in the near infrared region.
Transient metal complex is another extensive concern electrochromic material by everybody.This electrochromic material
With determining oxidation-reduction process and in the visibly different Electron absorption of different redox states, these properties keep transition golden
Metal complex has potential application value in electrochromism field.However the high redox potential of transient metal complex and
Being not easy to form film is hindered it in terms of electrochromism.
Summary of the invention
The object of the present invention is to provide a kind of amine-rutheniums to be conjugated metal complex, and the amine-ruthenium conjugation metal complex can lead to
It crosses and is adsorbed in nano-TiO certainly2Surface forms single thin film, and can be used as near-infrared electrochomeric films, to be used to prepare near-infrared electroluminescent
Electrochromic device.
Amine provided by the present invention-ruthenium is conjugated metal complex, has the characteristics that tri-state electrochromism, by triarylamine
Group and terminal carboxyl group modification three ring gear ruthenium complexes connected and composed by covalent bond, structural formula as shown in formula I,
Invention further provides the amine-ruthenium conjugation metal complex preparation methods, include the following steps:
(1) three chloro- 4,4 ', 4 "-front three ester group tris (bipyridine) ruthenium (III) and trifluoro-methane sulfonic acid silver progress ligand exchange are anti-
It answers；Into the filtrate of the ligand exchange reaction be added N- bis- (4- methoxyphenyl) -3 ', 5 '-two (pyridine -2- base)-[1,
1 '-diphenyl] the progress complexation reaction of -4- amine ligand, saturation KPF6 solution is added after post-treated and is precipitated, obtains 4 shown in formula II,
4 ', 4 "-three ester group terpyridyl ruthenium complexes；
(2) existing for the triethylamine under the conditions of, 4,4 ', 4 "-three ester group terpyridyl ruthenium complexes shown in formula II carry out water
Solution reaction；Then hydrochloric acid is added after hydrolysis and is conjugated metal complex up to amine described in claim 1-ruthenium.
In above-mentioned preparation method, in step (1), -3 ', 5 '-two (pyridine -2- of N- bis- (4- methoxyphenyl)
Base)-[1,1 '-diphenyl] -4- amine ligand structural formula as shown in formula III, reference literature (Shen J-J；Zhong Y-
W.Long-Range Ruthenium-Amine Electronic Communication through the para-
Oligophenylene Wire.Sci Rep.2015,5,13835-13843.) in record method prepared:
In above-mentioned preparation method, in step (1), the ligand exchange reaction carries out at reflux；
The time of the ligand exchange reaction can be 2~5 hours, concretely 3 hours；
The solvent of the ligand exchange reaction can be acetone；
The molar ratio of three chloro- 4,4 ', 4 "-front three ester group tris (bipyridine) ruthenium (III) and the trifluoro-methane sulfonic acid silver
It can be 1:3~4, concretely 1:3.5；
The complexation reaction carries out at reflux；
The time of the complexation reaction can be 10~15 hours, concretely 12 hours；
The solvent of the complexation reaction can be the mixed liquor of n,N-Dimethylformamide and the tert-butyl alcohol, and the volume ratio of the two can
For 1:1,
In step (1), the post-processing includes the steps that column chromatography for separation；
The eluant, eluent that the column chromatography for separation uses can be the mixing of the methylene chloride and acetonitrile of 10:1~3 for volume ratio
Liquid.
In above-mentioned preparation method, in step (2), the solvent of the hydrolysis can be n,N-Dimethylformamide and water
Mixed liquor；
The volume ratio of the n,N-Dimethylformamide, the triethylamine and the water can be 8~12:2~6:2~6, tool
Body can be 10:3:3；
The hydrolysis carries out at reflux；
The time of the hydrolysis can be 12~48 hours, concretely 24 hours.
In above-mentioned preparation method, in step (2), it is added before the hydrochloric acid, the method also includes following steps:
The solvent of system after the hydrolysis is removed, the methanol-water solution of 4-n-butyl ammonium hydroxide is then added, with
Product (carboxylic acid) more good dissolving after making the hydrolysis；
The methanol-water solution of the 4-n-butyl ammonium hydroxide is referred to the mixing of first alcohol and water (volume ratio 1:1)
Liquid is the solution of solvent；
The molar ratio of the 4-n-butyl ammonium hydroxide and the hydrochloric acid is not more than 1:1.
Amine of the present invention-ruthenium conjugation metal complex is adsorbed in nano-TiO certainly2Surface forms amine-ruthenium and is conjugated metal complex
Single thin film can be used as near-infrared electrochomeric films and be used to prepare near-infrared electrochromic device (as working electrode).
Near infrared light in the present invention refers to wavelength for 780nm to the light between 3000nm.
The amine-ruthenium conjugation metal complex single thin film (refers to that the amine-ruthenium conjugation metal complex is received described
Rice TiO2It is monolayer adsorption on surface) it can prepare by the following method:
Nano-TiO is prepared in substrate2Coating；Then it is impregnated in the amine-ruthenium conjugation metal complex solution i.e.
?；
The substrate can be FTO；
The concentration of the amine-ruthenium conjugation metal complex solution can be 0.25~0.35mM；
The amine-the solvent that the solution of ruthenium conjugation metal complex uses can be N, N-dimethylformamide；
The nano-TiO2Coating can be prepared by the following method:
Using the method for blade coating by TiO2Slurry (being dispersed in n-butanol) is applied in the substrate, is dried and is placed on horse
Not in furnace, 10~20min is calcined under conditions of 400~500 DEG C, is subsequently cooled to 70~90 DEG C.
It, can be according to when amine of the present invention-ruthenium conjugation metal complex single thin film prepares near-infrared electrochromic device
Following step assembling: using the amine-ruthenium conjugation metal complex single thin film as working electrode, FTO glass is used as to electrode,
The tetra-n-butyl amine perchlorate of 0.1M is as electrolyte solution, solvent 1,2- dichloroethanes.The glass of 200 μ m-thicks is electric by work
Pole and electrode is separated, makes to have certain gap filling electrolyte solution, be then packaged with epoxy resin.All tests
Electrochromic device, area are 1 × 1cm2。
The present invention tests the near-infrared assembled by the amine-ruthenium conjugation metal complex single thin film as working electrode
The performance of electrochromic device: there are two reversible redox peaks between 0.1V and 1.1V, have in 1,2- dichloroethanes
There is good stability；Lower input voltage is, it can be achieved that the bifurcation of significant tri-state electrochromism behavior and near-infrared absorbs.
The invention has the following beneficial effects:
Amine provided by the invention-ruthenium is conjugated metal complex, by being adsorbed in nano-TiO certainly2Surface forms single thin film.
Single thin film stability in different solvents is different, by electro-chemical test, has in 1,2- dichloroethanes good steady
It is qualitative.Electrochemistry map between 0.1V and 1.1V there are two obvious reversible redox peaks, and half wave potential difference compared with
Greatly, illustrate that intermediate oxidation state stability is preferable.It is tested by spectroelectrochemistry, which has shown in the near infrared region
Two step electrochromic process of meaning.Contrast ratio (T%) at the first step state of oxidation, wavelength 1300nm is 58%；?
Second oxidation state, the contrast ratio (T%) at wavelength 780nm are 59%.Tinctorial yield is in 210cm2/ C and 270cm2Between/C.Compared with
Low input voltage is, it can be achieved that the bifurcation of significant tri-state electrochromism behavior and near-infrared absorbs.Amine of the present invention-ruthenium conjugation gold
Metal complex has potential application value in the fields such as optical-fibre communications and electronic device.
Detailed description of the invention
Fig. 1 is FTO/TiO prepared by the embodiment of the present invention 22The SEM of matches film shown in/formula I schemes, wherein Fig. 1 (a)
It is respectively the SEM figure in film surface and section with Fig. 1 (b).
Fig. 2 is the schematic diagram of electrochromic device.
Fig. 3 is the electro-chemical test figure of electrochromic device prepared by the embodiment of the present invention 3, wherein Fig. 3 (a) is electroluminescent
Electrochromic device tests spectrogram in the electrochemical stability that 0V and 1.1V is scanned；Fig. 3 (b) is electrochromic device in different scanning speed
Cyclic voltammogram (50,150,250,350 and 450mV/s) under degree.
Fig. 4 is the spectroelectrochemistry test chart of electrochromic device prepared by the embodiment of the present invention 3.
Fig. 5 is at 1300nm, and electrochromic device prepared by the embodiment of the present invention 3 is between+0.4V and+0.65V
Chrono-amperometric spectrogram, wherein Fig. 5 (a) is current-time curvel, and Fig. 5 (b) is transmitance time graph, and Fig. 5 (c) is individually to follow
The transmitance time graph of ring.
Fig. 6 is at 780nm, and electrochromic device prepared by the embodiment of the present invention 3 is between+0.65V and+0.90V
Chrono-amperometric spectrogram, wherein Fig. 6 (a) is current-time curvel, and Fig. 6 (b) is transmitance time graph, and Fig. 6 (c) is individually to follow
The transmitance time graph of ring.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The present embodiment material therefor specifically includes that three chloro- 4,4 ', 4 "-front three ester group tris (bipyridine) rutheniums (III), fluoroform
Alkyl sulfonic acid silver, acetone, N,N-dimethylformamide, the tert-butyl alcohol, triethylamine, secondary water and 4-n-butyl ammonium hydroxide methanol-water
Solution.
The synthesis of embodiment 1, amine-ruthenium conjugation metal complex (formula I)
1) N, N- bis- (4- methoxyphenyl) -3 ', 5 '-two (pyridine -2- base)-[1,1 '-diphenyl] -4- amine ligand (formula
III) preparation
The synthesis of N, N- bis- (4- methoxyphenyl) -3 ', 5 '-two (pyridine -2- base)-[1,1 '-diphenyl] -4- amine ligand
Referring to Shen J-J；Zhong Y-W.Long-Range Ruthenium-Amine Electronic Communication
through the para-Oligophenylene Wire.Sci Rep.2015,5,13835-13843.
Reaction equation is as follows:
2) preparation of 4,4 ', 4 "-three ester group terpyridyl ruthenium complexes (formula II)
Reaction equation is as follows:
Three chloro- 4,4 ', 4 "-front three ester group tris (bipyridine) rutheniums (III) (62mg, 0.1mmol), trifluoromethayl sulfonic acid will be contained
The reaction flask reflux of silver-colored (90mg, 0.35mmol), 40mL acetone solvent, is filtered after reacting 3h, and N, N- bis- is added after filtrate revolving
(4- methoxyphenyl) -3 ', 5 '-two (pyridine -2- base)-[1,1 '-diphenyl] -4- amine ligand (27mg, 0.05mmol), 10mL
N,N-Dimethylformamide, the 10mL tert-butyl alcohol are heated to reflux 12h after being bubbled 20min, after the reaction was completed, stop reaction and are cooled to
Room temperature, vacuum rotary steam remove solvent, and column chromatography for separation purifies (eluant, eluent: methylene chloride/acetonitrile 10/1, v/v), a small amount of first is added
Alcohol dissolution adds saturation KPF6Solution is precipitated, and obtains 4,4 ', 4 "-three ester group terpyridyl shown in 47mg black solid formula II
Ruthenium complex, yield 78%.
1H NMR(300MHz,d6-acetone):δ9.67(s,2H),9.26(s,2H),8.69(s,2H),8.49(d,J
=8.2Hz, 2H), 7.91 (d, J=8.6Hz, 2H), 7.77-7.62 (m, 6H), 7.21-7.06 (m, 8H), 6.99 (d, J=
9.0Hz, 4H), 6.72 (t, J=6.0Hz, 2H), 4.20 (s, 3H), 3.92 (s, 6H), 3.84 (s, 6H) .13C NMR (75MHz,
d6-acetone):δ169.53,165.98,164.78,160.71,157.15,155.84,154.06,153.08,148.76,
142.64,141.79,139.29,137.39,136.81,134.99,133.09,128.37,127.44,126.68,123.78,
123.40,122.87,121.79,121.23,115.67,55.78,53.56,53.40.MALDI-MS(m/z):1043.0for
[M-PF6]+.Anal.Calcd for C57H45F6N6O8PRu·H2O:C,56.77；H,3.93；N,6.97.Found:C,
56.37；H,3.84；N,6.71.
By above-mentioned data it is found that the structure of prepared compound is correct.
3) preparation of 4,4 ', 4 "-tricarboxy terpyridyl ruthenium complexes (formula I):
Reaction equation is as follows:
To contain 4,4 ', 4 "-three ester group tris (bipyridine) rutheniums (60mg, 0.1mmol), 10mL N,N-dimethylformamide,
3mL triethylamine, 3mL secondary water are placed in a reaction flask, and are heated to reflux for 24 hours after being bubbled 20min, and after the reaction was completed, revolving removes molten
Agent is added the dissolution of 0.1M 4-n-butyl ammonium hydroxide methanol-water solution, dilute hydrochloric acid (itself and 4-n-butyl ammonium hydroxide is added
Molar ratio is 1:1) product is precipitated, filtering is successively washed with acetonitrile, secondary water, ether, 52mg violet solid is obtained after dry,
4,4 ', 4 "-tricarboxy terpyridyl ruthenium complex shown in formula I, yield 90%.
1H NMR(300MHz,CD3OD): δ 9.34 (s, 2H), 8.95 (s, 2H), 8.51 (s, 2H), 8.27 (d, J=
8.1Hz, 2H), 7.82 (d, J=8.6Hz, 2H), 7.62 (t, J=7.9Hz, 2H), 7.37 (dd, J=5.7,1.5Hz, 2H),
7.25 (d, J=5.7Hz, 2H), 7.11 (dd, J=8.8,3.1Hz, 6H), 7.01 (d, J=5.1Hz, 2H), 6.93 (d, J=
9.0Hz, 4H), 6.68 (t, J=6.4Hz, 2H), 3.82 (s, 6H) .MALDI-MS (m/z): 1001.6for [M-Cl]+
.Anal.Calcd for C54H39N6O8RuCl·H2O:C,61.51；H,3.94；N,7.97.Found:C,61.90；H,4.32；
N,7.82.
By above-mentioned data it is found that the structure of prepared target compound is correct.
The preparation of embodiment 2, amine-ruthenium conjugation metal complex monofilm
With the method for blade coating by TiO2Slurry is applied to using FTO after natural drying, to be put into Muffle on the sheet glass of substrate
In furnace, 450 DEG C are gradually heated to, 15min is calcined, is cooled to 80 DEG C after the completion of calcining, immerses the 4 of 0.30mM, 4 ', 4 "-tricarboxylics
In the n,N dimethylformamide solution of base terpyridyl ruthenium complex (formula I), in soaking at room temperature 12h, N, N- dimethyl are then used
Formamide, ethyl alcohol wash away the unadsorbed dyestuff in surface, obtain amine-ruthenium conjugation metal complex monofilm, i.e. FTO/TiO2/ formula I
Shown matches film, scanning electron microscope is as shown in Figure 1, wherein Fig. 1 (a) is that the scanning electron microscope on surface is shone
Piece, Fig. 1 (b) are the electron scanning micrograph in section, as seen from the figure, TiO2Nano particle size is 20nm or so,
TiO2For layer (including matches film shown in formula I) with a thickness of 3~4 μm, film surface is uniform, smooth.
The assembling of embodiment 3, electrochromic device
According to structural schematic diagram assembling electrochromic device shown in Fig. 2:
FTO/TiO prepared by embodiment 22Matches film shown in/formula I is used as working electrode, FTO glass to electricity
Pole, solvent 1,2- dichloroethanes, the tetra-n-butyl amine perchlorate of 0.1M is as electrolyte solution.The glass of 200 μ m-thicks is by work
Make electrode and electrode is separated, makes the gap filling electrolyte solution for having certain, be then packaged with epoxy resin.All
The electrochromic device of test, area are 1 × 1cm2。
Shown in the electro-chemical test of the electrochromic device of above-mentioned preparation such as Fig. 3 (a), it can be seen that be formed by FTO/
TiO2There are two reversible redox peaks (reference electrode Ag/ in+059V and+0.77V for matches film shown in/formula I
AgCl is platinum filament, solvent ClCH to electrode2CH2Cl, electrolyte 0.1MnBu4NClO4).Between potential 0V and+1.1V
After 1000 circle of scanning, current strength is reduced to original 60%, this shows FTO/TiO2Compound film shown in/formula I is in extraneous electricity
There is certain stability under gesture.Fig. 3 (b) shows FTO/TiO2The peak current of compound film shown in/formula I is in scanning speed
Linear relationship illustrates that redox reaction is that localization is carried out in electrode surface.
The spectroelectrochemistry test of the electrochromic device of above-mentioned preparation is as shown in Figure 4, it can be seen that with voltage liter
Height, FTO/TiO2Matches film shown in/formula I produces IVCT band at 1300nm, this band corresponds to I shownization of formula
Conjunction object+2 valence；Voltage continues to increase, and IVCT band weakens, and occurs new peak at 780nm, this peak belongs to compound
LMCT band, corresponding to complex shown in formula I+trivalent state (solvent ClCH2CH2Cl, electrolyte 0.1MnBu4NClO4, ginseng
It is Ag/AgCl than electrode, is platinum filament to electrode).
The chrono-amperometric of the electrochromic device of above-mentioned preparation is tested as it can be seen in figures 5 and 6, FTO/TiO2Cooperation shown in/formula I
For object film at the first step state of oxidation, wavelength 1300nm, contrast ratio is (T%) 58%, tinctorial yield 260cm2/ C, when response
Between be 20s；In the second step state of oxidation, wavelength is at 780nm, and contrast ratio is (T%) 59%, tinctorial yield 210cm2/ C is rung
It is 10s between seasonable.It was found that FTO/TiO2Matches film shown in/formula I is shorter than the first step in the second step oxidation process response time,
However TiO2Conduction level it is more negative than complex 1, therefore, this and TiO2Conduction band relationship it is little, may with occur in FTO table
The intermolecular charge transfer in face is related.
In conclusion the present invention provides one kind to have the electrochromic amine of near-infrared-ruthenium conjugated complex and its film,
The preparation method of film is simple, repeatable.Amine shown in formula I-ruthenium conjugation metal complex is adsorbed onto TiO certainly2Surface, in solvent
ClCH2CH2It is with good stability in Cl.FTO/TiO2There are two continuous in low potential region for matches film shown in/formula I
Redox peaks, two step electrochromism phenomenons, and the contrast ratio and coloration efficiency having had are presented in the near infrared region, because
This has potential application value in the fields such as optical-fibre communications and electronic device.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of amine-ruthenium is conjugated metal complex, structural formula as shown in formula I,
2. amine described in claim 1-ruthenium conjugation metal complex preparation method, includes the following steps:
(1) three chloro- 4,4 ', 4 "-front three ester group tris (bipyridine) ruthenium (III) and trifluoro-methane sulfonic acid silver carry out ligand exchange reaction；
N- bis- (4- methoxyphenyl) -3 ', 5 '-two (pyridine -2- base)-[1,1 '-is added into the filtrate after the ligand exchange reaction
Diphenyl] the progress complexation reaction of -4- amine ligand, obtain 4,4 ', 4 "-three ester group terpyridyl ruthenium complex shown in formula II；
The time of the ligand exchange reaction is 2~5 hours；
The molar ratio of three chloro- 4,4 ', the 4 "-front three ester group tris (bipyridine) ruthenium (III) and the trifluoro-methane sulfonic acid silver is 1:3
~4；
The time of the complexation reaction is 10~15 hours；
The method also includes shown in column chromatography for separation formula II the step of 4,4 ', 4 "-three ester group terpyridyl ruthenium complex；
The eluant, eluent that the column chromatography for separation uses is the mixed liquor of methylene chloride and acetonitrile that volume ratio is 10:1~3；
(2) existing for the triethylamine under the conditions of, 4,4 ', 4 "-three ester group terpyridyl ruthenium complexes shown in formula II are hydrolyzed instead
It answers；Then hydrochloric acid is added after hydrolysis and is conjugated metal complex up to amine described in claim 1-ruthenium；
The solvent of the hydrolysis is the mixed liquor of N,N-dimethylformamide and water；
The time of the hydrolysis is 12~48 hours；
It is added before the hydrochloric acid, the method also includes following steps:
The solvent of system after the hydrolysis is removed, the methanol-water solution of 4-n-butyl ammonium hydroxide is then added；
The methanol-water solution of the 4-n-butyl ammonium hydroxide is referred to using the mixed liquor of first alcohol and water as the solution of solvent；
The molar ratio of the 4-n-butyl ammonium hydroxide and the hydrochloric acid is not more than 1:1.
3. a kind of amine-ruthenium is conjugated metal complex single thin film, the amine as described in claim 1-ruthenium conjugation metal complex absorption
In nano-TiO2Surface is formed.
4. amine described in claim 3-ruthenium conjugation metal complex single thin film preparation method, includes the following steps:
Nano-TiO is prepared in substrate2Coating；Then it is impregnated in amine described in claim 1-ruthenium conjugation metal complex solution
In to obtain the final product；
The concentration of the amine-ruthenium conjugation metal complex solution is 0.25~0.35mM；
The solvent that the amine-ruthenium conjugation metal complex solution uses is N,N-dimethylformamide.
5. the preparation method according to claim 4, it is characterised in that: prepare the nano-TiO as steps described below2Coating:
Using the method for blade coating by TiO2Slurry is applied in the substrate, is dried and is placed in Muffle furnace, at 400~500 DEG C
Under the conditions of calcine 10~20min, be subsequently cooled to 70~90 DEG C.
6. amine-ruthenium described in amine described in claim 1-ruthenium conjugation metal complex or claim 3 is conjugated metal complex single layer
Film is preparing the application in near-infrared electrochomeric films or near-infrared electrochromic device.
7. a kind of near-infrared electrochromic device, it is characterised in that: the working electrode of the near-infrared electrochromic device is power
Benefit requires 3 amine-ruthenium conjugation metal complex single thin film.
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| CN111518141B (en) * | 2020-05-19 | 2023-08-08 | 中国科学院化学研究所 | Star-shaped trinuclear metal ruthenium complex and application thereof in near-infrared electrochromic film |
| CN113150036B (en) * | 2021-05-08 | 2023-03-24 | 衡阳师范学院 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
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