CN113150036B - Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof - Google Patents
Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN113150036B CN113150036B CN202110498344.XA CN202110498344A CN113150036B CN 113150036 B CN113150036 B CN 113150036B CN 202110498344 A CN202110498344 A CN 202110498344A CN 113150036 B CN113150036 B CN 113150036B
- Authority
- CN
- China
- Prior art keywords
- triarylamine
- substituted
- terpyridyl
- ruthenium complex
- terpyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 125000005259 triarylamine group Chemical group 0.000 title claims abstract description 43
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical class N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 6
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical class [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 150000003303 ruthenium Chemical class 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 3
- SUCQPHMWFOCTTR-UHFFFAOYSA-L dichlororuthenium;triphenylphosphane Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SUCQPHMWFOCTTR-UHFFFAOYSA-L 0.000 abstract description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- NLXVDXFRQYCPFX-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 NLXVDXFRQYCPFX-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004365 square wave voltammetry Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
A triarylamine substituted terpyridyl ruthenium complex and a preparation method and application thereof relate to the technical field of molecular leads, wherein the terpyridyl substituted by triarylamine is obtained by modifying the terpyridyl, and then the terpyridyl substituted by triarylamine is coordinated with triphenylphosphine ruthenium dichloride to obtain the terpyridyl ruthenium complex substituted by triarylamine, so that another organic (N) -inorganic (Ru) mixed molecular lead model is constructed, and the terminal groups of the triarylamine substituted terpyridyl ruthenium complex have stronger electronic interaction through electrochemical method tests. In addition, the chlorine atom in the triarylamine substituted terpyridyl ruthenium complex can be further substituted, so that a new way for constructing a complex molecular lead with multiple redox active centers can be provided.
Description
Technical Field
The invention relates to the technical field of molecular wires, in particular to a triarylamine substituted terpyridyl ruthenium complex and a preparation method and application thereof.
Background
Terpyridines have been widely used in the synthesis of metal complexes as important ligands for the synthesis of metal complexes. With the development of science and technology, a series of terpyridine ligand derivatives are also synthesized in a large quantity, so that a more complex terpyridine metal complex is constructed, and the generated metal complex is also applied to the fields of dye-sensitized solar cells, photocatalysis, ion recognition, molecular electrons and the like. Recent evidence shows that the mono-terpyridyl ruthenium can be further reacted to generate bis (terpyridyl ruthenium), namely, a cyclometalated ruthenium derivative, and a corresponding molecular lead model (chem. Commun, 2012, 48, 5680-5682) is constructed, wherein the molecular lead model is obtained by further coordinating the mono-terpyridyl ruthenium with other ligands, so that the mono-terpyridyl ruthenium has the characteristics of being further modified, and provides new possibility for constructing an organic (N) -inorganic (Ru) mixed molecular lead model.
Disclosure of Invention
The invention aims to provide a triarylamine substituted terpyridyl ruthenium complex, wherein the end groups of the complex have stronger electronic interaction.
The structural formula of the triarylamine substituted terpyridyl ruthenium complex is shown as a formula (1):
wherein R is H or Me (CH) 3 ) Or OMe (OCH) 3 )。
The invention also aims to provide a method for preparing the triarylamine substituted terpyridyl ruthenium complex, and a novel organic (N) -inorganic (Ru) mixed molecular wire model is constructed.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a triarylamine substituted terpyridyl ruthenium complex comprises the following steps:
1) Preparing triarylamine substituted terpyridine;
2) Sequentially adding triarylamine substituted terpyridine, tris (triphenylphosphine) ruthenium dichloride and methanol into a reaction vessel, reacting for 24-36 hours under stirring and refluxing, cooling to room temperature, concentrating a reaction system solvent, adding sodium hexafluorophosphate into the reaction system solvent to precipitate a solid, and recrystallizing with dichloromethane/methanol to obtain the triarylamine substituted terpyridine ruthenium complex.
Wherein the mass ratio of the triarylamine-substituted terpyridine to the tris (triphenylphosphine) ruthenium dichloride and sodium hexafluorophosphate is 1: (1 to 1.1): (15 to 20).
Wherein each millimole of triarylamine-substituted terpyridine corresponds to approximately 150 to 200mL of methanol.
The method for preparing triarylamine substituted terpyridine comprises the following steps: 4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine, diphenylamine substituted by different substituents and tris (dibenzylideneacetone) dipalladium (Pd (dba) are added into a reaction vessel in sequence 3 ) Tri-tert-butylphosphine (b) t Bu 3 P), potassium tert-butoxide and toluene are reacted for 4~6 hours under stirring and refluxing, the mixture is cooled, dichloromethane is used for extraction and liquid separation to obtain an organic phase, then the organic phase is dried by spinning, and dichloromethane/normal hexane is used for recrystallization to obtain a light yellow solid, namely triarylamine substituted terpyridine.
Wherein, the ratio of the 4'- (4-bromophenyl) -2,2':6',2' -terpyridine to the amounts of diphenylamine, tri (dibenzylidene acetone) dipalladium, tri-tert-butylphosphine and potassium tert-butoxide which are substituted by different substituents is 1: (1~3): (0.015 to 0.025): (0.015 to 0.050): (10 to 15).
Wherein each millimole of 4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine corresponds to about 10 to 15mL of toluene.
In addition, the invention also relates to the application of the triarylamine substituted terpyridyl ruthenium complex in a molecular wire.
According to the invention, firstly, terpyridine substituted by triarylamine is obtained by modifying terpyridine, and then the terpyridine is coordinated with triphenylphosphine ruthenium dichloride to obtain a terpyridine ruthenium complex substituted by triarylamine, so that another organic (N) -inorganic (Ru) mixed molecular wire model is constructed, and the terminal groups of the terpyridine ruthenium complex substituted by triarylamine have strong electronic interaction through electrochemical method tests. In addition, the chlorine atom in the triarylamine substituted terpyridyl ruthenium complex can be further substituted, so that a new way for constructing a complex molecular lead with multiple redox active centers can be provided.
Drawings
FIG. 1 shows the NMR phosphorus spectrum of a triarylamine-substituted ruthenium terpyridyl complex (R = OMe) (II-3).
FIG. 2 shows the NMR spectrum of triarylamine substituted ruthenium terpyridyl complex (R = OMe) (II-3).
FIG. 3 shows the NMR carbon spectra of triarylamine-substituted ruthenium terpyridyl complexes (R = OMe) (II-3).
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention. It should be noted that the following examples are carried out in the laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples are merely representative of the proportioning relationship between the components, and are not specifically limited.
1. Preparation of triarylamine substituted terpyridyl ruthenium complex:
the compound is synthesized by a continuous two-step reaction, and the reaction equation is as follows:
wherein R is H or Me (CH) 3 ) Or OMe (OCH) 3 )。
The method comprises the following specific steps:
step I: triarylamine substituted terpyridines were prepared (R = OMe).
4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine 0.580g (1.50 mmol), methoxy substituted diphenylamine 0.412g (1.80 mmol), tris (dibenzylideneacetone) dipalladium 0.023g (0.025 mmol), tri-tert-butylphosphine 0.006mL (0.025 mmol), potassium tert-butoxide 1.74g (0.015 mol) and 15mL of toluene are added into a round bottom flask in sequence, the mixture is stirred, heated and refluxed for 5h under the protection of inert gas, cooled, extracted and separated by dichloromethane to obtain an organic phase, and then the organic phase is dried by a rotary evaporator under the pressure of 0.005 to 0.01Kpa and the temperature of 40 to 45 ℃, and then directly recrystallized by dichloromethane/n-hexane without column chromatography to obtain 712mg of a light yellow solid, namely the triarylamine substituted terpyridine (R = OMe) with the yield of 88%. Wherein, toluene is the solvent needed by the reaction.
The structural formula of triarylamine substituted terpyridines (R = OMe) is shown in formula I-3:
elemental analysis (C) 35 H 28 N 4 O 2 ）：
Theoretical value: c,78.34; h,5.26. Measurement value: c,78.30; h,5.29.
1 H NMR (500 MHz, CDCl 3 ): δ 3.81 (s, 6H, -OCH 3 ), 6.87 (d, J(HH) = 5.0 Hz, 4H), 7.01 (d, J(HH) = 5.0 Hz, 2H), 7.11 (d, J(HH) = 10.0 Hz, 4H), 7.33 (t, J(HH) = 5.0 Hz, 2H), 7.75 (d, J(HH) = 10.0 Hz, 2H), 7.87 (t, J(HH) = 5.0 Hz, 2H), 8.66 (d, J(HH) = 5.0 Hz, 2H), 8.68 (s, 2H), 8.71 (d, J(HH) = 5.0 Hz, 2H).
13 C NMR (125 MHz, CDCl 3 ): δ 55.48 (-OCH 3 ), 114.75, 117.97, 119.92, 121.31, 123.67, 126.80, 126.90, 127.88, 129.59, 136.80, 140.43, 149.05, 149.63, 149.77, 155.73, 156.14, 156.43.
From the above data, the structures of the prepared compounds were correct.
Step II: a triarylamine substituted terpyridyl ruthenium complex was prepared (R = OMe).
0.134g (0.25 mmol) of triarylamine substituted terpyridine, 0.240g (0.25 mmol) of tris (triphenylphosphine) ruthenium dichloride and 40mL of methanol are sequentially added into a round-bottom flask, the mixed system is stirred, heated and refluxed for 24h under the protection of inert gas, cooled to room temperature, the solvent of the reaction system is concentrated by a rotary evaporator under the pressure of 0.005 to 0.01Kpa and the temperature of 40 to 45 ℃, 0.672g (4.00 mmol) of sodium hexafluorophosphate is added into the system to precipitate solids, and then dichloromethane/methanol is used for recrystallization to obtain 234mg of a reddish brown pure product, namely the triarylamine substituted terpyridine ruthenium complex (R = OMe), wherein the yield is 67%. Wherein, methanol is a solvent required by the reaction.
The structural formula of the triarylamine substituted terpyridyl ruthenium complex (R = OMe) is shown in a formula II-3:
elemental analysis (C) 74 H 66 ClF 6 N 4 O 2 P 3 Ru）：
Theoretical value: c,64.09; h,4.80. Measurement value: c,64.11; h,4.75.
1 H NMR (500 MHz, CDCl 3 ): δ 3.84 (s, 6H, -OCH 3 ), 6.92 (d, J(HH) = 10.0 Hz, 4H), 7.04-7.07 (m, 16H), 7.17-7.20 (m, 22H), 7.47 (d, J(HH) = 10.0 Hz, 2H), 7.53 (s, 2H), 7.70 (t, J(HH) = 10.0 Hz, 2H), 7.85 (d, J(HH) = 10.0 Hz, 2H), 9.01 (d, J(HH) = 5.0 Hz, 2H).
13 C NMR (125 MHz, CDCl 3 ): δ 55.53 (-OCH 3 ), 115.00, 119.41, 122.43, 126.04, 128.11, 128.15128.18, 129.63, 130.08, 130.23, 132.90, 132.94, 132.98, 136.54, 155.32, 156.79, 158.14.
31 P NMR (200 MHz, CDCl 3 ): δ 20.01 (s, PPh 3 ), −144.13 (septet, PF 6 ).
From the above data, the structures of the prepared compounds were correct.
Wherein, the attached figures 1-3 respectively show a phosphorus nuclear magnetic resonance spectrum, a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of the triarylamine substituted terpyridyl ruthenium complex (R = OMe) (II-3).
2. Electrochemical performance test
The measuring method comprises the following steps: electrochemical measurements were carried out using electrochemical workstation CHI 660C (CH Instruments Company, USA). Wherein, a glassy carbon electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and Ag is used + The | Ag electrode is a reference electrode; at 0.001mol ∙ L -1 n-Bu 4 NPF 6 CH (A) of 2 Cl 2 The solution is electrolyte, the concentration of the tested substrate is 0.001mol ∙ L -1 (ii) a Cyclic voltammetry is typically performed at a scan rate of 100mV ∙ s -1 Measured as square wave volt-amperef Measured under the condition of 10 Hz.
Data processing: the data were processed into pictures by OriginPro 8.0.
Performing cyclic voltammetry and square wave voltammetry tests on triarylamine substituted terpyridyl ruthenium complex (R = OMe) (II-3) by an electrochemical method to obtain a potential difference (delta) of two times of oxidation reductionE) And equilibrium constantK c The values, corresponding results are shown in table 1.
TABLE 1
| Compound (I) | E 1/2 (1)(V) | E 1/2 (2) (V) | ΔE (mV) b | K c c |
| II-3 | 0.78 | 1.15 | 370 | 1.79 × 10 6 |
Wherein, deltaE = E 1/2 (2) – E 1/2 (1)，K c = exp(ΔE/25.69) (298 K)。
The above test results are comprehensively analyzed, and it can be known that two continuous redox processes, delta, occur based on N in triphenylamine and the redox active center of terpyridyl rutheniumEThe results show that the metallic ruthenium end group of the compound has obvious electronic interaction with the organic nitrogen center. In addition, as the chlorine atom on the metal ruthenium atom can be further replaced by other groups, more complex and multi-redox active center compounds can be further constructed, thereby providing a new idea for designing long-distance molecular leads with long-distance charge transmission performance.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Finally, it should be emphasized that some of the descriptions of the present invention have been simplified to facilitate the understanding of the improvements of the present invention over the prior art by those of ordinary skill in the art, and that other elements have been omitted from this document for the sake of clarity, and those skilled in the art will recognize that these omitted elements may also constitute the content of the present invention.
Claims (8)
1. A triarylamine substituted terpyridyl ruthenium complex is characterized in that: the structural formula is shown as a formula (1),
2. a process for the preparation of a triarylamine-substituted ruthenium terpyridyl complex according to claim 1, which comprises the following steps:
1) Preparing triarylamine substituted terpyridine;
2) Sequentially adding triarylamine substituted terpyridine, tris (triphenylphosphine) ruthenium dichloride and methanol into a reaction vessel, reacting for 24-36 hours under stirring and refluxing, cooling to room temperature, concentrating a reaction system solvent, adding sodium hexafluorophosphate into the reaction system solvent to precipitate a solid, and recrystallizing by using dichloromethane/methanol to obtain the triarylamine substituted terpyridyl ruthenium complex.
3. A process for the preparation of a triarylamine substituted terpyridyl ruthenium complex as claimed in claim 2, wherein: in step 2), the ratio of the amounts of the triarylamine-substituted terpyridine to the tris (triphenylphosphine) ruthenium dichloride and sodium hexafluorophosphate is 1: (1 to 1.1): (15 to 20).
4. A process for the preparation of a triarylamine substituted terpyridyl ruthenium complex as claimed in claim 2, wherein: in step 2), each millimole of triarylamine-substituted terpyridine corresponds to 150 to 200mL of methanol.
5. The process for preparing a triarylamine-substituted terpyridyl ruthenium complex according to claim 2, wherein in step 1), the process for preparing the triarylamine-substituted terpyridyl comprises the following steps:
4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine, diphenylamine substituted by different substituents and tris (dibenzylideneacetone) dipalladium (Pd) are added into a reaction vessel in sequence 2 (dba) 3 ) Tri-tert-butylphosphine (b) t Bu 3 P), potassium tert-butoxide and toluene are reacted for 4~6 hours under stirring and refluxing, the mixture is cooled, dichloromethane is used for extraction and liquid separation to obtain an organic phase, then the organic phase is dried by spinning, and dichloromethane/normal hexane is used for recrystallization to obtain a light yellow solid, namely triarylamine substituted terpyridine.
6. A process for preparing a triarylamine substituted terpyridyl ruthenium complex according to claim 5, wherein: the ratio of the amount of 4'- (4-bromophenyl) -2,2':6',2' -terpyridine to the amount of different substituent substituted diphenylamine, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine, potassium tert-butoxide is 1: (1~3): (0.015 to 0.025): (0.015 to 0.050): (10 to 15).
7. A process for preparing a triarylamine substituted terpyridyl ruthenium complex according to claim 5, wherein: 10 to 15mL of toluene per millimole of 4' - (4-bromophenyl) -2,2' 6',2 "-terpyridine.
8. Use of a triarylamine-substituted terpyridyl ruthenium complex according to claim 1 in molecular wires.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498344.XA CN113150036B (en) | 2021-05-08 | 2021-05-08 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498344.XA CN113150036B (en) | 2021-05-08 | 2021-05-08 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113150036A CN113150036A (en) | 2021-07-23 |
| CN113150036B true CN113150036B (en) | 2023-03-24 |
Family
ID=76873675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110498344.XA Active CN113150036B (en) | 2021-05-08 | 2021-05-08 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113150036B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414965B (en) * | 2022-09-22 | 2023-11-28 | 河北科技大学 | Preparation method and application of terpyridyl supermolecular photocatalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163084B (en) * | 2017-06-02 | 2019-05-28 | 中国科学院化学研究所 | A kind of amine-ruthenium conjugation metal complex and its application in near-infrared electrochomeric films |
-
2021
- 2021-05-08 CN CN202110498344.XA patent/CN113150036B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113150036A (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oberhausen et al. | New tripodal Cu (II) complexes containing imidazole ligands | |
| Schulze et al. | 2, 2′: 6′, 2 ″-Terpyridine meets 2, 6-bis (1H-1, 2, 3-triazol-4-yl) pyridine: tuning the electro-optical properties of ruthenium (ii) complexes | |
| CN109535203B (en) | Conjugated ligand bridged diarylamine and ruthenium-acetylene end group compound and application thereof | |
| CN113150036B (en) | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof | |
| TW201602069A (en) | Zwitterionic compound and ion conductor | |
| CN109651449B (en) | Conjugated ligand bridged ferrocene and ruthenium acetylene end group compound and preparation method and application thereof | |
| Luo et al. | Synthesis of heteroleptic phosphine–copper (I) complexes: Fluorescence sensing and catalytic properties | |
| EP0647223A1 (en) | Ion-sensitive bipyridine complexes | |
| Goswami et al. | A bi-nuclear Cu (II)-complex for selective epoxidation of alkenes: Crystal structure, thermal, photoluminescence and cyclic voltammetry | |
| Wang et al. | Functionalized cyclopentadienyl rhodium (III) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones | |
| CN110372733B (en) | Metal organic copper complex with fluorescent property and preparation method thereof | |
| Şahin et al. | Synthesis, X-ray crystal structures, thermal and electrochemical properties of thiosemicarbazidatodioxouranium (VI) complexes | |
| CN113150035B (en) | Linear asymmetric N-Ru-N redox center terpyridyl ruthenium complex and preparation method and application thereof | |
| Tas et al. | Synthesis, characterization and redox properties of three new vic-dioximes and their nickel (II) metal complexes | |
| CN112851716B (en) | Terpyridyl ruthenium acetylene triphenylamine compound and preparation method and application thereof | |
| CN110358104A (en) | A kind of supermolecule cage and preparation method thereof based on asymmetric ligand assembling | |
| Fletcher et al. | New synthetic route to monocarbonyl polypyridyl complexes of ruthenium: their stereochemistry and reactivity | |
| Teramae et al. | Dinuclear copper–dioxygen intermediates supported by polyamine ligands | |
| CN110330527B (en) | Mononuclear copper complex with fluorescence property and preparation method thereof | |
| CN112778272B (en) | 2, 2' -biazaaryl ring bidentate ligand and preparation method and application thereof | |
| JP7330456B2 (en) | Curved aromatic compound and method for producing same | |
| CN110606937B (en) | Polymeric complex containing 4-vinylaniline derivative and Zn (II) and preparation method and application thereof | |
| Dincaa et al. | Synthesis and characterization of the cubic coordination cluster ½Co III | |
| Zhao et al. | Syntheses, structures and properties of cyclometalated iridium (III) complexes based on 2-phenyl-5-nitropyridyl and different strong-field ancillary ligands | |
| CN104098611A (en) | Carbon atom bridged chain type multi-ferrocene compound synthesizing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |