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 PDF

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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
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triarylamine
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terpyridyl
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欧亚平
朱小明
庾江喜
张复兴
张倩
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Hengyang Normal University
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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

Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof
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):
Figure 100002_DEST_PATH_IMAGE001
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:
Figure DEST_PATH_IMAGE002
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:
Figure DEST_PATH_IMAGE003
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:
Figure DEST_PATH_IMAGE004
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),
Figure DEST_PATH_IMAGE001
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.
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