CN109535203B - Conjugated ligand bridged diarylamine and ruthenium-acetylene end group compound and application thereof - Google Patents
Conjugated ligand bridged diarylamine and ruthenium-acetylene end group compound and application thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 44
- -1 ruthenium-acetylene end group compound Chemical class 0.000 title claims abstract description 41
- 125000005266 diarylamine group Chemical group 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims abstract description 4
- 239000002070 nanowire Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 54
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000011698 potassium fluoride Substances 0.000 claims description 27
- 235000003270 potassium fluoride Nutrition 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- GXZBISINOZEWRF-UHFFFAOYSA-K [Ru](Cl)(Cl)Cl.CC1=C(C(=C(C1(C(CP(C1=CC=CC=C1)C1=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)C)C)C)C Chemical compound [Ru](Cl)(Cl)Cl.CC1=C(C(=C(C1(C(CP(C1=CC=CC=C1)C1=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)C)C)C)C GXZBISINOZEWRF-UHFFFAOYSA-K 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 9
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- OVMFBUROZSKZPY-UHFFFAOYSA-N acetylene ruthenium Chemical group [Ru].C#C OVMFBUROZSKZPY-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- FSRXIRGQJIHEFB-UHFFFAOYSA-N diphenylphosphane;ethane Chemical compound CC.C=1C=CC=CC=1PC1=CC=CC=C1 FSRXIRGQJIHEFB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 125000005577 anthracene group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 125000005259 triarylamine group Chemical group 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004365 square wave voltammetry Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a conjugated ligand bridged diarylamine and ruthenium acetylene end group compound and application thereof, wherein the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound I is as follows:
wherein R is H, Me or OMe, and the conjugate ligand Ar is phenyl, naphthyl or anthryl. The electrochemical method tests show that the compound has extremely strong electronic interaction between the end groups, can present two continuous single-electron oxidation-reduction processes, and the potential difference delta E can reach 496-540 mV. The conjugated ligand bridged diarylamine and ruthenium acetylene end group compound can be widely applied to molecular wire materials, and provides a new research idea for the development of mixed redox active end group molecular wires and molecular electrons in the future.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a conjugated ligand bridged diarylamine and ruthenium acetylene end group compound and application thereof.
Background
The transition metal ruthenium end group is widely applied to the design of metal organic molecular wires, so that the electron transport capability of the conjugate bridge ligand is researched. Triarylamine and derivatives thereof are important organic molecules, and have wide application in the fields of medical intermediates, pesticides, dye chemical industry, organic materials and the like, and are also commonly researched as organic photoelectric materials due to excellent charge transfer performance.
The ruthenium metal end group and the triarylamine have excellent electrochemical activity and stability, for example, the excellent properties of the ruthenium metal end group and the triarylamine can be combined together, and a compound with strong electronic interaction between the end groups is synthesized, so that the development of the molecular lead material is greatly promoted, but no relevant report is found in the prior art at present.
Disclosure of Invention
The invention aims to provide a conjugated ligand bridged diarylamine and ruthenium acetylene end group compound with extremely strong electronic interaction between end groups.
In order to solve the technical problems, the invention adopts the following technical scheme: a conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has a structural formula I shown as follows:
wherein R is H, Me or OMe, and conjugate ligand Ar is phenyl, naphthyl or anthryl;
the phenyl is selected from:
one of (1);
the naphthyl group is selected from:
one of (1);
the anthracene group is selected from:
one kind of (1).
It will be clear to those skilled in the art that the above "Me" is methyl (CH)3) International acronym for english.
When the conjugated ligand Ar is
And when R is OMe, the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has the structural formula I-1 shown as follows:
the corresponding preparation method comprises the following steps:
a. under the protection of nitrogen, pentamethyl cyclopentadienyl (1, 2-bis diphenyl phosphine ethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-di (4-methoxyphenyl) -1-aniline) and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. performing suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. and (3) selecting acetone and petroleum ether as eluent to carry out column chromatography separation to obtain the product.
In the above preparation method, pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-aniline) and potassium fluoride in a molar ratio of 6: 5: 40, adding methanol according to the proportion that each 1mmol of potassium fluoride corresponds to 10ml of methanol, adding tetrahydrofuran according to the proportion that each 1mmol of potassium fluoride corresponds to 1.5-2ml of tetrahydrofuran, wherein the volume ratio of acetone to petroleum ether in the eluent is 1: 2.
II, when the conjugated ligand Ar is
And when R is OMe, the structural formula I-2 of the diarylamine and ruthenium acetylene end group compound bridged by the conjugated ligand is as follows:
the corresponding preparation method comprises the following steps:
a. under the protection of nitrogen, pentamethyl cyclopentadienyl (1, 2-bis diphenyl phosphine ethane) ruthenium chloride Cp*Ru (dppe) Cl, 3-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-aniline) and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22 to 28 hours, and then cooled to room temperature;
b. performing suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. and (3) selecting acetone and petroleum ether as eluent to carry out column chromatography separation to obtain the product.
In the above preparation method, pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 3-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-phenylamine) and potassium fluoride in a molar ratio of 6: 5: 40, adding methanol according to the proportion that each 1mmol of potassium fluoride corresponds to 10ml of methanol, adding tetrahydrofuran according to the proportion that each 1mmol of potassium fluoride corresponds to 1.5-2ml of tetrahydrofuran, wherein the volume ratio of acetone to petroleum ether in the eluent is 1: 2.
when the conjugated ligand Ar is
When R is OMe, the structural formula I-3 of the diarylamine and ruthenium acetylene end group compound bridged by the conjugated ligand is as follows:
the corresponding preparation method comprises the following steps:
a. pentamethylcyclopentadienyl (1, 2-bis-diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-naphthylamine) and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. and (4) carrying out suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane to obtain the compound.
In the above preparation method, pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-naphthylamine) and potassium fluoride in a molar ratio of 6: 5: 40, methanol is added in a ratio of 10ml per 1mmol of potassium fluoride, and tetrahydrofuran is added in a ratio of 1mmol of potassium fluoride1ml of tetrahydrofuran is added.
When the conjugated ligand Ar is
And when R is OMe, the structural formula I-4 of the diarylamine and ruthenium acetylene end group compound bridged by the conjugated ligand is as follows:
the corresponding preparation method comprises the following steps:
a. pentamethylcyclopentadienyl (1, 2-bis-diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 10-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -9-anthrylamine) and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. and (4) carrying out suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane to obtain the compound.
In the above preparation method, pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*The molar ratio between ru (dppe) Cl, 10-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -9-anthracenamine) and potassium fluoride was 6: 5: 40 methanol is added in a proportion of 10ml methanol per 1mmol potassium fluoride and tetrahydrofuran is added in a proportion of 1ml tetrahydrofuran per 1mmol potassium fluoride.
Compared with the prior art, the invention has the following beneficial effects: the invention selects ruthenium metal end group and diarylamine as oxidation-reduction active end group respectively, compounds with brand-new structure are synthesized by phenyl, naphthyl or anthryl bridging, and the electrochemical method tests show that the end groups of the compounds have extremely strong electronic interaction and can present two continuous single-electron oxidation-reduction processes, and the potential difference delta E reaches 496-540 mV. The conjugated ligand bridged diarylamine and ruthenium acetylene end group compound can be widely applied to molecular wire materials, and provides a new research idea for the development of mixed redox active end group molecular wires and molecular electrons in the future.
Drawings
FIG. 1 shows the NMR spectrum of the compound obtained in example 1.
FIG. 2 shows the NMR spectrum of the compound obtained in example 1.
FIG. 3 shows the NMR phosphorus spectrum of the compound obtained in example 1.
FIG. 4 shows the NMR spectrum of the compound obtained in example 2.
FIG. 5 shows the NMR spectrum of the compound obtained in example 2.
FIG. 6 shows the NMR phosphorus spectrum of the compound obtained in example 2.
FIG. 7 shows the NMR spectrum of the compound obtained in example 3.
FIG. 8 is a NMR spectrum of the compound obtained in example 3.
FIG. 9 shows the NMR phosphorus spectrum of the compound obtained in example 3.
FIG. 10 shows the NMR spectrum of the compound obtained in example 4.
FIG. 11 is a NMR spectrum of the compound obtained in example 4.
FIG. 12 shows the NMR phosphorus spectrum of the compound obtained in example 4.
Detailed Description
The following examples are given to illustrate the present invention and it should be noted that the following examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that the modification and modification of the present invention by those of ordinary skill in the art are not essential to the present invention.
Example 1
A conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has a structural formula I-1 shown as follows:
the method for preparing the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound comprises the following steps:
a. under the protection of nitrogen, 0.3mmol (1, 2-bis diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 0.25mmol of 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-aniline) and 2mmol of potassium fluoride were dissolved in a mixed solution of 20ml of methanol and 3-4ml of tetrahydrofuran, heated under reflux for 24 hours and then cooled to room temperature;
b. performing suction filtration, washing the obtained solid with 10ml of methanol and 10ml of n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. selecting a volume ratio of 1: 2, and performing column chromatography separation by using acetone and petroleum ether as eluent to obtain 150mg of yellow crystals with the yield of 62%.
The nuclear magnetic resonance carbon spectrogram, nuclear magnetic resonance hydrogen spectrogram and nuclear magnetic resonance phosphorus spectrogram of the product are respectively shown in figure 1, figure 2 and figure 3.
Elemental analysis (C)61H66NO2P2Ru): theoretical value: c, 72.67; h, 6.60. Measurement value: c, 72.59; h, 6.65.
Structural data:1H NMR(500MHz，CDCl3)：δ1.55(s，15H，CH3)，2.05(br，2H)，2.68(br，2H)，3.77(s，6H),6.66(dd，J(HH)＝10.0Hz，4H)，6.77(d，J(HH)＝10.0Hz，4H)，6.98(dd，J(HH)＝10.0Hz，4H)，7.19-7.33(m，16H，dppe-Ph and Ar)，7.79(s，4H)。
13C NMR(125MHz，CDCl3)：δ10.10(CH3)，29.47(CH2)，55.53(OCH3)，92.46(C5H5)，114.43，121.90，125.50，127.17，127.21，127.41，127.45，128.84，130.77，133.24，133.84，133.88，141.80，154.98。
31P NMR(200MHz，CDCl3)：δ80.93。
example 2
A conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has a structural formula I-2 shown as follows:
the method for preparing the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound comprises the following steps:
a. under the protection of nitrogen, 0.3mmol of pentamethylcyclopentadienyl (1, 2-bis-diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 0.25mmol of 3-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-aniline) and 2mmol of potassium fluoride were dissolved in a mixed solution of 20ml of methanol and 3-4ml of tetrahydrofuran, heated under reflux for 24 hours and then cooled to room temperature;
b. performing suction filtration, washing the obtained solid with 10ml of methanol and 10ml of n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. selecting a volume ratio of 1: 2, and carrying out column chromatography separation by using acetone and petroleum ether as eluent to obtain 167mg of light yellow crystals with the yield of 69%.
The nuclear magnetic resonance carbon spectrogram, nuclear magnetic resonance hydrogen spectrogram and nuclear magnetic resonance phosphorus spectrogram of the product are respectively shown in fig. 4, fig. 5 and fig. 6.
Elemental analysis (C)61H66NO2P2Ru): theoretical value: c, 72.67; h, 6.60. Measurement value: c, 72.49; h, 6.68.
Structural data:1H NMR(500MHz，CDCl3)：δ1.52(s，15H，CH3)，2.02(br，2H)，2.62(br，2H)，3.79(s，6H),6.43(d，J(HH)＝5.0Hz，1H)，6.52(d，J(HH)＝5.0Hz，1H)，6.56(s，1H)，6.81(d，J(HH)＝5.0Hz，4H)，6.86(t，J(HH)＝10.0Hz，1H)，7.01(d，J(HH)＝5.0Hz，1H)，7.14-7.33(m，16H，dppe-Ph andAr)，7.72(t，J(HH)＝10.0Hz，4H)。
13C NMR(125MHz，CDCl3)：δ9.99(CH3)，29.49(CH2)，55.53(OCH3)，92.52(C5H5)，109.52，114.47，117.22，123.75，124.19，125.88，127.04，127.08，127.11，127.31，127.34，127.38，127.90，128.77，133.19，133.62，133.66，133.70，136.65，137.03，138.86，139.12，141.88，147.93，155.21。
31P NMR(200MHz，CDCl3)：δ80.91。
example 3
A conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has a structural formula I-3 shown as follows:
the method for preparing the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound comprises the following steps:
a. 0.3mmol of pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 0.25mmol of 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-naphthylamine) and 2mmol of potassium fluoride were dissolved in a mixed solution of 20ml of methanol and 2ml of tetrahydrofuran, heated under reflux for 24 hours, and then cooled to room temperature;
b. suction filtration, washing the resulting solid with 10ml methanol and 10ml n-hexane respectively, followed by recrystallization with dichloromethane and n-hexane gave 180mg of a tea green solid, yield: 68 percent.
The nuclear magnetic resonance carbon spectrogram, nuclear magnetic resonance hydrogen spectrogram and nuclear magnetic resonance phosphorus spectrogram of the product are respectively shown in fig. 7, fig. 8 and fig. 9.
Elemental analysis (C)65H68NO2P2Ru): theoretical value: c, 73.77; h, 6.48. Measurement value: c, 73.69; h, 6.52.
Structural data:1H NMR(500MHz，CDCl3)：δ1.62(s，15H，CH3)，2.13(br，2H)，2.27(br，2H)，3.75(s，6H),6.72(s，2H)，6.73(d，J(HH)＝5.0Hz，2H)，6.91-6.93(m，6H)，7.16-7.33(m，16H)，7.80(d，J(HH)＝10.0Hz，6H)。
13C NMR(125MHz，CDCl3)：δ10.19(CH3)，29.48(CH2)，55.52(OCH3)，92.79(C5H5)，108.38，114.32，122.76，123.68，124.46，125.21，126.39，127.39，127.43，127.47，127.51，128.58，128.86，128.95，133.11，133.16，133.20，133.75，133.79，133.82，143.03，154.08。
31P NMR(200MHz，CDCl3)：δ81.20。
example 4
A conjugated ligand bridged diarylamine and ruthenium acetylene end group compound has a structural formula I-4 shown as follows:
the method for preparing the conjugated ligand bridged diarylamine and ruthenium acetylene end group compound comprises the following steps:
a. 0.3mmol of pentamethylcyclopentadienyl (1, 2-bisdiphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 0.25mmol of 10-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -9-anthracenamine) and 2mmol of potassium fluoride were dissolved in a mixed solution of 20ml of methanol and 2ml of tetrahydrofuran, heated under reflux for 24 hours, and then cooled to room temperature;
b. and (3) performing suction filtration, washing the obtained solid with 10ml of methanol and 10ml of n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane to obtain 170mg of tea green solid, wherein the yield is as follows: 61 percent.
The nuclear magnetic resonance carbon spectrogram, nuclear magnetic resonance hydrogen spectrogram and nuclear magnetic resonance phosphorus spectrogram of the product are respectively shown in fig. 10, fig. 11 and fig. 12.
Elemental analysis (C)69H70NO2P2Ru): theoretical value: c, 74.77; h, 6.37. Measurement value: c, 74.83; h, 6.34.
Structural data:1H NMR(500MHz，CDCl3)：δ1.69(s，15H，CH3)，2.16(br，2H)，2.90(br，2H)，3.70(s，6H)，6.68(d，J(HH)＝10.0Hz，4H)，6.81(t，J(HH)＝10.0Hz，2H)，6.98(d，J(HH)＝10.0Hz，4H)，7.11-7.38(m，18H，dppe-Ph andAn)，7.55(t，J(HH)＝10.0Hz，4H)，7.89(d，J(HH)＝10.0Hz，2H)，7.94(d，J(HH)＝5.0Hz，2H)。
13C NMR(125MHz，CDCl3)：δ10.37(CH3)，29.48(CH2)，55.47(OCH3)，93.16(C5H5)，109.05，114.31，120.83，123.15，123.69，125.79，127.47，127.50，127.55，129.01，129.18，129.58，133.28，133.70，137.21，138.46，138.73，142.27，146.78，153.41。
31PNMR(200MHz，CDCl3)：δ81.22。
electrochemical measurement test
The adopted equipment comprises the following steps: electrochemical workstation CHI 660C (CH Instruments Company, USA).
Using glassy carbon electrode as working electrode, platinum electrode as counter electrode, Ag+And the | Ag electrode is a reference electrode. At 0.001mol L-1n-Bu4NPF6CH (A) of2Cl2The solution is electrolyte, and the concentration of the measured substrate is 0.001mol L-1。
Cyclic voltammetry is usually performed at a scan rate of 100mV s-1The square wave voltammetry was measured at f ═ 10 Hz.
Data processing: the data were processed into pictures by OriginPro 8.0.
The conjugated ligand bridged diarylamine and ruthenium acetylene end group compounds are subjected to cyclic voltammetry and square wave voltammetry tests by an electrochemical method to obtain a potential difference delta E and an equilibrium constant Kc value of two times of oxidation reduction, and the results are shown in Table 1.
TABLE 1 electrochemical test data for conjugated ligand bridged diarylamines and ruthenium acetylene end-group compounds
| Compound (I) | E1/2(1)(V) | E1/2(2)(V) | ΔE(mV)b | Kc c |
| I-1 | 0.165 | 0.665 | 500 | 2.83×108 |
| I-2 | 0.357 | 0.853 | 496 | 1.98×108 |
| I-3 | 0.176 | 0.703 | 527 | 6.53×108 |
| I-4 | 0.170 | 0.710 | 540 | 1.07×109 |
As can be seen from Table 1, the compounds prepared by the invention all present two continuous single-electron redox processes, and the potential difference Delta E of the two redox processes obtained by testing can reach 496-540mV, and the results show that the terminal groups of the conjugated ligand bridged diarylamine and ruthenium acetylene terminal group compounds provided by the invention present extremely strong electronic interaction (coupling).
Claims (9)
1. A conjugated ligand bridged diarylamine and ruthenium acetylene end group compound is characterized in that the structural formula I is as follows:
wherein R is OMe, and the conjugate ligand Ar is phenyl, naphthyl or anthryl;
the phenyl is selected from:
one of (1);
the naphthyl group is:
the anthracene group is as follows:
2. the method for preparing the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound is characterized in that the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound have the structural formula I-1 shown as follows:
the corresponding preparation process comprises the following steps:
a. under the protection of nitrogen, pentamethyl cyclopentadienyl (1, 2-bis diphenyl phosphine ethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-phenylamine and potassium fluoride were dissolved in a mixed solution of methanol and tetrahydrofuran, and the mixture was refluxedCooling to room temperature after 22-28 h;
b. performing suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. and (3) selecting acetone and petroleum ether as eluent to carry out column chromatography separation to obtain the product.
3. The method for preparing the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound is characterized in that the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound have the structural formula I-2 shown as follows:
the corresponding preparation process comprises the following steps:
a. under the protection of nitrogen, pentamethyl cyclopentadienyl (1, 2-bis diphenyl phosphine ethane) ruthenium chloride Cp*Ru (dppe) Cl, 3-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-aniline and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. performing suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane;
c. and (3) selecting acetone and petroleum ether as eluent to carry out column chromatography separation to obtain the product.
4. A process according to claim 2 or 3 for the preparation of conjugated ligand bridged diarylamines and ruthenium acetylene end group compounds, characterized in that: the volume ratio of acetone to petroleum ether is 1: 2.
5. a process according to claim 2 or 3 for the preparation of conjugated ligand bridged diarylamines and ruthenium acetylene end group compounds, characterized in that: methanol is added in a ratio of 10ml methanol per 1mmol potassium fluoride, and tetrahydrofuran is added in a ratio of 1.5-2ml tetrahydrofuran per 1mmol potassium fluoride.
6. The method for preparing the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound is characterized in that the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound have the structural formula I-3 shown as follows:
the corresponding preparation process comprises the following steps:
a. pentamethylcyclopentadienyl (1, 2-bis-diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 4-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -1-naphthylamine and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. and (4) carrying out suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane to obtain the compound.
7. The method for preparing the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound is characterized in that the conjugated ligand bridged diarylamine and the ruthenium-acetylene end group compound have the structural formula I-4 shown as follows:
the corresponding preparation process comprises the following steps:
a. pentamethylcyclopentadienyl (1, 2-bis-diphenylphosphinoethane) ruthenium chloride Cp*Ru (dppe) Cl, 10-trimethylsilylethynyl-N, N-bis (4-methoxyphenyl) -9-anthrylamine and potassium fluoride are dissolved in a mixed solution of methanol and tetrahydrofuran, heated and refluxed for 22-28h, and then cooled to room temperature;
b. and (4) carrying out suction filtration, washing the obtained solid with methanol and n-hexane respectively, and then recrystallizing with dichloromethane and n-hexane to obtain the compound.
8. A process according to claim 6 or 7 for the preparation of conjugated ligand bridged diarylamines and ruthenium acetylene end group compounds, characterized in that: methanol was added in a ratio of 10ml of methanol per 1mmol of potassium fluoride, and tetrahydrofuran was added in a ratio of 1ml of tetrahydrofuran per 1mmol of potassium fluoride.
9. The use of a conjugated ligand-bridged diarylamine and ruthenium acetylene end group compound as claimed in claim 1 in molecular wire materials.
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