阅读说明：本技术 一种7号位乙烯基取代锇杂戊搭炔的制备方法及其应用 (Preparation method and application of 7-position vinyl substituted osmium heteropentadiyne ) 是由 夏海平 陈仕焰 张颖 朱永发 刘亚南 高翔 林祖樟 蔡亚鹏 欧阳普凡 卓庆德 何 于 2019-08-28 设计创作，主要内容包括：本发明公开了一种7号位乙烯基取代锇杂戊搭炔的制备方法,其反应式为：<Image he="179" wi="700" file="DDA0002182547120000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明制得的7号位乙烯基取代锇杂戊搭炔溶解度高,稳定性好,并且具有非常高的摩尔吸光系数和较好的电化学性能,可以广泛应用于染料敏化太阳能电池、有机太阳能电池、光动力学治疗、光解水、锂-空气电池等领域。本发明制得的制备方法的反应具有高效专一,反应条件温和,官能团容忍度好的特点。(The invention discloses a preparation method of 7-position vinyl substituted osmium hybrid pentyne, which has the following reaction formula: the 7-position vinyl substituted osmium heteropentadiyne prepared by the method has high solubility and good stability, has very high molar absorption coefficient and better electrochemical performance, and can be widely applied to the fields of dye-sensitized solar cells, organic solar cells, photodynamic therapy, water photolysis, lithium-air cells and the like. The preparation method has the characteristics of high efficiency, specificity, mild reaction conditions and good functional group tolerance.)

1. A preparation method of 7-position vinyl substituted osmium heteropentadiyne is characterized by comprising the following steps: the reaction formula is as follows:

above [ Os)]Is OsAL₂、OsA₂L or OsL₃Wherein, A is-H, halogen, -SCN or-CN, L is at least one of phosphine ligand, CO ligand, pyridine ligand, nitrogen heterocyclic carbene ligand, nitrile ligand and isocyan dual-electron ligand;

x is a quaternary phosphonium cation of 3 to 30 carbon atoms, a quaternary ammonium cation of 3 to 24 carbon atoms, -H, halogen, -SCN or-CN;

r is as defined above₁is-H, halogen, -SCN, -CN, alkyl of 1-20 carbon atoms, alkoxy of 1-20 carbon atoms, alkylthio of 1-20 carbon atoms, acyl of 1-20 carbon atoms, ester of 1-20 carbon atoms, amine of 1-20 carbon atoms, amide of 1-20 carbon atoms, carboxyl of 1-20 carbon atoms, substituted amide of 2-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, substituted or unsubstituted aryl of 3-20 carbon atoms, substituted or unsubstituted alkenyl of 2-80 carbon atoms, 2-80A substituted or unsubstituted alkynyl group of carbon atoms, an aryloxy group of 1 to 20 carbon atoms or an arylthio group of 1 to 20 carbon atoms;

r is as defined above₂Is a substituent at the 5-or 6-position of the osmium heteropentadienyl compound mentioned above, and R₂is-H, halogen, -SCN, -CN, alkyl of 1-20 carbon atoms, alkoxy of 1-20 carbon atoms, alkylthio of 1-20 carbon atoms, acyl of 1-20 carbon atoms, ester of 1-20 carbon atoms, amine of 1-20 carbon atoms, amide of 1-20 carbon atoms, carboxyl of 1-20 carbon atoms, substituted amide of 2-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, substituted or unsubstituted aryl of 3-20 carbon atoms, substituted or unsubstituted alkenyl of 2-80 carbon atoms, substituted or unsubstituted alkynyl of 2-80 carbon atoms, aryloxy of 1-20 carbon atoms or arylthio of 1-20 carbon atoms;

or the above R₂Is a cyclic substituent located in the 5-to 6-position of the osmium heteropentadienyl compound described above, and R is₂Is a four-membered, five-membered, six-membered, seven-membered or eight-membered ring substituent consisting entirely of carbon atoms, or a three-membered, four-membered, five-membered, six-membered, seven-membered or eight-membered ring substituent consisting of at least one heteroatom containing oxygen, sulfur, nitrogen and silicon;

r is as defined above₃Is substituted or unsubstituted aryl of 3 to 80 carbon atoms, substituted or unsubstituted alkenyl of 2 to 20 carbon atoms, substituted or unsubstituted alkynyl of 2 to 20 carbon atoms;

z is an anion or null.

2. The method of claim 1, wherein: the anion comprises F^-、Cl^-、Br^-、I^-、BF₄ ^-、H₂PO₄ ^-、C₂O₄ ^2-、SO₄ ^2-、CF₃SO₃ ^-、CH₃COO^-、(CF₃SO₂)₂N^-、NO₃ ^-、ClO₄ ^-、PF₆ ^-And BPh₄ ^-。

3. The method of claim 1, wherein: the [ Os ] is]L in (A) is at least one of triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, methylpyridine, ethylpyridine, 1, 4-bipyridine, 1, 2-bis (4-pyridyl) ethylene, vinylpyridine, ethynylpyridine, pyridineboronic acid, aminopyridine, cyanopyridine, mercaptopyridine, dimethylaminopyridine, phenylpyridine, 1, 2-bis (4-pyridyl) ethane, imidazole-type azacyclo-carbene, imidazoline-type azacyclo-carbene, thiazole-azacyclo-carbene, triazole-azacyclo-carbene, acetonitrile, propionitrile, benzonitrile, cyclohexyl isocyan, tert-butyl isocyan and phenyl isocyan, or [ Os ] s]L in (1)₂Is a whole and L₂Is ethylenediamine, 2' -bipyridine, 1, 10-phenanthroline, 1-bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, o-phenylpyridine or 8-hydroxyquinoline; or said [ Os]AL in₂Is a whole body, and AL₂Is a tridentate ligand of the terpyridine, PPP, PNP, PCP, NNN, NCN, NPN, ONO, OPO, OCO, SCS or CCC type.

4. The method of claim 1, wherein: the R is₁Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, tert-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl, tert-dodecyl, n-hexadecyl, n-dodecyl, n-eicosyl, n-dodecyl, n-hexadecyl,

5. As in claimThe method of claim 1, wherein: the R is₂Is a substituent at the 5-or 6-position of the osmium heteropentadienyl compound, and R is₂Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, tert-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl, tert-dodecyl, n-hexadecyl, n-dodecyl, n-eicosyl, n-dodecyl, n-hexadecyl,

6. The method of claim 1, wherein: the R is₂Is a cyclic substituent located in the 5-to 6-position of the osmium heteropentadienyl compound, and R is₂Is composed of

7. The method of claim 1, wherein: the R is₃Wherein the aryl group in R3 is phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thienyl, furyl, pyridyl, pyrrolyl, porphinyl, fluorenyl, carbazolyl, benzothiadiazolyl, tetraphenylethylene or perylenediimideA hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an acyl group of 1 to 20 carbon atoms, an ester group of 1 to 20 carbon atoms, an amine group of 1 to 20 carbon atoms, a nitro group, a cyano group or a halogen.

8. The method of claim 1, wherein: the acid includes inorganic acid and organic acid, and the inorganic acid includes HClO₄、HI、HBr、HCl、HNO₃、H₂SeO₄、H₂SO4、HClO₃、H₂C₂O₄、H₂SO₃、H₃PO₄、HNO₂、HF、H₂CO₃、H₂S、HClO、H₃BO₃And H₂SiO₃(ii) a The organic acid comprises CH₃SO₃H、CF₃COOH、CCl₃COOH、CHCl₂COOH、CH₃COOH and HCOOH.

9. The production method according to any one of claims 1 to 8, characterized in that: the halogen is F, Cl, Br or I.

10. The production method according to any one of claims 1 to 8, characterized in that: the osmium hybrid pentyne compound is prepared from an osmium hybrid pentyne precursor compound through a metal-carbon triple bond transfer reaction by adding acid, and the reaction formula is as follows:

11. the method of claim 1, wherein: a in the [ Os ] is H, F, Cl, Br or SCN;

l in the [ Os ] is at least one of a CO ligand, a triphenylphosphine ligand, a trimethylphosphine ligand and a triethylphosphine ligand;

the X is triphenylphosphine cation, trimethylphosphine cation, triethylphosphine cation, trimethylamine cation, triethylamine cation, F, Cl, Br or I;

z is Cl^-、Br^-、BF₄ ^-、CF₃SO₃ ^-、PF₆ ^-Or BPh₄ ^-；

The R is₁is-H, -F, -Cl, -Br, -SCN, -CN, -OPh, -SPh,

the R is₂Is a cyclic substituent located in the 5-to 6-position of the osmium heteropentadienyl compound, and R is₂Is composed of

12. The method of claim 1, wherein: the osmium heteropentadienyl compound is one of the following compounds:

the [ Os ] is]Is OsCl (PPh)₃)₂，[Os¹]Is Os (PPh)₃)₂，[Os²]Is OsCl₂(PPh₃)₃，[Os³]Is Os, [ Os⁴]Is Os (PMe)₃)₃，[Os⁵]Is OsCl (PPh)₃)₃；

The terminal alkyne compound is one of the following:

13. use of the vinyl-substituted osmium heteropentayne at position 7 prepared by the preparation method according to any one of claims 1 to 12 in a solar cell.

14. Use of the vinyl-substituted osmium heteropentayne at position 7 prepared by the method according to any one of claims 1 to 12 for the preparation of a material for photodynamic therapy.

15. Use of the vinyl-substituted osmium heteropentayne at position 7 prepared by the preparation method according to any one of claims 1 to 12 for photolysis of water.

16. Use of the vinyl-substituted osmium heteropentayne at position 7 prepared by the preparation method according to any one of claims 1 to 12 for preparing a lithium-air battery.

Technical Field

The invention belongs to the technical field of metal organic chemistry, and particularly relates to a preparation method and application of 7-position vinyl substituted osmium heteropentadiyne.

Background

Metal-organic chemistry is across inorganic and organic chemistry and is closely related to energy, materials, environment, and life sciences. In recent years, with the rapid development of metal organic chemistry, two traditional branches have been formed: one is the traditional metal organic chemistry, namely, designing and synthesizing a novel metal organic compound, and researching the structure, the reaction performance and the application prospect of the novel metal organic compound; and the other is metal organic chemistry oriented to organic synthesis, namely, the metal-promoted high-selectivity catalytic reaction is developed, so that a new method is provided for synthesizing medicines, new materials and the like. Metalorganic chemistry has become one of the leading areas of modern chemistry as an important discipline.

The transition metal atom is introduced into the aromatic ring, so that a brand new aromatic structural element, namely a transition metal heteroaromatic fused ring compound can be created. Different from p pi-p pi conjugation of a traditional pi conjugation system, the doped transition metal can form d pi-p pi conjugation, and due to the fact that the transition metal is multiple in types, adjustable in valence state, long in excited state service life and strong in functional ligand designability, the design space of an aromatic ring framework can be increased, and the performance of the compound can be remarkably improved. In recent years, the synthesis and characterization of heteroaromatic fused ring compounds containing transition metals have attracted much attention.

In 2013, Xia and the like (nat. chem.2013, 5, 698-containing 703) report a novel metal bridged metal hetero-fused ring compound, namely an osmium hetero-pentyne compound, which has the characteristics of aggregation-induced luminescence enhancement effect, large Stock displacement, long luminescence life and the like, and has an important application prospect in the field of organic photoelectricity. In 2014, Xia et al reported a specific substituent group osmium heteropentaeneyne compound which has very good ultraviolet-visible light absorption performance (Angew. chem. int. Ed.2014, 53, 6232-one 6236). Another class of metal-bridged osmium heterofused ring compounds was reported by Xia in 2015, which have good photoacoustic imaging and photothermal properties and potential application prospects in tumor diagnosis and treatment (angelw. chem. int. ed.2015, 54, 6181-. In 2017, Xia et al reported another class of rivet group-containing substituted metallic osmium heteropentaalkynes derivatives with good single-molecule conductance values (J.Am.chem.Soc., 2017, 139, 14344-one 14347).

However, although the osmium heteropentaeneyne series compounds show unique properties in the fields of light and electricity, which are not possessed by other materials, the synthesis method of the compounds is quite limited at present, and the structures of final products are quite limited. Therefore, it is important to develop a method for substituting osmium heteropentadiyne with different function-oriented functional groups.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of 7-position vinyl substituted osmium heteropentadiyne.

The invention also aims to provide application of the 7-position vinyl-substituted osmium heteropentayne prepared by the method.

The technical scheme of the invention is as follows:

a preparation method of 7-position vinyl substituted osmium heteropentadiyne has the following reaction formula:

above [ Os)]Is OsAL₂、OsA₂L or OsL₃Wherein, A is-H, halogen, -SCN or-CN, L is at least one of phosphine ligand, CO ligand, pyridine ligand, N-Heterocyclic carbene NHC ligand, nitrile ligand and isocyanic two-electron ligand; the pyridine ligand is a ligand containing a pyridine or bipyridine structural unit; the N-heterocyclic carbene ligand is a ligand containing an N-heterocyclic carbene structural unit; the nitrile ligand is a ligand containing a nitrile group structural unit; the above-mentioned isocyanide type two-electron ligand is a ligand containing an isocyanide structural unit.

X is a quaternary phosphonium cation of 3 to 30 carbon atoms, a quaternary ammonium cation of 3 to 24 carbon atoms, -H, halogen, -SCN or-CN;

r is as defined above₁is-H, halogen, -SCN, -CN, alkyl of 1-20 carbon atoms, alkoxy of 1-20 carbon atoms, alkylthio of 1-20 carbon atoms, acyl of 1-20 carbon atoms, ester of 1-20 carbon atoms, amine of 1-20 carbon atoms, amide of 1-20 carbon atoms, carboxyl of 1-20 carbon atoms, substituted amide of 2-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, substituted or unsubstituted aryl of 3-20 carbon atoms, substituted or unsubstituted alkenyl of 2-80 carbon atoms, substituted or unsubstituted alkynyl of 2-80 carbon atoms, aryloxy of 1-20 carbon atoms, arylthio of 1-20 carbon atoms, polyethylene glycol residue, hyaluronic acid, Polyacrylic acid or saccharide derivative residues;

r is as defined above₂Is a substituent at the 5-or 6-position of the osmium heteropentadienyl compound mentioned above, and R₂is-H, halogen, -SCN, -CN, alkyl of 1-20 carbon atoms, alkoxy of 1-20 carbon atoms, alkylthio of 1-20 carbon atoms, acyl of 1-20 carbon atoms, ester of 1-20 carbon atoms, amine of 1-20 carbon atoms, amide of 1-20 carbon atoms, carboxyl of 1-20 carbon atoms, substituted amide of 2-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, substituted or unsubstituted aryl of 3-20 carbon atoms, substituted or unsubstituted alkenyl of 2-80 carbon atomsUnsubstituted alkynyl, aryloxy of 1 to 20 carbon atoms, arylthio of 1 to 20 carbon atoms, polyethylene glycol residue, hyaluronic acid residue, polyacrylic acid or saccharide derivative residue;

or the above R₂Is a cyclic substituent positioned on 5-6 positions of the osmium heteropentadiene compound, and R2 is a four-membered, five-membered, six-membered, seven-membered or eight-membered ring substituent all composed of carbon atoms, or a three-membered, four-membered, five-membered, six-membered, seven-membered or eight-membered ring substituent composed of at least one heteroatom containing oxygen, sulfur, nitrogen and silicon;

r is as defined above₃Is substituted or unsubstituted aryl of 3 to 80 carbon atoms, substituted or unsubstituted alkenyl of 2 to 20 carbon atoms, substituted or unsubstituted alkynyl of 2 to 20 carbon atoms;

z is an anion or null.

In a preferred embodiment of the invention, the anion comprises F^-、Cl^-、Br^-、I^-、BF₄ ^-、H₂PO₄ ^-、C₂O₄ ^2-、SO₄ ^2-、CF₃SO₃ ^-、CH₃COO^-、(CF₃SO₂)₂N^-、NO₃ ^-、ClO₄ ^-、PF₆ ^-And BPh₄ ^-。

In a preferred embodiment of the invention, the phosphine ligand is an alkyl phosphine of 3 to 24 carbon atoms, a cycloalkyl phosphine of 3 to 24 carbon atoms or an aryl phosphine of 3 to 24 carbon atoms.

Further preferably, the phosphine ligand is an alkyl phosphine of 5 to 20 carbon atoms, a cycloalkyl phosphine of 5 to 20 carbon atoms or an aryl phosphine of 5 to 20 carbon atoms.

Even more preferably, the phosphine ligand is an alkyl phosphine of 6 to 18 carbon atoms, a cycloalkyl phosphine of 6 to 18 carbon atoms or an aryl phosphine of 6 to 18 carbon atoms.

Specifically, L in the [ Os ] is at least one of triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, methylpyridine, ethylpyridine, 1, 4-bipyridine, 1, 2-bis (4-pyridyl) ethene, vinylpyridine, ethynylpyridine, pyridineboronic acid, aminopyridine, cyanopyridine, mercaptopyridine, dimethylaminopyridine, phenylpyridine, 1, 2-bis (4-pyridyl) ethane, imidazole-type azacyclo-carbene, imidazoline-type azacyclo-carbene, thiazole-azacyclo-carbene, triazole-azacyclo-carbene, acetonitrile, propionitrile, benzonitrile, cyclohexyl isocyan, tert-butyl isocyan, and phenyl isocyan.

In a preferred embodiment of the present invention, the [ Os ] is]L in (1)₂Is a whole and L2 is a bidentate nitrogen ligand, a bidentate phosphine ligand, a bidentate carbon-nitrogen ligand or a bidentate oxygen-nitrogen ligand, in particular, L₂Is ethylenediamine, 2' -bipyridine, 1, 10-phenanthroline, 1-Bis (diphenylphosphino) methane (DPPM, Bis- (diphenylphosphino) methane), 1, 2-Bis (diphenylphosphino) ethane (DPPE, 1, 2-Bis (diphenylphosphino) ethane), 1, 3-Bis (diphenylphosphino) propane (DPPP, 1, 3-Bis (diphenylphosphino) propane), orthophenylpyridine or 8-hydroxyquinoline.

In a preferred embodiment of the present invention, the [ Os ] is]AL in₂Is a whole body, and AL₂Is a terpyridine or tridentate Pincer (Pincer) ligand, in particular, AL₂Is a tripyridyl, PPP, PNP, PCP, NNN, NCN, NPN, ONO, OPO, OCO, SCS or CCC type tridentate clamp ligand.

In a preferred embodiment of the invention, X is a quaternary phosphonium cation of 5 to 23 carbon atoms, a quaternary ammonium cation of 5 to 20 carbon atoms, -H, halogen, -SCN or-CN.

Further preferably, X is a quaternary phosphonium cation of 6 to 18 carbon atoms, a quaternary ammonium cation of 6 to 18 carbon atoms, -H, halogen, -SCN or-CN.

The quaternary phosphonium cation is an alkyl quaternary phosphine cation, a cycloalkyl quaternary phosphine cation or an aryl quaternary phosphine cation, and specifically, the quaternary phosphonium cation is a trimethyl phosphine cation, a triethyl phosphine cation, a tripropyl phosphine cation, a triisopropyl phosphine cation, a tri-tert-butyl phosphine cation, a tricyclohexyl phosphine cation or a triphenyl phosphine cation.

The quaternary ammonium cation is trimethylamine cation, triethylamine cation, dimethyl monoethylamine cation, tripropylammonium cation, triisopropyl ammonium cation or tri-tert-butyl ammonium cation.

In a preferred embodiment of the present invention, said R₂is-H, halogen, -SCN, -CN, alkyl of 1-17 carbon atoms, alkoxy of 1-17 carbon atoms, alkylthio of 1-17 carbon atoms, acyl of 1-17 carbon atoms, ester of 1-17 carbon atoms, amine of 1-17 carbon atoms, amide of 1-17 carbon atoms, carboxyl of 1-17 carbon atoms, substituted amide of 2-17 carbon atoms, cycloalkyl of 3-17 carbon atoms, substituted or unsubstituted aryl of 3-17 carbon atoms, substituted or unsubstituted alkenyl of 2-60 carbon atoms, substituted or unsubstituted alkynyl of 2-60 carbon atoms, aryloxy of 2-17 carbon atoms, arylthio of 2-17 carbon atoms, polyethylene glycol residue, hyaluronic acid, Polyacrylic acid or saccharide derivative residues.

Further preferably, R is₂is-H, halogen, -SCN, -CN, alkyl of 1-8 carbon atoms, alkoxy of 1-8 carbon atoms, alkylthio of 1-8 carbon atoms, acyl of 1-8 carbon atoms, ester of 1-8 carbon atoms, amine of 1-8 carbon atoms, amide of 1-8 carbon atoms, carboxyl of 1-8 carbon atoms, substituted amide of 2-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, substituted or unsubstituted aryl of 3-8 carbon atoms, substituted or unsubstituted alkenyl of 2-45 carbon atoms, substituted or unsubstituted alkynyl of 2-45 carbon atoms, aryloxy of 2-8 carbon atoms, arylthio of 2-8 carbon atoms, polyethylene glycol residue, hyaluronic acid, Polyacrylic acid or saccharide derivative residues.

Specifically, the R is₁Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctylSec-octyl, tert-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl,

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, isohexoxy, neohexoxy, sec-hexoxy, tert-hexoxy, n-heptoxy, isoheptoxy, neoheptoxy, sec-heptoxy, tert-heptoxy, n-octoxy, isooctoxy, neooctyloxy, sec-octyloxy, tert-octyloxy, n-dodecyloxy, n-hexadecyloxy, n-octadecyloxy, n-eicosyloxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, neopentylthio, sec-pentylthio, tert-pentylthio, n-hexylthio, isohexylthio, neohexylthio, sec-hexylthio, tert-hexylthio, n-heptylthio, isopentylthio, sec-, Isoheptylthio, neoheptylthio, sec-heptylthio, tert-heptylthio, n-octylthio, isooctylthio, neooctylthio, sec-octylthio, tert-octylthio, n-dodecylthio, n-hexadecylthio, n-octadecylthio, n-eicosylthio, tert-octylthio,

Methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, n-dodecylaminoAmino, n-hexadecylamino, n-octadecylamino, n-eicosylamino,

Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, cyclooctadecyl, cycloeicosanyl, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, thienyl, dithionyl, tritenyl, furyl, pyridyl, pyrrolyl, porphinyl, fluorenyl, carbazolyl, benzothiadiazolyl, tetraphenylethylene, perylenediimido-yl,

Phenoxy, naphthoxy, anthracenoxy, phenanthreneoxy, pyreneoxy, thiophenoxy, furyloxy, pyridyloxy, pyrrolyloxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, p-nitrophenoxy, p-methoxyphenoxy, thiophenyl, naphthylthio, anthracenylthio, phenanthrenethio, pyrenethio, thiophenylthio, furanthio, pyridylthio, pyrrolylthio, p-tolylthio, m-tolylthio, o-tolylthio, p-nitrophenylthio, p-methoxyphenylthio, a polyethylene glycol residue, a hyaluronic acid residue, polyacrylic acid and a saccharide derivative residue, wherein n is a positive integer of more than 0 and less than 32.

In a preferred embodiment of the present invention, said R₂Is a substituent at the 5-or 6-position of the osmium heteropentadienyl compound, and R is₂is-H, halogen, -SCN, -CN, alkyl of 1-17 carbon atoms, alkoxy of 1-17 carbon atoms, alkylthio of 1-17 carbon atoms, acyl of 1-17 carbon atoms, ester of 1-17 carbon atoms, amine of 1-17 carbon atoms, amide of 1-17 carbon atoms, carboxyl of 1-17 carbon atoms, substituted amide of 2-17 carbon atoms, cycloalkyl of 3-17 carbon atoms, substituted or unsubstituted aryl of 3-17 carbon atoms, substituted or unsubstituted alkenyl of 2-60 carbon atoms, substituted or unsubstituted alkynyl of 2-60 carbon atoms, aryloxy of 2-17 carbon atoms, arylthio of 2-17 carbon atoms, polyethylene glycol residue, hyaluronic acid, Polyacrylic acid or saccharide derivative residues.

Still further preferably, said R₂is-H, halogen, -SCN, -CN, alkyl of 1-8 carbon atoms, alkoxy of 1-8 carbon atoms, alkylthio of 1-8 carbon atoms, acyl of 1-8 carbon atoms, ester of 1-8 carbon atoms, amine of 1-8 carbon atoms, amide of 1-8 carbon atoms, carboxyl of 1-8 carbon atoms, substituted amide of 2-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, substituted or unsubstituted aryl of 3-8 carbon atoms, substituted or unsubstituted alkenyl of 2-45 carbon atoms, substituted or unsubstituted alkynyl of 2-45 carbon atoms, aryloxy of 2-8 carbon atoms, arylthio of 2-8 carbon atoms, polyethylene glycol residue, hyaluronic acid, Polyacrylic acid or saccharide derivative residues.

Specifically, the R is₂Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexylAn alkyl group, an isohexyl group, a neohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a neoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a neooctyl group, a sec-octyl group, a tert-octyl group, an n-dodecyl group, an n-hexadecyl group, an n-octadecyl group, an n-eicosyl group, an N-eicosyl,

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, isohexoxy, neohexoxy, sec-hexoxy, tert-hexoxy, n-heptoxy, isoheptoxy, neoheptoxy, sec-heptoxy, tert-heptoxy, n-octoxy, isooctoxy, neooctyloxy, sec-octyloxy, tert-octyloxy, n-dodecyloxy, n-hexadecyloxy, n-octadecyloxy, n-eicosyloxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, neopentylthio, sec-pentylthio, tert-pentylthio, n-hexylthio, isohexylthio, neohexylthio, sec-hexylthio, tert-hexylthio, n-heptylthio, isopentylthio, sec-, Isoheptylthio, neoheptylthio, sec-heptylthio, tert-heptylthio, n-octylthio, isooctylthio, neooctylthio, sec-octylthio, tert-octylthio, n-dodecylthio, n-hexadecylthio, n-octadecylthio, n-eicosylthio, tert-octylthio,

Methylamino, ethylamineA group, a propylamino group, an butylamine group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an n-dodecylamino group, an n-hexadecylamino group, an n-octadecylamino group, an n-eicosylamino group, a substituted aminol group,

Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, cyclooctadecyl, cycloeicosanyl, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, thienyl, dithionyl, tritenyl, furyl, pyridyl, pyrrolyl, porphinyl, fluorenyl, carbazolyl, benzothiadiazolyl, tetraphenylethylene, perylenediimido-yl,

Phenoxy, naphthoxy, anthracenoxy, phenanthrenoxy, pyreneoxy, thiophenoxy, furanoxy, pyridyloxy, pyrrolyloxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, p-nitroPhenoxy, p-methoxyphenoxy, phenylthio, naphthylthio, anthracenylthio, phenanthrenylthio, pyrenethio, thiophenylthio, furanthio, pyridylthio, pyrrolylthio, p-tolylthio, m-tolylthio, o-tolylthio, p-nitrophenylthio, p-methoxyphenylthio, a polyethylene glycol residue, a hyaluronic acid residue, polyacrylic acid and a saccharide derivative residue, wherein n is a positive integer of more than 0 and less than 32.

In a preferred embodiment of the present invention, said R₂Is a cyclic substituent located in the 5-to 6-position of the osmium heteropentadienyl compound,

further preferably, R is₂The substituent group is alkyl of 1-20 carbon atoms, ester of 1-20 carbon atoms, acyl of 1-20 carbon atoms, carboxyl of 1-20 carbon atoms, substituted or unsubstituted aryl, cycloalkyl of 3-8 carbon atoms, nitrile group, nitro and

wherein R is₃₀Alkyl of 1 to 20 carbon atoms and substituted or unsubstituted phenyl.

Still further preferably, said R₃₀Alkyl of 1 to 17 carbon atoms and substituted or unsubstituted phenyl.

Still further preferably, said R₃₀Alkyl of 1 to 14 carbon atoms and substituted or unsubstituted phenyl.

Specifically, the R₂Is composed of

The n is a positive integer greater than 0 and less than 32.

In a preferred embodiment of the present invention, said R₃Is substituted or unsubstituted aryl of 3-60 carbon atoms, 2-17 carbon atomsSubstituted or unsubstituted alkenyl or substituted or unsubstituted alkynyl of 2 to 17 carbon atoms.

Further preferably, R is₃Is a substituted or unsubstituted aryl group of 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group of 2 to 8 carbon atoms, or a substituted or unsubstituted alkynyl group of 2 to 8 carbon atoms.

In a preferred embodiment of the present invention, said R₃The aryl in (1) is phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thienyl, furyl, pyridyl, pyrrolyl, porphinyl, fluorenyl, carbazolyl, benzothiadiazolyl, tetraphenylethylene or perylenediimide.

Further preferably, R is₃The substituent on the substituted aryl in (1) is at least one of a hydrocarbon group of 1-20 carbon atoms, an alkoxy group of 1-20 carbon atoms, an alkylthio group of 1-20 carbon atoms, an acyl group of 1-20 carbon atoms, an ester group of 1-20 carbon atoms, an amine group of 1-20 carbon atoms, an amide group of 2-20 carbon atoms, a cycloalkyl group of 2-20 carbon atoms, an alkenyl group of 2-20 carbon atoms, an alkynyl group of 2-20 carbon atoms, a nitro group, a cyano group and a halogen.

Still more preferably, the substituent on the substituted aryl group in R3 is at least one of a hydrocarbon group of 1 to 17 carbon atoms, an alkoxy group of 1 to 17 carbon atoms, an alkylthio group of 1 to 17 carbon atoms, an acyl group of 1 to 17 carbon atoms, an ester group of 1 to 17 carbon atoms, an amine group of 1 to 17 carbon atoms, an amide group of 2 to 17 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an alkenyl group of 2 to 17 carbon atoms, an alkynyl group of 2 to 17 carbon atoms, a nitro group, a cyano group and a halogen.

Still further preferably, said R₃The substituent on the substituted aryl in (1) is at least one of a hydrocarbon group of 1 to 14 carbon atoms, an alkoxy group of 1 to 14 carbon atoms, an alkylthio group of 1 to 14 carbon atoms, an acyl group of 1 to 14 carbon atoms, an ester group of 1 to 14 carbon atoms, an amine group of 1 to 14 carbon atoms, an amide group of 2 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkenyl group of 2 to 14 carbon atoms, an alkynyl group of 2 to 14 carbon atoms, a nitro group, a cyano group and a halogen.

In a preferred embodiment of the present invention, the organic solvent includes dichloromethane, dichloroethane, chloroform, methanol, ethanol, acetone, butanone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, toluene, benzene, dioxane, diethyl ether, and acetonitrile.

In a preferred embodiment of the present invention, the acid includes inorganic acids and organic acids.

Further preferably, the inorganic acid comprises HClO₄、HI、HBr、HCl、HNO₃、H₂SeO₄、H₂SO4、HClO₃、H₂C₂O₄、H₂SO₃、H₃PO₄、HNO₂、HF、H₂CO₃、H₂S、HClO、H₃BO₃And H₂SiO₃。

Further preferably, the organic acid comprises CH₃SO₃H、CF₃COOH、CCl₃COOH、CHCl₂COOH、CH₃COOH and HCOOH.

In a preferred embodiment of the present invention, the reaction temperature is from 0 to 60 ℃.

In a preferred embodiment of the invention, the reaction time is from 0.5h to 1 d.

In a preferred embodiment of the invention, the halogen is F, Cl, Br or I.

In a preferred embodiment of the present invention, the osmium heteropentayne compound is prepared from an osmium heteropentayne precursor compound by a metal-carbon triple bond transfer reaction with the addition of an acid, according to the following reaction formula:

in a preferred embodiment of the present invention, the polyethylene glycol residue is a residue of polyethylene glycol in which a hydroxyl group at one terminal is removed H, and the polyethylene glycol has a weight average molecular weight of 200-; the hyaluronic acid residue is the part left after H is removed from any one of hydroxyl groups of D-glucuronic acid or N-acetylglucosamine of hyaluronic acid, or the part left after hydroxyl groups (-OH) are removed from carboxyl groups of D-glucuronic acid of hyaluronic acid, and the weight-average molecular weight of the hyaluronic acid is 2000-2000000; the saccharide derivative residue is the residue of saccharide derivative obtained by removing hydrogen atom from any one hydroxyl group, and the saccharide derivative can be glucose, sucrose, maltose, galactose, lactose, fructose or sialic acid derivative.

Further preferably, the saccharide derivative is glucuronic acid, glucose acetal, glucose hemiacetal or carboxymethyl lactose.

In a preferred embodiment of the present invention, A in said [ Os ] is H, F, Cl, Br or SCN;

l in the [ Os ] is at least one of a CO ligand, a triphenylphosphine ligand, a trimethylphosphine ligand and a triethylphosphine ligand;

the X is triphenylphosphine cation, trimethylphosphine cation, triethylphosphine cation, trimethylamine cation, triethylamine cation, F, Cl, Br or I;

z is Cl^-、Br^-、BF₄ ^-、CF₃SO₃ ^-、PF₆ ^-Or BPh₄ ^-；

The R is₁is-H, -F, -Cl, -Br, -SCN, -CN, -OPh, -SPh,

N is a positive integer greater than 0 and less than 32;

the R is₂Is a cyclic substituent located in the 5-to 6-position of the osmium heteropentadienyl compound, and R is₂Is composed of

In a preferred embodiment of the present invention, the osmium heteropentadienyl compound is one of the following:

the [ Os ] is]Is OsCl (PPh)₃)₂，[Os¹]Is Os (PPh)₃)₂，[Os²]Is OsCl₂(PPh₃)₃，[Os³]Is Os, [ Os⁴]Is Os (PMe)₃)₃，[Os⁵]Is OsCl (PPh)₃)₃；

The terminal alkyne compound is one of the following:

the application of the 7-position vinyl substituted osmium heteropentadiyne prepared by the preparation method is as follows:

the 7-position vinyl substituted osmium heteropentadiyne prepared by the preparation method is applied to dye-sensitized solar cells. Preferably, the solar cell is a dye-sensitized solar cell or an organic solar cell.

The application of the 7-position vinyl substituted osmium heteropentadiyne prepared by the preparation method in preparing materials for photodynamic therapy.

The 7-position vinyl substituted osmium heteropentadiyne prepared by the preparation method is applied to photolysis of water.

The 7-position vinyl substituted osmium heteropentadiyne prepared by the preparation method is applied to the preparation of a lithium-air battery.

The invention has the beneficial effects that:

1. the 7-position vinyl substituted osmium heteropentadiyne prepared by the method has high solubility and good stability, has very high molar absorption coefficient and better electrochemical performance, and can be widely applied to the fields of dye-sensitized solar cells, organic solar cells, photodynamic therapy, water photolysis, lithium-air cells and the like.

2. The reaction of the preparation method has the characteristics of high efficiency, specificity, 100% of atom conversion efficiency, mild reaction conditions and good functional group tolerance.

Drawings

FIG. 1 is a graph showing data on the crystal structure of Compound III-2 obtained in example 2 of the present invention.

FIG. 2 is a crystal data representation of compound III-4 obtained in example 4 of the present invention (omitting the triphenylphosphine group).

FIG. 3 is a chart showing the UV-VIS absorption spectrum of osmium heteropentayne derivative III-4 according to example 4 of the present invention.

FIG. 4 is a representation of crystal data of the compound III-30-1 obtained in example 31 of the present invention (omitting the triphenylphosphine group).

FIG. 5 is a second characterization chart of crystal data of compound III-30-1 obtained in example 31 according to the present invention (omitting the triphenylphosphine group).

FIG. 6 is a chart showing an ultraviolet-visible absorption spectrum of compound III-31 in example 32 of the present invention.

FIG. 7 is a crystal structure representation diagram (omitting the triphenylphosphine group) of compound III-32 in example 33 of the present invention.

FIG. 8 is a crystal structure representation diagram (omitting the triphenylphosphine group) of compound III-39 in example 40 of the present invention.

FIG. 9 is a J-V curve of compound III-30-1 of example 41 of the present invention tested in an organic solar cell.

Detailed Description

The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.

In the following examples, osmium heteropentadienyl compounds can be prepared according to the literature Zhu, C.; li, S.; luo, m.; zhou, x.; niu, y.; lin, m.; zhu, j.; cao, z.; lu, x.; wen, t.; xie, z.; schleyer, p.v.r.; xia, H.Stabilisation of Anti-aromatic and Strained Five-member Rings with an aTransition Metal. Nat. chem.2013, 5, 698-; lin, j.; hua, y.; zhou, x.; shao, y.; chen, s.; chen, z.; zhu, j.; zhang, h.; xia, H.multidyne Chains chemistry Via Three Metal carbonyl sigma bonds. Nat. Commun.2017, 8, 1912. that the osmium heteropentaeneyne precursor compound is prepared by the metal-carbon triple bond transfer reaction of an osmium heteropentaeneyne precursor compound with the addition of an acid, according to the following reaction scheme: