CN115010653A - Metal double terpyridyl ligand, ruthenium-containing supramolecular compound, and preparation method and application thereof - Google Patents
Metal double terpyridyl ligand, ruthenium-containing supramolecular compound, and preparation method and application thereof Download PDFInfo
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- CN115010653A CN115010653A CN202110246170.8A CN202110246170A CN115010653A CN 115010653 A CN115010653 A CN 115010653A CN 202110246170 A CN202110246170 A CN 202110246170A CN 115010653 A CN115010653 A CN 115010653A
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- terpyridine
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 55
- 239000003446 ligand Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 239000002246 antineoplastic agent Substances 0.000 claims abstract description 3
- 229940041181 antineoplastic drug Drugs 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 117
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 47
- -1 4- (4-pyridyl) phenyl Chemical group 0.000 claims description 22
- 238000001338 self-assembly Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003495 polar organic solvent Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 206010028980 Neoplasm Diseases 0.000 abstract description 11
- 201000011510 cancer Diseases 0.000 abstract description 9
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 239000003534 dna topoisomerase inhibitor Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 229940044693 topoisomerase inhibitor Drugs 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 67
- 239000000243 solution Substances 0.000 description 37
- 239000007787 solid Substances 0.000 description 27
- 239000011701 zinc Substances 0.000 description 20
- 239000000370 acceptor Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 239000006228 supernatant Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 14
- 238000000921 elemental analysis Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001093 anti-cancer Effects 0.000 description 5
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 210000000056 organ Anatomy 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 101100532679 Caenorhabditis elegans scc-1 gene Proteins 0.000 description 2
- 101100240606 Caenorhabditis elegans scc-2 gene Proteins 0.000 description 2
- 101100532685 Caenorhabditis elegans scc-3 gene Proteins 0.000 description 2
- 206010009944 Colon cancer Diseases 0.000 description 2
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 208000029742 colonic neoplasm Diseases 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000012091 fetal bovine serum Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 201000007270 liver cancer Diseases 0.000 description 2
- 208000014018 liver neoplasm Diseases 0.000 description 2
- 201000005202 lung cancer Diseases 0.000 description 2
- 208000020816 lung neoplasm Diseases 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- TXPVQASIALYEDY-UHFFFAOYSA-L Cl[Ru](C1=C(C=C(C=C1)C)C(C)C)(C1=C(C=C(C=C1)C)C(C)C)Cl Chemical compound Cl[Ru](C1=C(C=C(C=C1)C)C(C)C)(C1=C(C=C(C=C1)C)C(C)C)Cl TXPVQASIALYEDY-UHFFFAOYSA-L 0.000 description 1
- 102100029952 Double-strand-break repair protein rad21 homolog Human genes 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 101000584942 Homo sapiens Double-strand-break repair protein rad21 homolog Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QMPSUPWBJMOGPS-UHFFFAOYSA-N [Ru].CC(C)C1=CC=C(C)C=C1 Chemical compound [Ru].CC(C)C1=CC=C(C)C=C1 QMPSUPWBJMOGPS-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229940009456 adriamycin Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 1
- 229960004316 cisplatin Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002008 hemorrhagic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- JUDUFOKGIZUSFP-UHFFFAOYSA-M silver;4-methylbenzenesulfonate Chemical compound [Ag+].CC1=CC=C(S([O-])(=O)=O)C=C1 JUDUFOKGIZUSFP-UHFFFAOYSA-M 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 231100000588 tumorigenic Toxicity 0.000 description 1
- 230000000381 tumorigenic effect Effects 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
Abstract
The invention provides a metal bis-terpyridine ligand with a structure shown in the following formula. The metal bis-terpyridyl ligand provided by the invention fuses essential metal for a human body and derivatives of a topoisomerase inhibitor terpyridyl, has the characteristic of low toxicity for the human body, and is a novel ligand. The invention also provides ruthenium-containing hexanuclear homo/dissimilar metal supramolecular compounds which are novel ruthenium-containing supramolecular compounds, and ruthenium-containing hexanuclear homo/dissimilar metal supramolecular compounds containing different anions, wherein the ruthenium-containing supramolecular compounds have good inhibition effects on human cancer cell lines HepG-2, A549 and HCT-116, and have application prospects in preparation of anti-cancer drugs.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a ruthenium-containing supramolecular compound, a preparation method and application thereof, a benzimidazole ligand and a preparation method thereof.
Background
Tumor refers to a lump formed by abnormal proliferation of cells of local tissues under the action of various tumorigenic factors. Tumors can be classified into benign tumors and malignant tumors, and malignant tumors (also called cancers) can destroy the structure and function of tissues and organs, cause hemorrhagic necrosis and infection of the tissues and organs, and finally, patients can die due to exhaustion of the organ function. The ruthenium-based compound has good anticancer activity, and an important class of the ruthenium-based compound is arene ruthenium (II) supermolecule self-assembly anticancer compound constructed by coordination bond driving.
Suss-Fink synthesized the first aromatic ruthenium (II) supramolecular coordination compound in 1997. An arene ruthenium (II) acceptor is a partially encapsulated ruthenium-based coordination compound that has a structure similar to a piano stool (also known as a molecular clip), and is two ruthenium (II) ions connected by a bridging ligand, leaving one coordinatable site on each metal ion. Aromatic ruthenium (II) acceptors and ligands with different angles or different types are used for obtaining the polynuclear supramolecular self-assembly compound with a two-dimensional or three-dimensional structure by a self-assembly means. Most of anticancer p-cymene ruthenium self-assembly compounds in the prior art mostly adopt double-headed pyridine or carboxylic acid ligands.
Disclosure of Invention
In view of this, the present invention aims to provide a ruthenium-containing supramolecular compound, a preparation method and applications thereof, a terpyridine metalloid bridged ligand, and a preparation method thereof. The invention also provides a novel ruthenium-containing supermolecular polynuclear iso/iso metal compound and a compound containing different anion structures.
In order to achieve the above object, the present invention provides the following technical solutions:
a metal bis-terpyridine ligand having the structure shown in formula I:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - (ii) a Or M is Ru 2+ N is 2 and X is PF 6 - And R is 4-pyridyl, 4- (4-pyridyl) phenyl or 4- (1H-imidazol-1-yl) phenyl.
The invention also provides a preparation method of the bridged ligand of terpyridine metal in the technical scheme, which comprises the following steps:
(1) using 2-acetylpyridine with R-pyridylaldehydeConventional (C)
Pyridine synthesis reaction and classical Suzuki reaction are reacted with Ullmann to obtain 2,2 ': 6 ', 2 ' -terpyridine compounds with different R groups;
(2) mixing the terpyridine product obtained in the step (1) with metal (Fe) 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ ) The salt is subjected to chelating coordination reaction to obtain a double terpyridine metal bridging compound containing two coordination sites.
(3) And (3) mixing the bridging compound obtained in the step (2) with silver salts or ammonium hexafluorophosphate with different anions to perform anion exchange to obtain the terpyridine metal bridging ligand with different anions and the structure shown in the formula I.
The invention provides an acceptor A with a structure shown in a formula II:
the invention also provides a ruthenium-containing supramolecular compound which has a structure shown in a formula II:
wherein L is a compound having the structure shown in formula L1, L2, L4 or formula I:
a is a compound having a structure represented by formula A1, A2, A3, or A4:
the invention also provides a preparation method of the hexanuclear ruthenium-containing supramolecular compound in the technical scheme, which comprises the following steps: and mixing the compound A, the compound L and a polar organic solvent to perform coordination-driven self-assembly reaction to obtain the ruthenium-containing supramolecular compound.
Preferably, the time for the coordination-driven self-assembly reaction is 48 h.
Preferably, the coordination-driven self-assembly reaction further comprises: removing the polar organic solvent in the coordination-driven self-assembly reaction product, and adding diethyl ether for centrifugal treatment.
Preferably, the rotation speed of the centrifugal treatment is 2900rpm, and the time of the centrifugal treatment is 10 min.
Preferably, the polar organic solvent is dichloromethane and/or methanol.
The invention also provides the application of the ruthenium-containing supramolecular compound in the technical scheme in the preparation of anti-cancer drugs.
The invention provides a terpyridine metal bridged ligand which introduces non-toxic transition metal necessary for human body into a novel ligand in the field of cancer resistance, and has non-toxicity to medium toxicity to cancer cells.
The invention also provides a ruthenium-containing supramolecular compound, which is a novel ruthenium-containing supramolecular compound and has good inhibition effect on human liver cancer cells HepG-2, human lung cancer cells A549 and colon cancer HCT-116.
Detailed Description
The invention provides a metal bis-terpyridine ligand with a structure shown in formula I:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - (ii) a Or M is Ru 2+ N is 2 and X is PF 6 - R is 4-pyridyl or 4- (4-pyridyl) phenyl or 4- (1H-imidazol-1-yl) phenyl
The main preparation process of L1-L12:
(1) using 2-acetylpyridine with R-pyridylaldehyde with the conventional
The pyridine synthesis reaction and the classical Suzuki reaction react with Ullmann to obtain 4-pyridyl-2, 2 ': 6 ', 2 ' -terpyridine, 4- (4-pyridyl) phenyl-2, 2 ': 6 ', 2 ' -terpyridine, 4- (1H-imidazole-1-yl) phenyl-2, 2 ': 6 ', 2 ' -terpyridine,
(2) the terpyridine product with the R of 4-pyridyl obtained in the step (1) and metal (Fe) 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ ) The salt is subjected to chelating coordination reaction to obtain a double terpyridine metal bridging compound containing two coordination sites.
(3) And (3) mixing the bridged compound obtained in the step (2) with silver salt or ammonium hexafluorophosphate to perform anion exchange to obtain the bis-terpyridine metal bridged ligand with the structure shown in the formula I.
The preparation method of L1 comprises the following steps: the zinc trifluoromethanesulfonate dissolved in the methanol solution is slowly dripped into a dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, and stirred while being dripped, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) cooling the reaction system to room temperature, filtering to obtain light purple solid powder, washing with methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L2 comprises the following steps: under the nitrogen atmosphere, ferrous chloride dissolved in methanol solution is slowly dripped into dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, and the mixture is stirred while being dripped, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) when the reaction system is cooled to room temperature, adding silver trifluoromethanesulfonate with the equivalent of 2 times of ferrous chloride, and continuously stirring for 2 hours. And filtering the reaction system to remove solid impurities, distilling the purple solution under reduced pressure to obtain solid powder, washing with dichloromethane, and drying to obtain the target product.
The preparation method of L3 comprises the following steps: slowly dripping ferric chloride dissolved in methanol solution into dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine while stirring, and violently stirring at 60 ℃ for reaction for 12 hours. And (3) when the reaction system is cooled to room temperature, adding silver trifluoromethanesulfonate with the equivalent of 3 times of ferric chloride, and continuously stirring for 2 hours. Filtering to remove solid impurities in the reaction system, distilling the reddish brown solution under reduced pressure to obtain solid powder, washing with dichloromethane, and drying to obtain the target product.
The preparation method of L4 comprises the following steps: slowly dripping cobalt chloride dissolved in methanol solution into dichloromethane solution of 2 times of 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, stirring while dripping, and violently stirring at 60 ℃ for reaction for 12 h. And (3) after the reaction system is cooled to room temperature, adding silver trifluoromethanesulfonate with 2 times of the equivalent weight of cobalt chloride, and continuously stirring for 2 hours. Adding a large amount of methanol into the reaction system to dissolve the precipitated product, filtering to remove solid impurities, distilling the tawny solution under reduced pressure to obtain solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L5 comprises the following steps: slowly dripping copper chloride dissolved in methanol solution into dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine while stirring, and violently stirring at 60 ℃ for reaction for 12 hours. And (3) after the reaction system is cooled to room temperature, adding silver trifluoromethanesulfonate with 2 times of equivalent of copper chloride, and continuously stirring for 2 hours. Adding a large amount of methanol into the reaction system to dissolve the precipitated product, filtering to remove solid impurities, distilling the blue solution under reduced pressure to obtain solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L6 comprises the following steps: in the nitrogen atmosphere, ruthenium chloride and 2 times of equivalent of 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine are put into a glycol solution, and the mixture is subjected to light-shielding reflux reaction for 4 hours. After the reaction is finished, cooling the reaction system to room temperature, adding ammonium hexafluorophosphate which is excessive by 2 times of ruthenium chloride, continuously stirring for 2 hours,the celite was filtered to give the crude solid product. Water, ether wash and acetonitrile to dissolve the crude product. By CH 3 CN：KNO 3 Saturated solution: h 2 And (3) performing silica gel column chromatography on an O system (V: V: V: 7:1:0.5), collecting a second part, adding ammonium hexafluorophosphate to precipitate a solid, and drying to obtain a dark red target product.
The preparation method of L7 comprises the following steps: the zinc nitrate dissolved in the methanol solution is slowly dripped into a dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, and the mixture is stirred while being dripped, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) cooling the reaction system to room temperature, distilling the colorless transparent solution under reduced pressure to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L8 comprises the following steps: the zinc p-toluenesulfonate dissolved in methanol solution is slowly dripped into a dichloromethane solution of 2 times of 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine by stirring while dripping, and the mixture is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) cooling the reaction system to room temperature, distilling the colorless transparent solution under reduced pressure to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L9 comprises the following steps: the zinc tetrafluoroborate dissolved in the methanol solution is slowly dripped into the dichloromethane solution of 2 times of equivalent 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, and the mixture is stirred while dripping, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) cooling the reaction system to room temperature, distilling the colorless transparent solution under reduced pressure to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L10 comprises the following steps: slowly dripping zinc acetate dissolved in methanol solution into 2 times of the equivalent of the ethanol solution of 4-pyridyl-2, 2 ', 6 ', 2 ' -terpyridine, stirring while dripping, and carrying out reflux reaction for 2 hours. And (3) after the reaction system is cooled to room temperature, adding ammonium hexafluorophosphate in an excess amount of 2 times of zinc acetate, continuously stirring for 2 hours, filtering to obtain white solid powder, washing with ethanol, methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L11 comprises the following steps: the zinc trifluoromethanesulfonate dissolved in the methanol solution is slowly dripped into a dichloromethane solution of 2 times of equivalent 4- (4-pyridyl) phenyl-2, 2 ', 6 ', 2 ' -terpyridine, and the mixture is stirred while being dripped, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) cooling the reaction system to room temperature, filtering to obtain white solid powder, washing with methanol and dichloromethane, and drying to obtain the target product.
The preparation method of L12 comprises the following steps: the zinc trifluoromethanesulfonate dissolved in the methanol solution is slowly dripped into a 2-fold equivalent dichloromethane solution of 4- (1H-imidazole-1-yl) phenyl-2, 2 ', 6 ', 2 ' -terpyridine, and is stirred while being dripped, and is vigorously stirred at 60 ℃ for reaction for 12 hours. And cooling the reaction system to room temperature, filtering to obtain white solid powder, washing with methanol and dichloromethane, and drying to obtain the target product.
The invention provides an acceptor A with a structure shown in a formula II:
the source of the A is not particularly limited in the invention, and the A can be prepared by a preparation method well known to those skilled in the art, specifically, the A comprises the following steps:
A1-A4 preparation method:
(1) adding dichlorobis (4-methyl isopropylphenyl) ruthenium (II), nerchinaberry root and sodium acetate into a pear-shaped bottle, adding ethanol, and refluxing for 24 hours under vigorous stirring. Cooling the reaction system to room temperature, centrifuging (2500r/min) for 10min, discarding supernatant, and washing the solid twice with ethanol, acetone and diethyl ether to obtain brown solid;
(2) and (2) respectively dissolving the solid obtained in the step (1) with silver trifluoromethanesulfonate, silver nitrate, silver p-toluenesulfonate and hexafosetyl silver phosphate in methanol, stirring at room temperature for 2-4 hours to separate out a white AgCl precipitate, then filtering with diatomite to obtain a filtrate, rotating to be slightly dry, adding ether to separate out a green solid. Centrifuging (2500r/min) for 10min to obtain target products A1-A4 containing different anions respectively, and then drying in vacuum.
The invention also provides a ruthenium-containing supramolecular compound which has a structure shown in a formula III:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ N is 2 or 3, X is OTf - (ii) a Or M is Ru 2+ N is 2 and X is PF 6 - 。
In the invention, the time of the coordination-driven self-assembly reaction is preferably 48h, and the temperature of the coordination-driven self-assembly reaction is preferably room temperature, and no additional heating or cooling is required.
In the present invention, the coordination-driven self-assembly reaction preferably further comprises: removing the polar organic solvent in the coordination-driven self-assembly reaction product, and adding diethyl ether for centrifugal treatment. The manner of removing the polar organic solvent is not particularly limited in the present invention, and may be performed in a manner known to those skilled in the art, specifically, such as purging. The invention has no special limit on the use amount of the diethyl ether, and can separate out the ruthenium-containing supramolecular compound.
In the present invention, the rotation speed of the centrifugation is preferably 2900rpm, and the time of the centrifugation is preferably 10 min.
After obtaining the centrifuged product, the present invention preferably further comprises washing the centrifuged product with diethyl ether as well. The amount of ether and the number of times of centrifugation are not particularly limited in the present invention, and any method known to those skilled in the art may be used.
In the invention, the supramolecular compound obtained by ligands L1-L6 and A1 of different metal M with the structure shown in formula I is provided.
Wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ N is 2 or 3, X is OTf - (ii) a Or M is Ru 2+ N is 2, X is PF 6 - 。
Ruthenium-containing supramolecular compounds are provided having the structure shown in formula iii:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ N is 2 or 3, X is OTf-; or M is Ru 2+ N is 2 and X is PF 6 - And Y is OTf-.
Example 1
Ligand L1(3.9280mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) are accurately weighed into a 8mL catalytic vial, dissolved by methanol, stirred at room temperature to perform coordination-driven self-assembly for 24h, the solvent is blown to 0.2mL and added with ether to separate out a solid, a centrifuge (2900r/min) is used for centrifuging for 10min, a supernatant is discarded, and the solution is washed once by ether to obtain the metal rectangular ruthenium-containing supramolecular compound SCC 1.
Characterization of the metallic rectangle ruthenium-containing supramolecular compound SCC 1:
1 H NMR(400MHz,CD 3 OD):δ9.04(s,8H),8.80(d,J＝6.1Hz,8H),8.63(d,J＝8.1Hz,8H),8.18(d,J＝6.1Hz,8H),7.78(d,J＝4.9Hz,8H),7.73(t,J＝7.8Hz,8H),7.37(s,8H),7.11-6.79(m,8H),5.96(d,J＝6.1Hz,8H),5.74(d,J＝6.1Hz,8H),3.00-2.86(m,4H),2.20(s,12H),1.40(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.7,153.9,153.7,151.2,149.1,148.8,148.7,142.2,138.6,128.7,126.0,124.7,123.8,121.6(q,J C-F ＝320.0Hz),113.0,105.1,101.2,86.0,84.1,32.1,22.5,17.5.
19 F NMR(376MHz,CD 3 OD):δ-79.96.
MS(ESI):m/z calcd for[SCC1-3OTf] 3+ :1145.06；found:1145.14,calcd for[SCC1-4OTf] 4+ :821.56；found:821.56.Elemental analysis:calcd(％)for C 148 H 120 N 16 O 32 F 24 S 8 Ru 4 Zn 2 :C 45.79,H3.12,N 5.77；found:C 45.69,H 3.27,N 5.48.
example 2
Ligand L2(3.8990mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were accurately weighed into a 8mL catalytic vial, dissolved with methanol, self-assembled by coordination driven stirring at room temperature for 24h, the solvent was blown to 0.2mL and ether was added to precipitate solids, centrifuged (2900r/min) for 10min, the supernatant was discarded, and washed once with ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 2.
Characterization of the metallic rectangle ruthenium-containing supramolecular compound SCC 2:
1 H NMR(400MHz,CD 3 OD):δ9.26(s,8H),8.85(d,J＝6.0Hz,8H),8.53(d,J＝8.0Hz,8H),8.32(d,J＝6.0Hz,8H),7.40(s,8H),7.27(t,J＝7.8Hz,8H),7.10(d,J＝5.5Hz,8H),6.68(t,J＝6.5Hz,1H),6.00(d,J＝6.1Hz,8H),5.78(d,J＝6.1Hz,8H),3.12-3.12(m,4H),2.24(s,12H),1.42(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD)δ172.8,161.6,159.0,154.0,153.9,149.2,147.7,139.6,138.6,128.5,125.9,125.3,123.6,123.2,120.0,113.1,105.0,101.2,86.0,84.0,32.1,22.6,17.5.
19 F NMR(376MHz,CD 3 OD):δ-79.98.
MS(ESI):m/z calcd for[SCC2-3OTf] 3+ :1138.73；found:1138.80,calcd for[SCC2-4OTf] 4+ :816.81；found:816.81.Elemental analysis:calcd(％)for C 148 H 120 N 16 O 32 F 24 S 8 Ru 4 Fe 2 :C 46.02,H3.13,N 5.80；found:C 45.77,H 2.95,N 5.64.
example 3
Ligand L3(4.4950mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) are accurately weighed into a 8mL catalytic vial, dissolved by methanol, stirred at room temperature to perform coordination-driven self-assembly for 24h, the solvent is blown to 0.2mL and added with ether to separate out a solid, a centrifuge (2900r/min) is used for centrifuging for 10min, a supernatant is discarded, and the solution is washed once by ether to obtain the metal rectangular ruthenium-containing supramolecular compound SCC 3.
Characterization of the metal rectangular ruthenium-containing supramolecular compound SCC 3:
Elemental analysis:calcd(％)for C 150 H 120 N 16 O 38 F 30 S 10 Ru 4 Fe 2 :C 43.30,H 2.91,N 5.39；found:C 42.99,H 3.02,N 5.19.
example 4
Ligand L4(3.9115mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) are accurately weighed into a 8mL catalytic vial, dissolved by methanol, stirred at room temperature to perform coordination-driven self-assembly for 24h, the solvent is blown to 0.2mL and added with ether to separate out a solid, a centrifuge (2900r/min) is used for centrifuging for 10min, a supernatant is discarded, and the solution is washed once by ether to obtain the metal rectangular ruthenium-containing supramolecular compound SCC 4.
Characterization of the metal rectangular ruthenium-containing supramolecular compound SCC 4:
MS(ESI):m/z calcd for[SCC4-4OTf] 4+ :821.31；found:821.31.Elemental analysis:calcd(％)for C 148 H 120 N 16 O 32 F 24 S 8 Ru 4 Co 2 :C 45.94,H 3.13,N 5.79；found:C 45.80,H 2.95,N 5.46.
example 5
Ligand L5(3.9297mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) are accurately weighed into a 8mL catalytic vial, dissolved by methanol, stirred at room temperature to perform coordination-driven self-assembly for 24h, the solvent is blown to 0.2mL and added with ether to separate out a solid, a centrifuge (2900r/min) is used for centrifuging for 10min, a supernatant is discarded, and the solution is washed once by ether to obtain the metal rectangular ruthenium-containing supramolecular compound SCC 5.
Characterization of the metal rectangular ruthenium-containing supramolecular compound SCC 5:
MS(ESI):m/z calcd for[SCC5-3OTf] 3+ :1144.15；found:1144.06.[SCC5-4OTf] 4+ :820.56；found:820.56.Elemental analysis:calcd(％)for C 148 H 120 N 16 O 32 F 24 S 8 Ru 4 Cu 2 :C 45.83,H 3.12,N5.78；found:C 45.50,H 3.02,N 5.56.
example 6
Ligand L6(4.0473mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) are accurately weighed into a 8mL catalytic vial, dissolved with methanol, stirred at room temperature for coordination-driven self-assembly for 24h, the solvent is blown to 0.2mL and added with ether to precipitate a solid, a centrifuge (2900r/min) is used for centrifugation for 10min, the supernatant is discarded, and the solid is washed once with ether to obtain the metallic rectangular ruthenium-containing supramolecular compound SCC 6.
Characterization of the metal rectangular ruthenium-containing supramolecular compound SCC 6:
1 H NMR(400MHz,CD 3 CN):δ8.82(s,8H),8.68(d,J＝6.1Hz,8H),8.39(d,J＝8.1Hz,8H),8.05(d,J＝6.1Hz,8H),7.37-7.26(m,16H),7.19(d,J＝5.5Hz,8H),6.64(t,J＝6.5Hz8H),5.79(d,J＝6.1Hz,8H),5.59(d,J＝6.1Hz,8H),2.95-2.82(m,4H),2.17(s,12H),1.35(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 CN)δ172.2,158.4,156.2,153.6,153.3,148.6,144.5,138.6,138.4,128.2,125.6,125.3,123.3,112.6,104.4,100.8,100.4,85.2,83.9,31.5,22.3,17.4.
19 F NMR(376MHz,CD 3 OD):δ-71.68,-73.56,-79.33.
MS(ESI):m/z calcd for[SCC6-2OTf-PF 6 ] 3+ :1164.72；found:1164.68.Elemental analysis:calcd(％)for C 144 H 120 N 16 O 20 F 36 S 4 Ru 6 P 4 :C 43.93,H 3.07,N 5.69；found:C 43.69,H 3.11,N5.42.
in the present invention, the supramolecular compounds SCC7 and SCC8 obtained from ligands L7 and a2 and L8 and A3 having the same anion are provided.
Wherein M is Zn 2+ X is NO 3 - Or OTs - 。
Example 7
Ligand L7(3.2405mg,0.004mmol) and metal acceptor A2(3.1309mg,0.004mmol) were weighed into a 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 7.
Performing structural characterization on the metal rectangular ruthenium-containing supramolecular compound SCC 7:
1 H NMR(400MHz,CD 3 OD):δ9.00(s,8H),8.82(d,J＝6.0Hz,8H),8.60(d,J＝8.0Hz,8H),8.16(d,J＝6.0Hz,8H),7.92-7.72(m,8H),7.40(s,8H),6.92-6.76(m,8H),5.98(d,J＝6.1Hz,8H),5.77(d,J＝6.1Hz,8H),2.99-2.87(m,4H),2.22(s,12H),1.42(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.6,153.9,153.8,151.2,149.3,149.2,148.7,142.3,138.7,128.7,126.1,124.6,123.7,112.9,105.2,101.2,86.0,84.2,32.1,22.6,17.4.
Elemental analysis:calcd(％)for C 140 H 120 N 24 O 32 Ru 4 Zn 2 :C 52.78,H 3.80,N 10.55；found:C52.62,H 3.84,N 10.29.
example 8
Ligand L8(4.1140mg,0.004mmol) and metal acceptor A3(4.0124mg,0.004mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 8.
Performing structural characterization on the metal rectangular ruthenium-containing supramolecular compound SCC 8:
1 H NMR(400MHz,CD 3 OD):δ8.90(s,8H),8.71(d,J＝6.6Hz,8H),8.61(d,J＝8.1Hz,8H),8.06(d,J＝6.6Hz,8H),7.77(d,J＝5.1Hz,8H),7.74(td,J＝8.0,1.6Hz,8H),7.46(d,J＝8.1Hz,16H),7.41(s,8H),7.01(d,J＝8.0Hz,16H),6.88(dd,J＝7.4,5.8Hz,8H),5.92(d,J＝6.3Hz,8H),5.70(d,J＝6.3Hz,8H),2.93-2.83(m,4H),2.25(s,24H),2.15(s,12H),1.37(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.6,153.8,153.3,151.1,149.2,148.7,148.5,143.8,142.4,141.6,138.9,129.7,128.7,126.8,126.1,124.9,123.7,113.0,105.1,101.4,101.3,86.1,84.1,32.1,22.6,21.4,17.5.
Elemental analysis:calcd(％)for C 196 H 176 N 16 O 32 S 8 Ru 4 Zn 2 :C 58.00,H 4.37,N 5.52；found:C57.70,H 4.23,N 5.31.
in the present invention, there is provided a metal-containing Zn having a structure represented by formula I 2+ The different anionic ligands L7-L10 and A1 respectively.
Supramolecular compounds of different anions X, Y having the structure of formula iii are provided.
Wherein M is Zn 2+ X is NO 3 - 、OTs - 、BF 4 - Or PF 6 - . Y is OTf - 。
Example 9
Ligand L7(3.2405mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into a 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 9.
Performing structural characterization on the metal rectangle ruthenium-containing supramolecular compound SCC 9:
1 H NMR(400MHz,CD 3 OD):δ9.03(s,1H),8.82(d,J＝6.0Hz,8H),8.62(d,J＝8.0Hz,8H),8.18(d,J＝6.0Hz,8H),7.82-7.76(m,16H),7.39(s,8H),7.00-6.81(m,8H),5.98(d,J＝6.1Hz,8H),5.76(d,J＝6.1Hz,8H),2.99-2.86(m,4H),2.21(s,12H),1.41(d,J＝6.9Hz,24H). 13 C NMR(100MHz,CD 3 OD):δ172.6,153.9,153.7,151.2,149.2,148.9,148.7,142.2,138.7,128.7,126.1,124.6,123.7,123.2,120.1,112.9,105.1,101.2,86.0,84.1,32.1,22.6,17.5. 19 F NMR(376MHz,CD 3 OD):δ-79.95.Elemental analysis:calcd(％)for C 144 H 120 N 20 O 32 F 12 S 4 Ru 4 Zn 2 :C 48.94,H 3.42,N 7.93；found:C 48.58,H 3.39,N 7.79.
example 10
Ligand L8(4.1140mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 10.
Performing structural characterization on the metal rectangle ruthenium-containing supramolecular compound SCC 10:
1 H NMR(400MHz,CD 3 OD):δ8.98(s,8H),8.76(d,J＝6.0Hz,8H),8.62(d,J＝8.1Hz,8H),8.12(d,J＝6.0Hz,8H),7.78(d,J＝4.9Hz,H),7.74(t,J＝7.8Hz,8H),7.46(d,J＝7.9Hz,8H),7.39(s,8H),7.00(d,J＝7.9Hz,8H),6.96-6.89(m,8H),5.94(d,J＝6.1Hz,8H),5.72(d,J＝6.1Hz,8H),2.97-2.85(m,4H),2.25(s,12H),2.18(s,12H),1.39(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.7,153.9,153.5,151.2,149.1,148.7,148.6,143.8,142.3,141.5,138.7,129.7,128.7,126.8,126.1,124.8,123.8,121.6(q,J C-F ＝317.0Hz),113.0,105.1,101.2,86.0,84.1,32.1,22.6,21.3,17.5.
19 F NMR(376MHz,CD 3 OD):δ-79.96.
Elemental analysis:calcd(％)for C 172 H 148 N 16 O 32 F 12 S 8 Ru 4 Zn 2 :C 52.03,H 3.76,N 5.64；found:C 51.73,H 3.54,N 5.58.
example 11
Ligand L9(3.4389mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 11.
Performing structural characterization on the metal rectangle ruthenium-containing supramolecular compound SCC 11:
1 H NMR(400MHz,CD 3 OD):δ9.00(s,8H),8.79(d,J＝6.0Hz,8H),8.59(d,J＝8.0Hz,8H),8.15(d,J＝6.0Hz,8H),7.77-7.73(m,16H),7.37(s,8H),7.00-6.82(m,8H),5.95(d,J＝6.1Hz,8H),5.73(d,J＝6.1Hz,8H),2.98-2.85(m,4H),2.19(s,12H),1.40(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.7,153.9,153.8,151.2,149.1,148.9,148.8,142.2,138.7,128.7,126.1,124.6,123.8,121.6(q,J C-F ＝317.0Hz),113.0,105.1,101.2,86.0,84.1,32.1,22.5,17.5.
19 F NMR(376MHz,CD 3 OD):δ-79.96,-153.25,153.30.
Elemental analysis:calcd(％)for C 144 H 120 B 4 N 16 O 20 F 28 S 4 Ru 4 Zn 2 :C 47.61,H 3.33,N 6.17；found:C 47.49,H 3.27,N 5.92.
example 12
Ligand L10(3.4389mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into a 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 12.
Performing structural characterization on the metal rectangular ruthenium-containing supramolecular compound SCC 12:
1 H NMR(400MHz,CD 3 OD):δ9.02(s,8H),8.80(d,J＝6.4Hz,8H),8.61(d,J＝8.1Hz,8H),8.17(d,J＝6.4Hz,8H),7.75(d,J＝5.4Hz,8H),7.73(t,J＝7.8Hz,8H),7.38(s,8H),6.94(dd,J＝7.1,5.5Hz,8H),5.96(d,J＝6.2Hz,8H),5.73(d,J＝6.2Hz,8H),2.97-2.87(m,4H),2.20(s,12H),1.40(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.7,153.9,151.2,149.1,148.8,142.2,139.9,138.7,138.6,128.7,126.0,124.6,123.8,118.2,113.0,105.1,101.4,101.2,86.0,84.0,32.1,22.5,17.5.
19 F NMR(376MHz,CD 3 OD):δ-72.67,-74.56,-80.00.
Elemental analysis:calcd(％)for C 144 H 120 P 4 N 16 O 20 F 36 S 4 Ru 4 Zn 2 :C 44.74,H 3.13,N 5.80；found:C 44.53,H 3.24,N 5.66.
in the present invention, the supramolecular compounds obtained from ligands L11-L12 and A1 having different R groups are first provided.
Supramolecular compounds having different R groups with the structure of formula iii are provided.
Wherein M is Zn 2+ R is 4- (4-pyridyl) phenyl or 4- (1H-imidazol-1-yl) phenyl
Example 13
Ligand L11(4.5458mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into a 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 13.
Performing structural characterization on the metal rectangle ruthenium-containing supramolecular compound SCC 13:
1 H NMR(400MHz,CD 3 OD):δ9.14(s,8H),8.76(d,J＝8.0Hz,8H),8.60(d,J＝5.9Hz,8H),8.36(d,J＝8.1Hz,8H),8.03(d,J＝8.1Hz,8H),7.89(d,J＝6.0Hz,8H),7.84-7.80(m,16H),7.34(s,8H),7.02-6.95(m,8H),5.92(d,J＝6.1Hz,8H),5.69(d,J＝6.1Hz,8H),2.97-2.84(m,4H),2.18(s,12H),1.40(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.6,157.1,153.4,151.6,151.0,149.2,149.0,142.2,139.5,139.4,138.7,130.3,129.5,128.6,124.9,124.6,123.0,121.8(q,J C-F ＝317.0Hz),112.9,105.0,101.0,85.8,84.1,32.1,22.5,17.4.
19 F NMR(376MHz,CD 3 OD):δ-79.88.
MS(ESI):m/z calcd for[SCC13-3OTf] 3+ :1247.01；found:1247.27,calcd for[SCC13-4OTf] 4+ :897.59；found:897.60.Elemental analysis:calcd(％)for C 172 H 136 N 16 O 32 F 24 S 8 Ru 4 Zn 2 :C 49.35,H 3.27,N 5.35；found:C 49.18,H 3.16,N 5.08.
example 14
Ligand L12(4.4576mg,0.004mmol) and metal acceptor A1(3.9520mg,0.004mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged using a centrifuge (2500r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metallic rectangular ruthenium-containing supramolecular compound SCC 14.
Performing structural characterization on the metal rectangle ruthenium-containing supramolecular compound SCC 14:
1 H NMR(400MHz,CD 3 OD):δ9.15(s,8H),8.78(d,J＝8.1Hz,8H),8.65(s,4H),8.41(d,J＝8.4Hz,8H),7.90(d,J＝8.4Hz,8H),7.85(d,J＝5.1Hz,8H),7.81(t,J＝7.9Hz,8H),7.78(s,4H),7.29(s,8H),7.11(s,4H),7.06-7.00(m,8H),5.92(d,J＝6.0Hz,8H),5.71(d,J＝6.0Hz,8H),2.95-2.82(m,4H),2.21(s,12H),1.39(d,J＝6.9Hz,24H).
13 C NMR(100MHz,CD 3 OD):δ172.6,156.7,151.1,149.2,149.0,142.2,139.3,139.0,138.5,137.7,131.2,130.5,128.6,124.6,123.2,122.9,121.8(q,J C-F ＝317.0Hz),121.2,113.0,104.1,101.3,86.0,83.0,32.1,22.6,17.6.
19 F NMR(376MHz,CD 3 OD):δ-79.81.
MS(ESI):m/z calcd for[SCC14-4OTf] 4+ :886.58；found:886.61,calcd for[SCC14-5OTf] 5+ :679.48；found:679.46.Elemental analysis:calcd(％)for C 164 H 132 N 20 O 32 F 24 S 8 Ru 4 Zn 2 :C 47.55,H3.21,N 6.76；found:C 47.37,H 3.28,N 6.55.
application example
MTT experiments are carried out on the ruthenium-containing supramolecular compounds SCC 1-SCC 14, unassembled ligands L1-L12 and acceptors A1-A4 prepared in the embodiment of the invention to verify whether the compounds have anticancer activity. Placing frozen cancer cells HepG-2 (human liver cancer cells), A549 (human lung cancer cells) and HCT-116 (human colon cancer cells) in a water bath, and recovering at 37 ℃. HCT-116 cells were cultured in DMEM medium and A549 cells were cultured in F-12K medium. All media used were supplemented with 10% heat-extinguished Fetal Bovine Serum (FBS) and 1% penicillin-streptomycin solution. Cancer cells cultured at 37 deg.C and containing CO 2 5% cell culture box. The growth of the cells was observed daily using a microscope and the experiment was started after passage 3 for both cancer cells.
Dissolving the ruthenium-containing supramolecular compounds SCC 1-SCC 14 and contrast drugs adriamycin and cisplatin in DMSO respectively to prepare 5 mg/mL -1 The stock solution was stored in a freezer at-20 ℃ for further use. The cancer cell suspension was transferred to a 96-well plate with a pipette gun, and the number of cells per well was controlled to 0.5X 10 4 ～1.0×10 4 In each well plate, the plate was pre-incubated in an incubator for 12/24h, the drug stock was added to the medium and diluted in a gradient, and then the drug-containing medium (DMSO concentration in the medium) was used<0.5%) of the culture medium in the well plate, and the reaction time of the cells and the drugs is 48 h.
After the reaction was completed, MTT was added to Phosphate Buffer (PBS) at pH 7.2 and filtered through a 0.22M microporous filter (care should be taken to avoid light during preparation). 20L of MTT solution was added to each well and incubated in an incubator for 4 hours. After the reaction, the solution in the well plate was removed, 100L DMSO was added to each well, the well plate was placed on a shaker and shaken for 30min, and then absorbance (λ. about.492 nm) was measured using a microplate reader, and the percentage of viable cells was calculated from the ratio of the absorbance of the cells after the drug action to that of the negative control group. Finally, IC was determined by fitting a linear regression function to the log percent viable cells versus drug concentration 50 As shown in table 1, all of the ruthenium supramolecular compounds SCC1 to SCC14 had anticancer activity.
TABLE 1IC 50 Test results
Survival rate ═ 100% (control a value-treatment well a value)/(control a value-blank a value) × (control a value-treatment well a value) × (control a value-blank a value)
Inhibition rate (1-survival rate) × 100%
lgIC 50 ＝Xm-I(P-(3-Pm-Pn)/4)
Xm is lg maximum dose;
lg (maximum dose/adjacent dose);
p: sum of positive reaction rates;
pm: the maximum positive reaction rate;
pn: minimal positive reaction rate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The metal bis-terpyridine ligand is characterized by having a structural formula shown as the following formula I:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - ；
Or
M is Ru 2+ N is 2 and X is PF 6 - R is 4-pyridyl, 4- (4-pyridyl) phenyl or 4- (1H-imidazole-1-yl) phenyl.
2. A method of preparing a metal bis-terpyridine ligand as in claim 1, comprising the steps of:
(1) using 2-acetylpyridine with R-pyridylaldehyde with the conventional
Pyridine synthesis reaction and classical Suzuki reaction react with Ullmann to obtain 2,2 ': 6 ', 2 ' -terpyridyl compounds with different R groups;
(2) and (2) carrying out chelating coordination reaction on the terpyridine product obtained in the step (1) and a metal salt to obtain a double terpyridine metal bridging compound containing two coordination sites.
(3) And (3) mixing the bridging compound obtained in the step (2) with silver salts or ammonium hexafluorophosphate of different anions to perform anion exchange to obtain the metal bis-terpyridine bridging compound with different anions and a structure shown in the formula I.
3. The ruthenium-containing supramolecular compound is characterized by having a structural formula shown as the following formula III:
wherein, L is a metal bis-terpyridyl ligand with a structure shown in formula I:
m is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - ；
Or
M is Ru 2+ N is 2, X is PF 6 - R is 4-pyridyl, 4- (4-pyridyl) phenyl or 4- (1H-imidazol-1-yl) phenyl;
a is a compound having the structure shown in formula II:
4. a process for the preparation of ruthenium-containing supramolecular compounds as claimed in claim 3, characterized in that it comprises the following steps: and mixing the compound A, the compound L and a polar organic solvent to perform coordination-driven self-assembly reaction to obtain the ruthenium-containing supramolecular compound.
5. The method of claim 4, wherein the coordination-driven self-assembly reaction is carried out for a period of 48 hours.
6. The method of claim 4, wherein the coordination-driven self-assembly reaction further comprises: removing the polar organic solvent in the coordination-driven self-assembly reaction product, and adding diethyl ether for centrifugal treatment.
7. The method according to claim 6, wherein the rotation speed of the centrifugation is 2900rpm, and the time of the centrifugation is 10 min.
8. The method according to claim 4 or 6, wherein the polar organic solvent is methanol.
9. Use of the ruthenium-containing supramolecular compounds as claimed in claim 3 for the preparation of anticancer drugs.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286199A (en) * | 2017-08-07 | 2017-10-24 | 南京师范大学 | A kind of double-core aryl ruthenium metal complex and its synthetic method and application |
| CN110627772A (en) * | 2019-10-24 | 2019-12-31 | 郑州大学 | Pinene-fused chiral terpyridine bidentate compound and preparation method thereof |
| FR3088200A1 (en) * | 2018-11-12 | 2020-05-15 | Universite De Lorraine | USE OF AN ORGANOMETALLIC COMPOUND AS A DNA DEMETHYLATION AGENT |
| CN111484447A (en) * | 2020-04-30 | 2020-08-04 | 江苏师范大学 | Bipyridyl ligand and preparation method thereof, ruthenium supermolecule self-assembly containing bipyridyl ligand and preparation method and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286199A (en) * | 2017-08-07 | 2017-10-24 | 南京师范大学 | A kind of double-core aryl ruthenium metal complex and its synthetic method and application |
| FR3088200A1 (en) * | 2018-11-12 | 2020-05-15 | Universite De Lorraine | USE OF AN ORGANOMETALLIC COMPOUND AS A DNA DEMETHYLATION AGENT |
| CN110627772A (en) * | 2019-10-24 | 2019-12-31 | 郑州大学 | Pinene-fused chiral terpyridine bidentate compound and preparation method thereof |
| CN111484447A (en) * | 2020-04-30 | 2020-08-04 | 江苏师范大学 | Bipyridyl ligand and preparation method thereof, ruthenium supermolecule self-assembly containing bipyridyl ligand and preparation method and application thereof |
Non-Patent Citations (9)
| Title |
|---|
| ALEXANDER A. PAVLOV，等: "Probing Spin Crossover in a Solution by Paramagnetic NMR Spectroscopy", INORG. CHEM., vol. 56, no. 24, pages 14759 * |
| EMI KUBOTA，等: "Synthesis, structure, and luminescence properties of arylpyridine-substituted terpyridine Zn(II) and Cd(II) complexes", POLYHEDRON, vol. 52, pages 435 - 441, XP028992072, DOI: 10.1016/j.poly.2012.08.054 * |
| JING-JING LIU, 等: "Box-like Heterometallic Macrocycles Derived from Bis-Terpyridine Metalloligands", ORGANOMETALLICS, vol. 33, no. 05, pages 1283 * |
| KELLY CHICHAK，等: "Self-assembly of a linear multicomponent porphyrin array through axial coordination", CHEM. COMMUN, no. 06, pages 523 - 524 * |
| MOHAMMED A. AL-ANBER，等: "Synthesis, solid-state structure and supramolecularity of [Cu(pyterpy)2](ClO4)2", ARABIAN JOURNAL OF CHEMISTRY, vol. 8, no. 5, pages 678 - 684 * |
| NATALIA BUSTO，等: "Targeting G-quadruplex structures with Zn(ii) terpyridine derivatives: a SAR study", DALTON TRANSACTIONS, vol. 49, no. 38, pages 13372 - 13385 * |
| S. A. KOZYUKHIN，等: "Iron Complex Redox System as a Mediator for a DyeSensitized Solar Cell", RUSSIAN JOURNAL OF INORGANIC CHEMISTRY, vol. 58, no. 01, pages 62 * |
| SHI-SHEN ZHANG，等: "A Rare Chiral Self-Catenated Network Formed by Two Cationic and One Anionic Frameworks", INORG. CHEM., vol. 46, no. 11, pages 4365 * |
| 李欣: "含联吡啶类电致变色材料的制备及表征", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, no. 02, pages 014 - 602 * |
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