CN115010653B - Metal bis-terpyridine ligand, ruthenium-containing supermolecule compound, and preparation method and application thereof - Google Patents
Metal bis-terpyridine ligand, ruthenium-containing supermolecule compound, and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 25
- 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 abstract description 14
- 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 compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 111
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000001338 self-assembly Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 206010028980 Neoplasm Diseases 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 7
- 201000011510 cancer Diseases 0.000 abstract description 6
- 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 35
- 239000007787 solid Substances 0.000 description 29
- 239000011701 zinc Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000000370 acceptor Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 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
- -1 ruthenium (II) arene Chemical class 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 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
- 238000001914 filtration Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000001093 anti-cancer Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction 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
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- 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
- 206010009944 Colon cancer Diseases 0.000 description 2
- 102100029952 Double-strand-break repair protein rad21 homolog Human genes 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
- 101000584942 Homo sapiens Double-strand-break repair protein rad21 homolog Proteins 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 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 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
- 238000005349 anion exchange Methods 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
- 238000001816 cooling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 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
- 125000002962 imidazol-1-yl group Chemical group [*]N1C([H])=NC([H])=C1[H] 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
- 239000002609 medium Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000002953 phosphate buffered saline Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 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
- 101100532684 Arabidopsis thaliana SCC3 gene Proteins 0.000 description 1
- 101100532679 Caenorhabditis elegans scc-1 gene Proteins 0.000 description 1
- 101100240606 Caenorhabditis elegans scc-2 gene Proteins 0.000 description 1
- 101100532685 Caenorhabditis elegans scc-3 gene Proteins 0.000 description 1
- 102100035590 Cohesin subunit SA-1 Human genes 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 101001093139 Homo sapiens MAU2 chromatid cohesion factor homolog Proteins 0.000 description 1
- 101001024120 Homo sapiens Nipped-B-like protein Proteins 0.000 description 1
- 101100043640 Homo sapiens STAG1 gene Proteins 0.000 description 1
- 102100036309 MAU2 chromatid cohesion factor homolog Human genes 0.000 description 1
- 102100035377 Nipped-B-like protein Human genes 0.000 description 1
- 206010053159 Organ failure Diseases 0.000 description 1
- 101100062195 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CPR4 gene Proteins 0.000 description 1
- 101100532687 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) IRR1 gene 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
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000010261 cell growth Effects 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
- 229960004679 doxorubicin Drugs 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 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
- 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
- 150000002739 metals Chemical class 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 150000003378 silver Chemical class 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
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-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
- 238000009987 spinning Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 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
- 238000001291 vacuum drying Methods 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)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention provides a metal double terpyridine ligand with a structure shown in the following formula. The metal double terpyridine ligand provided by the invention fuses the necessary metal of the human body and the derivative of the topoisomerase inhibitor terpyridine, has the characteristic of low toxicity of the human body, and is a novel ligand. The invention also provides a ruthenium-containing hexanuclear homonuclear/heterometallic supermolecular compound, which is a novel ruthenium-containing supermolecular compoundThe ruthenium hexanuclear homonuclear/heterometallic supermolecular compounds containing different anions have good inhibition effects on human cancer cell lines HepG-2, A549 and HCT-116, and have application prospects in the aspect of preparing anticancer drugs.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a ruthenium-containing supermolecular compound, a preparation method and application thereof, a benzimidazole ligand and a preparation method thereof.
Background
Tumors refer to tumors formed by abnormal proliferation of cells of local tissues under the action of various tumorigenic factors. Tumors can be classified as benign tumors and malignant tumors, which (also called cancers) can destroy the structure and function of tissues and organs, cause hemorrhagic necrosis and infection of tissues or organs, and ultimately, the patient may die due to organ failure. The ruthenium-based compound has good anticancer activity, and an important class is an arene ruthenium (II) supermolecule self-assembled anticancer compound constructed through coordination bond driving.
Suss-Fink synthesized the first ruthenium (II) arene supermolecular complex in 1997. The arene ruthenium (II) acceptor is a partially encapsulated ruthenium-based coordination compound, which is structurally similar to a piano stool (also known as a molecular clamp), and is two ruthenium (II) ions connected by a bridging ligand, and one coordination site is left on each metal ion. The polynuclear supermolecule self-assembled compound with a two-dimensional or three-dimensional structure is obtained by applying self-assembly means to arene ruthenium (II) acceptors and ligands with different angles or different types. Most of the prior art related to anticancer p-cymene ruthenium self-assembled compounds mostly adopt double-headed pyridine or carboxylic acid ligands.
Disclosure of Invention
In view of the above, the invention aims to provide a ruthenium-containing supermolecule compound, a preparation method and application thereof, a terpyridine hetero-metal bridged ligand and a preparation method thereof. The invention also provides novel ruthenium-containing supermolecule polynuclear homo/heterometallic compounds and provides compounds 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 a structure represented by formula I:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - The method comprises the steps of carrying out a first treatment on the surface of the 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.
The invention also provides a preparation method of the terpyridine metal bridged ligand, which comprises the following steps:
(1) The use of 2-acetylpyridine with R-pyridylaldehyde is conventionalPyridine synthesis reaction, classical Suzuki reaction and Ullmann reaction to obtain 2,2':6', 2' -terpyridine compounds with different R groups;
(2) Combining the terpyridine product from step (1) with a metal (Fe) 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ ) And carrying out chelating coordination reaction on the salt to obtain the double terpyridine metal bridging compound containing two coordination points.
(3) And (3) mixing the bridged compound obtained in the step (2) with silver salts or ammonium hexafluorophosphate of different anions to perform anion exchange, so as to obtain the terpyridine metal bridged ligand with the structure shown in the formula I of different anions.
The present invention provides an a-receptor having a structure represented by formula ii:
the invention also provides a ruthenium-containing supermolecule compound, which has a structure shown in a formula II:
wherein L is a compound having the structure of 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 supermolecule compound, which comprises the following steps: and mixing the A compound, the L compound and the polar organic solvent to perform coordination-driven self-assembly reaction, thus obtaining the ruthenium-containing supermolecule compound.
Preferably, the time for the coordination driven self-assembly reaction is 48 hours.
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 rotational speed of the centrifugal treatment is 2900rpm, and the time of the centrifugal treatment is 10min.
Preferably, the polar organic solvent is dichloromethane and/or methanol.
The invention also provides application of the ruthenium-containing supermolecule compound in preparation of anticancer drugs.
The invention provides a terpyridine metal bridging ligand which introduces nontoxic transition metal necessary for human body into a novel ligand in the field of anticancer, and has no toxicity to moderate toxicity to cancer cells.
The invention also provides a ruthenium-containing supermolecular compound, which is a novel ruthenium-containing supermolecular 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 double terpyridine ligand with a structure shown in a formula I:
wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ N is 2 or 3, X is OTf - The method comprises the steps of carrying out a first treatment on the surface of the Or M is Ru 2+ N is 2, X is PF 6 - R is 4-pyridyl or 4- (4-pyridyl) phenyl or 4- (1H-imidazol-1-yl) phenyl
The main preparation flow of L1-L12 is as follows:
(1) The use of 2-acetylpyridine with R-pyridylaldehyde is conventionalPyridine synthesis reaction, classical Suzuki reaction and Ullmann reaction to obtain 4-pyridyl-2, 2':6', 2' -terpyridine, 4- (4-pyridyl) phenyl-2, 2':6', 2' -terpyridine, 4- (1H-imidazol-1-yl) phenyl-2, 2':6', 2' -terpyridine,
(2) Combining the terpyridine product of step (1) wherein R is 4-pyridyl with a metal (Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ ) And carrying out chelating coordination reaction on the salt to obtain the double terpyridine metal bridging compound containing two coordination points.
(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 double terpyridine metal bridged ligand with the structure shown in the formula I.
The preparation method of L1 comprises the following steps: zinc trifluoromethane sulfonate dissolved in methanol solution is slowly added dropwise to 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine in dichloromethane solution, and the mixture is stirred while being dropwise added, and the reaction is vigorously stirred at 60 ℃ for 12 hours. And (3) after the reaction system is cooled to room temperature, filtering to obtain light purple solid powder, washing with methanol and dichloromethane, and drying to obtain a target product.
The preparation method of L2 comprises the following steps: under the nitrogen atmosphere, ferrous chloride dissolved in methanol solution is slowly added into 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine dichloromethane solution in a dropwise manner, stirring is carried out, and the reaction is carried out for 12h under intense stirring at 60 ℃. And (3) after the reaction system is cooled to room temperature, adding 2 times of ferrous chloride equivalent silver trifluoromethane sulfonate, and continuously stirring for 2 hours. 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 a target product.
The preparation method of L3 comprises the following steps: ferric chloride dissolved in methanol solution is slowly added into 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine dichloromethane solution in a dropwise manner, and the mixture is stirred while stirring, and the reaction is vigorously stirred at 60 ℃ for 12h. And (3) after the reaction system is cooled to room temperature, adding 3 times of ferric chloride equivalent of silver trifluoromethane sulfonate, and continuously stirring for 2 hours. Filtering to remove solid impurities of 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: cobalt chloride dissolved in methanol solution is slowly added into 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine dichloromethane solution in a dropwise manner, and the mixture is stirred while stirring, and the reaction is vigorously stirred at 60 ℃ for 12 hours. And (3) after the reaction system is cooled to room temperature, adding 2 times of cobalt chloride equivalent of silver trifluoromethane sulfonate, and continuously stirring for 2 hours. Adding a large amount of methanol into the reaction system to dissolve precipitated products, filtering to remove solid impurities, distilling the tan 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: copper chloride dissolved in methanol solution is slowly added dropwise to a dichloromethane solution of 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine, and the mixture is stirred while being dropwise added, and the reaction is vigorously stirred at 60 ℃ for 12 hours. And (3) after the reaction system is cooled to room temperature, adding 2 times of copper chloride equivalent of silver trifluoromethane sulfonate, and continuously stirring for 2 hours. Adding a large amount of methanol into the reaction system to dissolve precipitated products, 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 target products.
The preparation method of L6 comprises the following steps: under nitrogen atmosphere, ruthenium chloride and 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine are reacted in ethylene glycol solution under the condition of shading reflux for 4 hours. After the reaction is finished, the reaction system is cooled to room temperature, ammonium hexafluorophosphate which is excessive in 2 times of ruthenium chloride is added, stirring is continued for 2 hours, and diatomite is filtered to obtain a solid crude product. Water, diethyl ether and acetonitrile 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 band 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: zinc nitrate dissolved in methanol solution was slowly added dropwise to a 2-fold equivalent of 4-pyridyl-2, 2':6',2 "-terpyridine in methylene chloride solution with stirring, and the reaction was vigorously stirred at 60 ℃ for 12h. And (3) after the reaction system is cooled to room temperature, decompressing and distilling the colorless transparent solution to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain a target product.
The preparation method of L8 comprises the following steps: the zinc p-toluenesulfonate dissolved in methanol solution was slowly added dropwise to a 2-fold equivalent of 4-pyridyl-2, 2':6',2 "-terpyridine in methylene chloride solution with stirring, and the reaction was vigorously stirred at 60℃for 12 hours. And (3) after the reaction system is cooled to room temperature, decompressing and distilling the colorless transparent solution to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain a target product.
The preparation method of L9 comprises the following steps: zinc tetrafluoroborate dissolved in methanol solution was slowly added dropwise to a 2-fold equivalent of 4-pyridyl-2, 2':6',2 "-terpyridine in methylene chloride solution with stirring, and the reaction was vigorously stirred at 60 ℃ for 12 hours. And (3) after the reaction system is cooled to room temperature, decompressing and distilling the colorless transparent solution to obtain white solid powder, washing with a small amount of methanol and dichloromethane, and drying to obtain a target product.
The preparation method of L10 comprises the following steps: zinc acetate dissolved in methanol solution is slowly added into ethanol solution of 2 times equivalent of 4-pyridyl-2, 2':6', 2' -terpyridine, and the mixture is stirred while being added dropwise, and the mixture is subjected to reflux reaction for 2 hours. And (3) cooling the reaction system to room temperature, adding ammonium hexafluorophosphate which is excessive by 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 a target product.
The preparation method of L11 comprises the following steps: zinc trifluoromethane sulfonate dissolved in methanol solution is slowly added dropwise to 2 times equivalent of 4- (4-pyridyl) phenyl-2, 2':6', 2' -terpyridine in dichloromethane solution, and the mixture is stirred while being dropwise added, and the reaction is vigorously stirred at 60 ℃ for 12 hours. And (3) after the reaction system is cooled to room temperature, filtering to obtain white solid powder, washing with methanol and dichloromethane, and drying to obtain a target product.
The preparation method of L12 comprises the following steps: zinc trifluoromethane sulfonate dissolved in methanol solution is slowly added dropwise to 2 times equivalent of 4- (1H-imidazol-1-yl) phenyl-2, 2':6', 2' -terpyridine in dichloromethane, and the mixture is stirred while being dropwise added, and the mixture is vigorously stirred at 60 ℃ for reaction for 12 hours. And (3) after the reaction system is cooled to room temperature, filtering to obtain white solid powder, washing with methanol and dichloromethane, and drying to obtain a target product.
The present invention provides an a-receptor having a structure represented by formula ii:
the source of the A is not particularly limited, and the A can be prepared by a preparation method well known to a person skilled in the art, specifically, the A is as follows:
the preparation method of A1-A4 comprises the following steps:
(1) Adding dichlorobis (4-cymene) ruthenium (II), nepadine and sodium acetate into a pear-shaped bottle, adding ethanol, and refluxing for 24 hours under vigorous stirring. After the reaction system is cooled to room temperature, centrifuging (2500 r/min) for 10min, discarding supernatant, and respectively washing the solid with ethanol, acetone and diethyl ether twice to obtain brown solid;
(2) Dissolving the solid obtained in the step (1) with silver triflate, silver nitrate, silver paratoluenesulfonate and silver hexafophosphate in methanol respectively, stirring for 2-4 hours at room temperature, precipitating white AgCl precipitate, filtering with diatomite to obtain filtrate, spinning to a little dry, adding diethyl ether, and precipitating green solid. Centrifuging (2500 r/min) for 10min to obtain target products A1-A4 containing different anions respectively, and vacuum drying.
The invention also provides a ruthenium-containing supermolecule 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 - The method comprises the steps of carrying out a first treatment on the surface of the Or M is Ru 2+ N is 2, X is PF 6 - 。
In the invention, the time of the coordination-driven self-assembly reaction is preferably 48 hours, the temperature of the coordination-driven self-assembly reaction is preferably room temperature, and no additional heating or cooling is needed.
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 method for removing the polar organic solvent is not particularly limited, and may be any method known to those skilled in the art, such as purging. The amount of diethyl ether is not particularly limited in the invention, and the ruthenium-containing supermolecule compound can be precipitated.
In the present invention, the rotational speed of the centrifugal treatment is preferably 2900rpm, and the time of the centrifugal treatment is preferably 10min.
After the centrifugation product is obtained, the invention preferably also includes the ability to wash the centrifugation product with diethyl ether. The amount of diethyl ether and the number of centrifugation are not particularly limited in the present invention, and may be any one known to those skilled in the art.
In the present invention, there are provided supermolecular compounds obtained by ligands L1 to L6 and A1 of different metals M having the structure shown in formula I.
Wherein M is Fe 2+ /Fe 3+ /Co 2+ /Cu 2+ /Zn 2+ /Ru 2+ N is 2 or 3, X is OTf - The method comprises the steps of carrying out a first treatment on the surface of the Or M is Ru 2+ N is 2, X is PF 6 - 。
Provided are ruthenium-containing supramolecular compounds 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, X is PF 6 - Y is OTf-.
Example 1
Ligand L1 (3.9280 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were precisely weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature to perform coordination-driven self-assembly for 24h, the solvent was blown to 0.2mL, diethyl ether was added to precipitate a solid, the solid was centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and the metal rectangular ruthenium-containing supermolecular compound SCC1 was obtained by washing once with diethyl ether.
Characterization of a metallic rectangular ruthenium containing supermolecular 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 (3.8990 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were accurately weighed into an 8mL catalytic vial, dissolved using methanol, stirred at room temperature to undergo coordination driven self-assembly for 24h, the solvent was blown to 0.2mL and diethyl ether was added to precipitate a solid, centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC2.
Characterization of a metallic rectangular ruthenium-containing supermolecular 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 (4.4950 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were accurately weighed into an 8mL catalytic vial, dissolved using methanol, stirred at room temperature to undergo coordination driven self-assembly for 24h, the solvent was blown to 0.2mL and diethyl ether was added to precipitate a solid, centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC3.
Characterization of a metallic rectangular ruthenium-containing supermolecular 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 (3.9115 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were accurately weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature to undergo coordination-driven self-assembly for 24h, the solvent was blown to 0.2mL and diethyl ether was added to precipitate a solid, and the solid was centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC4.
Characterization of a metallic rectangular ruthenium containing supermolecular 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 (3.9297 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were accurately weighed into an 8mL catalytic vial, dissolved using methanol, stirred at room temperature to undergo coordination driven self-assembly for 24h, the solvent was blown to 0.2mL and diethyl ether was added to precipitate a solid, centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC5.
Characterization of a metallic rectangular ruthenium containing supermolecular 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 (4.0473 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were accurately weighed into an 8mL catalytic vial, dissolved using methanol, stirred at room temperature to undergo coordination driven self-assembly for 24h, the solvent was blown to 0.2mL and diethyl ether was added to precipitate a solid, centrifuged for 10min using a centrifuge (2900 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC6.
Characterization of a metallic rectangular ruthenium containing supermolecular 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, supermolecular compounds SCC7 and SCC8 obtained by 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 (3.2405 mg,0.004 mmol) and metal acceptor A2 (3.1309 mg, 0.04 mmol) were weighed into an 8mL catalytic vial, dissolved using methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL, diethyl ether was added, centrifuged using a centrifuge (2500 r/min) for 10min, the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC7.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 (4.1140 mg, 0.04 mmol) and metal acceptor A3 (4.0124 mg, 0.04 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24h, the solvent was blown to 0.2mL, diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC8.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 to L10 of A1.
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 (physical pattern) 6 - . Y is OTf - 。
Example 9
Ligand L7 (3.2405 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24 hours, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC9.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 (4.1140 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24 hours, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to obtain a metal rectangular ruthenium-containing supermolecular compound SCC10.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 (3.4389 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24 hours, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC11.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 (3.4389 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24 hours, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC12.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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, there is provided a supermolecular compound obtained by first providing ligands L11 to L12 having different R groups and A1.
Supramolecular compounds having different R groups of 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 (4.5458 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) 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 for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC13.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 (4.4576 mg,0.004 mmol) and metal acceptor A1 (3.9520 mg,0.004 mmol) were weighed into an 8mL catalytic vial, dissolved with methanol, stirred at room temperature for 24 hours, the solvent was blown to 0.2mL and diethyl ether was added, centrifuged for 10min using a centrifuge (2500 r/min), the supernatant was discarded, and washed once with diethyl ether to give a metal rectangular ruthenium-containing supermolecular compound SCC14.
Structural characterization of a metallic rectangular ruthenium-containing supermolecular 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 ruthenium-containing supermolecular compounds SCC 1-SCC 14, unassembled ligands L1-L12 and acceptors A1-A4 prepared in the embodiment of the invention to verify whether the ruthenium-containing supermolecular compounds have anticancer activity. Taking frozen cancer cells HepG-2 (human liver cancer cells), A549 (human lung cancer cells), and HCT-116 (human colon cancer cells) to be placed in a water bath kettle for resuscitation at 37 ℃. HCT-116 cells were cultured using DMEM medium, and A549 cells were cultured using F-12K medium. All media used were supplemented with 10% hot Fetal Bovine Serum (FBS) and 1% penicillin-streptomycin solution. Cancer cells were cultured at 37℃and CO-containing 2 5% in a cell incubator. The cell growth was observed daily using a microscope and experiments were started after passage 3.
Dissolving ruthenium-containing supermolecular compound SCC 1-SCC 14 and control drug doxorubicin and cisplatin in DMSO to prepare 5 mg.mL -1 The stock solution is stored in a refrigerator at the temperature of minus 20 ℃ for standby. The cancer cell suspension was transferred to a 96-well plate with a pipette gun, and the number of cells per well was controlled at 0.5X10 4 ～1.0×10 4 The well plate was previously cultured in an incubator for 12/24 hours, the stock solution of the drug was added to the culture medium, and was diluted in a gradient, and then a culture solution containing the drug was used (DMSO concentration in the culture solution<0.5%) of the original culture solution was replaced in the well plate, and the reaction time of the cells and the drug was 48 hours.
After the reaction was completed, MTT was formulated into Phosphate Buffered Saline (PBS) at ph=7.2 and filtered using a 0.22M microporous filter (formulation should be taken to avoid light). 20L of MTT solution was added to each well, and the mixture was incubated in an incubator for 4 hours. After the reaction was completed, the solution in the well plate was removed, 100L of DMSO was added to each well, the well plate was placed on a shaker for 30min, and then absorbance (lambda=492 nm) was measured using a microplate reader, and then the percentage of surviving cells was calculated using the absorbance ratio with the cells after the drug action and the negative control group. Finally, using a linear regression function to fit the log percent of surviving cells to drug concentration to determine IC 50 The values are shown in Table 1, and the ruthenium-containing supermolecular compounds SCC1 to SCC14 have anticancer activity.
TABLE 1IC 50 Test results
Survival = (control a-treated well a)/(control a-blank a) ×100%
Inhibition rate = (1-survival rate) ×100%
lgIC 50 ＝Xm-I(P-(3-Pm-Pn)/4)
Xm: lg maximum dose;
lg (maximum dose/adjacent dose);
p: the sum of positive reaction rates;
pm: maximum positive response rate;
pn: minimal positive response rate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The metal double terpyridine ligand is characterized in that the structural formula is shown in any one of the following formulas:
2. the preparation method of the ruthenium-containing supermolecular compound is characterized by comprising the following steps: mixing the A compound, the L compound and methanol to perform coordination driving self-assembly reaction to obtain a ruthenium-containing supermolecule compound;
a is a compound represented by the following formula A1, A2 or A3:
l is a compound of any one of the following formulas:
3. the method of claim 2, wherein the coordination driven self-assembly reaction is performed for 48 hours.
4. The method of claim 2, wherein the coordination driven self-assembly reaction is followed by: removing methanol in the coordination-driven self-assembly reaction product, and adding diethyl ether for centrifugation.
5. The method according to claim 4, wherein the rotational speed of the centrifugation is 2900rpm and the time of the centrifugation is 10 minutes.
6. A ruthenium-containing supramolecular compound prepared by the process of claim 2.
7. The use of a ruthenium-containing supermolecular compound according to claim 6 for preparing anticancer drugs.
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