WO2023023898A1 - Rare earth ion-containing bionic water cracking catalyst, and preparation method therefor and use thereof - Google Patents
Rare earth ion-containing bionic water cracking catalyst, and preparation method therefor and use thereof Download PDFInfo
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- WO2023023898A1 WO2023023898A1 PCT/CN2021/114107 CN2021114107W WO2023023898A1 WO 2023023898 A1 WO2023023898 A1 WO 2023023898A1 CN 2021114107 W CN2021114107 W CN 2021114107W WO 2023023898 A1 WO2023023898 A1 WO 2023023898A1
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000005336 cracking Methods 0.000 title abstract description 4
- 239000011664 nicotinic acid Substances 0.000 title abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 201
- -1 rare earth ion Chemical class 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
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- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical group [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 4
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
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- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the invention relates to a biomimetic water splitting catalyst containing rare earth ions, a preparation method and application thereof, and belongs to the technical field of catalysts.
- the photosystem II of photosynthetic organisms is the only biological system in nature that can efficiently and safely use cheap metal ions to split water, obtain electrons and protons, and release oxygen at the same time.
- the reason why Photosystem II can efficiently and safely split water is that it has a unique [Mn 4 CaO 5 ] heteronuclear metal cluster biocatalyst, whose periphery is provided by six carboxyl groups, an imidazole ring and four water molecules to provide ligands .
- the biocatalyst undergoes five different states (S 0 , S 1 , S 2 , S 3 , S 4 ); among them, the S 1 state is a dark stable state, and the valence states of the four manganese ions correspond to (+ 3, +3, +4, +4).
- S 0 , S 1 , S 2 , S 3 , S 4 the S 1 state is a dark stable state
- the valence states of the four manganese ions correspond to (+ 3, +3, +4, +4).
- Patent ZL201510065238.7 discloses a water splitting catalyst containing [Mn 4 CaO 4 ] core structure, its preparation method and its application;
- patent ZL201711059799.1 discloses a catalyst containing [Mn 3 SrO 4 ] and [Mn 4 SrO 4 ] Clusters with core structure and their preparation methods and applications.
- R 1 is selected from H or C 1-8 linear or branched chain alkyl
- L 1 , L 2 , L 3 , L 4 are four identical or different ligands, each independently selected from Carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their derivatives, or water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters, etc. can be exchanged of small molecules.
- the present invention uses rare earth ions X (such as selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) At least one of ) is introduced into the synthesis catalyst, providing three types of rare earth manganese heteronuclear metal clusters with core structures of [Mn 3 XO 2 ], [Mn 4 XO 4 ] and [Mn 4 XO 5 ] and their preparation methods and applications.
- rare earth ions X such as selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium,
- a rare earth manganese heteronuclear metal cluster compound which has a [Mn n XO m ] heteronuclear metal cluster skeleton core, wherein, n is 3 or 4; m is 2, 4 or 5; X is selected from rare earth elements.
- the rare earth manganese heteronuclear metal cluster has one of the following core structures: [Mn 3 XO 2 ] heteronuclear metal cluster skeleton core, [Mn 4 XO 4 ] heteronuclear Metal cluster skeleton core and [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core, wherein X is selected from rare earth elements.
- said X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
- the chemical formula of the cluster is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , which has a structure as shown in Formula I, which contains a rare earth ion X and three Mn ions, which are connected by two ⁇ 3 -O bridges to form the [Mn 3 XO 2 ] heteronuclear metal cluster skeleton core;
- peripheral ligands of the [Mn 3 XO 2 ] heteronuclear metal cluster framework core are provided by nine carboxylate anions R 1 CO 2 - and three neutral carboxylic acid ligands R 1 CO 2 H, of which the valence of three Mn ions The states are +3, +3, +4 respectively, and the whole cluster is electrically neutral;
- X is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
- R 1 are the same or different, independently selected from H or C 1-8 straight or branched chain alkyl.
- the carboxylate anion R 1 CO 2 - may be formate, acetate, propionate, isopropionate, butyrate, isobutyrate, tert-butyrate, valerate, isovalerate, pivalate At least one of acid radical, hexanoic acid radical and the like.
- R 1 can be hydrogen (H), methyl (-CH 3 ), ethyl (-C 2 H 5 ), n-propyl (-CH 2 CH 2 CH 3 ), isopropyl (-CH(CH 3 ) 2 ), n-butyl (-(CH 2 ) 3 CH 3 ), isobutyl (-CH(CH 3 )C 2 H 5 ), tert-butyl (-C(CH 3 ) 3 ), n-pentyl (-(CH 2 ) 4 CH 3 ), isopentyl (-CH 2 CH 2 CH(CH 3 ) 2 ), pentyl (-CH 2 C(CH 3 ) 3 ) or n-hexyl (-(CH 2 ) One of 5 CH 3 ) and the like.
- R 1 CO 2 H may be at least A sort of.
- the cluster compound having the structure shown in formula I is selected from any cluster compound in the following cluster compounds 1 to 5:
- the cluster compound 1 is a single crystal; its structure is shown in formula I-1:
- the cluster compound 2 is a single crystal; its structure is shown in formula I-2:
- the cluster compound 3 is a single crystal; its structure is shown in formula I-3:
- the cluster compound 4 is a single crystal; its structure is shown in formula I-4:
- the cluster compound 5 is a single crystal; its structure is shown in formula I-5:
- the chemical formula of the cluster is Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), which has a structure as shown in formula II, which Containing four Mn ions and one rare earth ion X, they are connected into [Mn 4 XO 4 ] heteronuclear metal cluster skeleton core through four ⁇ -O bridges;
- peripheral ligands of the [Mn 4 XO 4 ] heteronuclear metal cluster framework core are provided by eight carboxylate anions R 1 CO 2 - and three ligands L 1 , L 2 and L 3 ; the valence states of four Mn ions They are +3, +3, +4, +4 respectively.
- L 1 and L 2 are the same or different, each independently selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, Ethers, ketones, nitriles, esters, amides and their respective derivatives, or L1 and L2 are connected as a bidentate chelating ligand;
- L3 is selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters , amides and their respective derivatives.
- L 1 and L 2 are preferably connected as pivalate, and L 3 is preferably isoquinoline.
- the nitriles may be, for example, acetonitrile.
- the esters are, for example, ethyl acetate; the amides are, for example, N-methylformamide, N-methylacetamide, N,N-dimethylformamide and N,N-dimethylacetamide kind of.
- the cluster compound having the structure shown in formula II is selected from any cluster compound in the following cluster compounds 6 to 8:
- the cluster compound 6 is a single crystal; its structure is shown in formula II-1:
- the cluster compound 7 is a single crystal; its structure is shown in formula II-2:
- the cluster compound 8 is a single crystal; its structure is shown in formula II-3:
- the chemical formula of the cluster is Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), which has a structure shown in formula III, which contains four Mn ions and a rare earth ion, they are connected by five ⁇ -O to form the [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core;
- the peripheral ligands of the [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core are composed of eight carboxylate anions Provided by R 1 CO 2 - and two ligands L 4 and L 5 ;
- the valence states of the four manganese ions are +3, +3 , +4, +4;
- the rare earth ion X and R have the above meanings; L and L are the same or different, and are independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and Their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and their respective derivatives, or L4 and L5 linked as a bidentate chelating ligand .
- L 4 and L 5 are the same or different, independently selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylformamide A sort of.
- the cluster compound having the structure shown in formula III is selected from any one of the following cluster compounds 9 to 11:
- the cluster compound 9 is a single crystal; its structure is shown in formula III-1:
- the cluster compound 10 is a single crystal; its structure is shown in formula III-2:
- the cluster compound 11 is a single crystal; its structure is shown in formula III-3:
- the present invention also provides a method for preparing the rare earth manganese heteronuclear metal cluster, the method comprising the following steps: adding permanganate anion oxidant, rare earth salt and ligand, optionally adding water or divalent manganese salt, and react in solution to prepare the cluster.
- the present invention provides a method for preparing a cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I, said The method includes the following steps:
- the cluster compound is prepared by reacting organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt, optionally adding water or divalent manganese salt in an acetonitrile solution.
- the method specifically includes: reacting organic carboxylic acid R 1 COOH, permanganate anion-type oxidizing agent, rare earth salt and water in an acetonitrile solution to prepare the chemical formula Mn 3 XO having the structure shown in formula I 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 clusters.
- the method specifically includes: reacting organic carboxylic acid R 1 COOH, permanganate anion-type oxidizing agent, rare earth salt and divalent manganese salt in an acetonitrile solution to prepare a chemical formula having the structure shown in formula I: Clusters of Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 .
- the molar ratio of the organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt, water or divalent manganese salt is (10 ⁇ 120):(1 ⁇ 10):1:(0 ⁇ 5); preferably (20-120):(2-8):1:(1-2).
- the organic carboxylic acid R 1 COOH is, for example, selected from carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and their derivatives At least one of, preferably isobutyric acid or pivalic acid.
- the permanganate anionic oxidizing agent is, for example, tetrabutylammonium permanganate ((C 4 H 9 ) 4 N ⁇ MnO 4 ).
- the rare earth salt can be at least one of trifluoromethanesulfonate, nitrate, perchlorate and carboxylate of rare earth ions, or the rare earth salt also contains crystal water;
- the carboxylate of the rare earth ion contains carboxylate anion (R 1 CO 2 - ), and the carboxylate anion has the aforementioned definition.
- the divalent manganese salt has the following structural formula: MnA 2 ⁇ tH 2 O; wherein, A is selected from carboxylate anion (R 1 CO 2 - ), chloride ion, ClO 4 - , NO 3 - , CF 3 SO 3 ⁇ , acetylacetonate, and carboxylate anions have the meanings described above; t is 0-6, preferably 1-5, and more preferably 2-4.
- the divalent manganese salt is selected from Mn(ClO 4 ) 2 , MnCl 2 , Mn(NO 3 ) 2 , Mn(CF 3 SO 3 ) 2 , manganese acetylacetonate, or their respective manganese salts containing water of crystallization at least one of the
- acetonitrile 60-100 milliliters of acetonitrile is used for every millimole of rare earth salt.
- the present inventors found that the preparation method of the cluster compound with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I can only be carried out in acetonitrile solvent, and in alcohol Or other organic solvents can not obtain the target clusters.
- the reaction temperature is 60°C to 90°C.
- it may be 60°C, 70°C, 80°C, or 90°C.
- the reaction time may be 10-60 minutes.
- the reaction further includes a post-treatment step: filter the reaction product to remove the precipitate, and after the liquid is static, the purified chemical formula with the structure shown in formula I is obtained as Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 Clusters of CO 2 H) 3 .
- the resting time is, for example, 1 to 7 days.
- the specific steps of the preparation method of the cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I are as follows: :
- the specific steps of the preparation method of the cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I are as follows: :
- the present invention also provides a cluster compound having the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) having the structure shown in formula II
- Preparation method described method specifically comprises the following steps:
- organic carboxylic acid R 1 COOH, permanganate anion oxidant, divalent manganese salt, rare earth salt, and L 1 , L 2 and L 3 have the above meanings.
- the molar ratio of the organic carboxylic acid R 1 COOH, permanganate anion oxidant, divalent manganese salt and rare earth salt is (10-120):(1-10):1:1, preferably ( 20 ⁇ 100):(2 ⁇ 8):1:1.
- the content of acetonitrile per millimole of rare earth salt is about 60-100 milliliters.
- This reaction can only be carried out in acetonitrile solvent, and the target cluster cannot be obtained in alcohol or other organic solvents.
- step (2) the intermediate is firstly dissolved in a halogenated hydrocarbon organic solvent and a nitrile solvent, and then reacted with a ligand.
- halogenated hydrocarbon organic solvent can be a kind of in methylene dichloride, dichloroethane or chloroform and derivative thereof; Described nitrile solvent can be acetonitrile, propionitrile or butyronitrile and one of its derivatives.
- step (2) the ligand accounts for 0.1-3% of the total volume of the solvent.
- step (1) a post-processing step is also included: the intermediate is filtered to remove the precipitate, and after the liquid is static at 0° C., the precipitated solid is the purified intermediate.
- step (2) a post-processing step is also included: the reaction product is filtered to remove the precipitate, and after the liquid is still, crystals are precipitated, washed and dried to obtain the purified chemical formula Mn 4 XO 4 ( Clusters of R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ).
- the resting time is, for example, 1 to 7 days.
- the reaction temperature is 60°C to 90°C.
- the reaction time may be 10-60 minutes.
- the preparation method is specifically:
- the first step the organic carboxylic acid R 1 COOH, permanganate anionic oxidant, divalent manganese salt and rare earth salt, according to the molar ratio of (10 ⁇ 120): (1 ⁇ 10): 1: 1, in the acetonitrile solution Heating and reacting in medium temperature for 10-60 minutes, a brown solution was obtained, and the precipitate was removed by filtration; standing at 0°C for 1-6 days to obtain a brown crystal, that is, an intermediate;
- the second step dissolve the synthetic intermediate in a mixed solvent of halogenated hydrocarbon organic solvent and nitrile, add ligand L 3 , further react, optionally react with ligand L 1 and/or L 2 , and crystallize to obtain the formula (II) The cluster compound of the structure shown.
- the present invention also provides a method for preparing a cluster with the chemical formula Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) having the structure shown in formula III,
- the methods include:
- Clusters of the shown structure Dissolving the cluster compound having the structure shown in formula II in halogenated hydrocarbon and/or ester solvent, adding water, optionally adding or not adding ligand L 4 and ligand L 5 , and reacting to obtain Clusters of the shown structure.
- the ester solvent may be one of methyl acetate, ethyl acetate and the like.
- halogenated hydrocarbons ligands L 4 , and L 5 have the above meanings.
- the preparation method also includes a post-processing step: filter the reaction product, remove a small amount of precipitate, the reaction solution is still, wash the precipitated crystals with n-hexane, and dry to prepare the purified chemical formula with the structure shown in formula III: Clusters of Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ).
- the reaction temperature is 20°C to 60°C.
- the reaction time may be 1-15 minutes.
- the present invention also provides a biomimetic water splitting catalyst, which contains the above-mentioned rare earth manganese heteronuclear metal clusters.
- the present invention also provides the application of the above biomimetic water splitting catalyst, which is used to catalyze the splitting of water.
- the catalytic process takes place on the surface of the electrodes, or in the presence of an oxidizing agent.
- the present invention introduces rare earth ions X with stronger coordination ability, and synthesizes a series of clusters with [Mn n XO m ] heteronuclear metal cluster skeleton core, for example, the core structure is [Mn 3 XO 2 ], [Mn 4 XO 4 ] and [Mn 4 XO 5 ] clusters.
- This series of clusters is a new type of biomimetic water splitting catalyst. Especially the clusters whose core structures are [Mn 4 XO 4 ] and [Mn 4 XO 5 ], their geometric structure and Mn ion valence are very similar to the catalytic center of biological water splitting.
- This series of new biomimetic clusters containing rare earth breaks through the shackles of traditional concepts, and is no longer limited to alkaline earth metals that are exactly the same as living things.
- the introduction of rare earth metal ions greatly improves the stability.
- On the electrode surface there may be oxidants (either a stable oxidant or a light-induced transient oxidant) drives the catalytic splitting of water.
- oxidants either a stable oxidant or a light-induced transient oxidant
- combining the unique magnetic characteristics of tetravalent Mn ions in clusters and some rare earth elements has important application value in magnetic materials, and combined with spectroscopy tracking and characterization may lay an important foundation for future mechanism research.
- This application uses rare earth ions, manganese ions, and carboxylic acids as raw materials, and uses permanganate anion as an oxidant to synthesize the core structures as [Mn 3 XO 2 ], [Mn 4 XO 4 ], and [Mn 4 XO 5 ]
- the clusters of these clusters have a manganese ion valence of +3 or +4 and are of great value in magnetic materials.
- the clusters whose core structures are [Mn 4 XO 4 ] and [Mn 4 XO 5 ] obtained in the present invention can be used as artificial water splitting catalysts on the surface of electrodes, or by oxidants (which can be stable oxidants or can be a photoinduced transient oxidant) drives the catalytic splitting of water.
- the present invention uses rare earth ions, water or divalent manganese salts, permanganate and simple organic carboxylic acids as starting materials to synthesize a cluster with a core structure of [Mn 3 XO 2 ].
- the ligands are provided by nine carboxylate anions and three neutral carboxylic acid molecules, among which the valence states of the three manganese ions are +3, +3, +4 respectively.
- Such [Mn 3 XO 2 ] clusters containing mixed valence states and ligands provided entirely by carboxylic acids have not been reported before.
- the present invention uses rare earth ions, permanganate, divalent manganese ions (Mn 2+ ) and simple organic carboxylic acids as starting materials to successfully realize the use of simple metal ions (Mn 2+ , X 3+ ions), simple Organic carboxylic acid and MnO 4 - were used as starting materials, and the biomimetic core structure [Mn 4 XO 4 ] clusters were obtained through multi-step synthesis.
- [Mn 4 XO 4 ] cluster [Mn 3 XO 4 ] cubane and an outer Mn ion are connected by a ⁇ -O bridge to form a [Mn 4 XO 4 ] core structure, and the peripheral ligands are composed of eight A carboxylate anion R 1 CO 2 - , ligands L 1 and L 2 and an exchangeable ligand L 3 .
- the valence states of the four manganese ions are +3, +3, +4, +4 respectively.
- the present invention adopts the above-mentioned cluster compound having the structure of formula II to further react with water, successfully introduces ⁇ 2 -O bridges into the core, that is, two-coordinated oxygen bridges, and obtains a bionic core structure [Mn 4 XO 5 ] of clusters.
- peripheral ligands consist of eight carboxylate anions and two exchangeable ligands.
- the valence states of the four manganese ions are +3, +3, +4, +4 respectively.
- This kind of clusters not only successfully simulated the ten-atom core framework and coordination environment of biological OECs, but also simulated the oxidation-reduction characteristics of biological OECs. In particular, such clusters can be used as catalysts to stably catalyze water splitting reactions and release oxygen.
- Fig. 1 is a diagram of the crystal structure of cluster compound 1 prepared in Example 1 of the present invention.
- Fig. 2 is a diagram of the crystal structure of cluster compound 2 prepared in Example 2 of the present invention.
- Fig. 3 is a crystal structure diagram of cluster compound 3 prepared in Example 3 of the present invention.
- Fig. 4 is a crystal structure diagram of cluster compound 4 prepared in Example 4 of the present invention.
- Fig. 5 is a crystal structure diagram of cluster compound 5 prepared in Example 5 of the present invention.
- Fig. 6 is a crystal structure diagram of cluster compound 6 prepared in Example 6 of the present invention.
- Fig. 7 is a crystal structure diagram of cluster compound 7 prepared in Example 7 of the present invention.
- Fig. 8 is a crystal structure diagram of cluster compound 8 prepared in Example 8 of the present invention.
- Fig. 9 is a crystal structure diagram of cluster compound 9 prepared in Example 9 of the present invention.
- FIG. 10 is a diagram of the crystal structure of the cluster compound 10 prepared in Example 10 of the present invention.
- Fig. 11 is a crystal structure diagram of cluster compound 11 prepared in Example 11 of the present invention.
- Fig. 12 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 1, 2, 3, 4 and 5 in 1,2-dichloroethane.
- Fig. 13 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 6 and 8 in 1,2-dichloroethane.
- Fig. 14 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 9 and 11 in 1,2-dichloroethane.
- Fig. 15 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 6 in Example 13.
- Fig. 16 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 8 in Example 13.
- Fig. 17 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 9 in Example 13.
- Fig. 18 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 11 in Example 13.
- Fig. 19 is a graph showing the catalytic stability test of cluster compound 9 in Example 13.
- Fig. 20 is an oxygen test graph of cluster 9 in Example 13 catalyzed water splitting.
- Examples 1-11 in order to make the structural formulas of clusters 1-11 clear, the core skeleton and ligands are shown in the form of ball sticks and lines, respectively, and hydrogen atoms have been omitted.
- Example 1 Cluster 1, Mn 3 YO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- the preparation method is selected from any one of the following:
- cluster 1 The chemical structure of cluster 1 is shown in the following formula I-1, the specific parameters of its single crystal determination are shown in Table 1, and its crystal spatial structure is shown in Figure 1.
- Example 2 Cluster 2, Mn 3 LaO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- Example 2 The preparation method of Example 2 is the same as that of Method 2 in Example 1, except that lanthanum trifluoromethanesulfonate is used instead of yttrium trifluoromethanesulfonate.
- the yield was about 31% (based on the moles of La ions).
- cluster 2 The chemical structure of cluster 2 is shown in the following formula I-2, the specific parameters of its single crystal determination are shown in Table 2, and its crystal spatial structure is shown in Figure 2.
- Example 3 Cluster 3, Mn 3 GdO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- Example 3 The preparation method of Example 3 is the same as that of Method 2 in Example 1, except that gadolinium trifluoromethanesulfonate (Gd(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate.
- Gd(CF 3 SO 3 ) 3 gadolinium trifluoromethanesulfonate
- the yield was about 48% (based on moles of Gd ions).
- the chemical structure of the cluster compound 3 is shown in the following formula I-3, the specific parameters of its single crystal determination are shown in Table 3, and its crystal spatial structure is shown in Figure 3.
- Example 4 Cluster 4, Mn 3 DyO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- Example 4 The preparation method of Example 4 is the same as that of Method 2 in Example 1, except that dysprosium trifluoromethanesulfonate (Dy(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate.
- the yield was about 43% (based on moles of Dy ions).
- cluster 4 The chemical structure of cluster 4 is shown in the following formula I-4, the specific parameters of its single crystal determination are shown in Table 4, and its crystal spatial structure is shown in Figure 4.
- Example 5 Cluster 5, Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- Example 5 The preparation method of Example 5 is the same as that of Method 2 in Example 1, except that lutetium trifluoromethanesulfonate (Lu(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate.
- the yield was about 48% (based on the moles of Lu ions).
- the chemical formula is Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
- the molecular formula is: C 60 H 111 LuMn 3 O 26 .
- cluster 5 The chemical structure of cluster 5 is shown in the following formula I-5, the specific parameters of its single crystal determination are shown in Table 5, and its crystal spatial structure is shown in Figure 5.
- Example 6 Cluster 6, Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
- the preparation method is as follows:
- tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 4 mmol)
- yttrium trifluoromethanesulfonate (Y(CF 3 SO 3 ) 3 , 1 mmol)
- acetylacetone was added to a 100 ml round bottom flask.
- the obtained intermediate was dissolved in dichloromethane and acetonitrile (1:2 volume ratio), and then 1% isoquinoline was added to the total volume, and brown crystals were precipitated after a few days. The resulting crystals were collected, washed with n-hexane, and dried in vacuo in ⁇ 19% yield (based on moles of Y ions).
- cluster compound 6 The chemical structure of cluster compound 6 is shown in the following formula II-1, the specific parameters of its single crystal determination are shown in Table 6, and its crystal spatial structure is shown in Figure 6.
- Example 7 Cluster 7, Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
- the preparation method is as follows:
- tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 8 mmol)
- gadolinium trifluoromethanesulfonate (Gd(CF 3 SO 3 ) 3 , 2 mmol)
- acetylacetonate were added to a 100 ml round bottom flask.
- the obtained intermediate was dissolved in dichloromethane and acetonitrile (volume ratio 1:2), and then 1% isoquinoline by volume ratio was added, and brown crystals were precipitated after a few days.
- cluster 7 the chemical formula is Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), and the molecular formula is: C 54 H 88 GdMn 4 NO 22 .
- cluster 7 The chemical structure of cluster 7 is shown in the following formula II-2, the specific parameters of its single crystal determination are shown in Table 7, and its crystal spatial structure is shown in Figure 7.
- Example 8 Cluster 8, Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
- Example 8 The preparation method of cluster 8 in Example 8 is the same as that in Example 6, except that lutetium trifluoromethanesulfonate (Lu(CF 3 SO 3 )) is used instead of yttrium trifluoromethanesulfonate in Example 6.
- lutetium trifluoromethanesulfonate Li(CF 3 SO 3 )
- cluster 8 the chemical formula is Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), and the molecular formula is: C 54 H 88 LuMn 4 NO 22 .
- cluster 8 The chemical structure of cluster 8 is shown in the following formula II-3, the specific parameters of its single crystal determination are shown in Table 8, and its crystal spatial structure is shown in Figure 8.
- Example 9 Cluster 9, Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
- the preparation method is as follows:
- cluster 9 The chemical structure of cluster 9 is shown in the following formula III-1, the specific parameters of its single crystal determination are shown in Table 9, and its crystal spatial structure is shown in Figure 9.
- Example 10 Cluster 10, Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
- the preparation method is as follows:
- Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 is similar to that of Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 , It is only necessary to replace yttrium trifluoromethanesulfonate in the synthetic raw materials with dysprosium trifluoromethanesulfonate (Dy(CF 3 SO 3 ) 3 ).
- cluster 10 the chemical formula is Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 .
- the chemical structure of the cluster compound 10 is shown in the following formula III-2, the specific parameters of its single crystal determination are shown in Table 10, and its crystal spatial structure is shown in Figure 10.
- Example 11 Cluster 11, Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
- the preparation method is as follows:
- Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 is similar to that of Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 , It is only necessary to replace the yttrium triflate in the starting material with lutetium triflate. Brown crystals precipitated out after a few days. The resulting crystals were collected, washed with n-hexane, and dried in vacuo in ⁇ 39% yield (based on moles of Lu ions).
- Cluster 11 the chemical formula is Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 is tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
- cluster 11 the chemical formula is Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 ⁇ (C 2 H 5 NO) 0.5 (Note: N,N-dimethyl acetamide solvent molecule), molecular formula: H 95.5 C 50 N 2.5 O 23.5 Mn 4 Lu. Elemental Analysis Theoretical value (%): C, 39.99; H, 6.41; N, 2.33; Experimental value (%): C, 40.08; H, 6.39; N, 2.33.
- cluster 11 The chemical structure of cluster 11 is shown in formula III-3, the specific parameters of its single crystal determination are shown in Table 11, and its crystal spatial structure is shown in Figure 11.
- Example 13 Determination of oxygen release by catalytic water splitting of clusters 6, 8, 9 and 11 on the electrode surface
- the test adopts a three-electrode device, wherein the working electrode is an ITO-nanoITO electrode that adsorbs clusters, the counter electrode is a platinum mesh electrode, and the reference electrode is a silver/silver nitrate electrode (the reference solution is 10mM AgNO 3 and 100mM LiClO 4 acetonitrile solution).
- the electrolyte was a propylene carbonate solution containing 100 mM LiClO 4 and 1.2 M water (H 2 O).
- the scanning speed is 10mV/s.
- Figures 15, 16, 17, and 18 correspond to the catalytic water splitting currents generated by the working electrodes of adsorbed clusters 6, 8, 9, and 11, respectively, while no significant catalytic current was observed in the unadsorbed clusters.
- the electrolytic cell used is an H-type electrolytic cell, and the two chambers are separated by an anion exchange membrane.
- the measured current-time curve is shown in Figure 19, indicating that the cluster compound with the core structure [Mn 4 YO 5 ] prepared in Example 9 can be stably catalyzed in the above electrolyte for more than 10 hours, and has excellent catalytic stability sex.
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Abstract
A rare earth ion-containing bionic water cracking catalyst, and a preparation method therefor and the use thereof. The catalyst contains a [MnnXOm] cluster, wherein n is 3 or 4, m is 2, 4 or 5, and the cluster is a rare earth manganese heteronuclear metal cluster, which contains a rare earth ion X and one of following core structures: a [Mn3XO2] heteronuclear metal cluster skeleton core, a [Mn4XO4] heteronuclear metal cluster skeleton core and a [Mn4XO5] heteronuclear metal cluster skeleton core, and X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. The manganese ion valence state of the clusters is +3 or +4, and the clusters are of great value in the aspect of magnetic materials. In addition, [Mn4XO4] and [Mn4XO5] clusters can be used as an artificial water cracking catalyst to drive the catalytic cracking of water on the surface of an electrode or by means of an oxidant.
Description
本发明涉及一种含稀土离子的仿生水裂解催化剂及其制备方法和应用，属于催化剂技术领域。The invention relates to a biomimetic water splitting catalyst containing rare earth ions, a preparation method and application thereof, and belongs to the technical field of catalysts.
能源危机和环境污染问题是二十一世纪制约人类社会持续发展的两个关键问题。如果能利用取之不尽、用之不竭的太阳能裂解地球上丰富的水，释放出氧气，获得电子、质子，产生电能或氢能，则可从根本上解决人类所面临的能源危机和环境污染问题。但水是热力学非常稳定的物质，要实现它的高效、安全裂解必须有合适的催化剂。最近，现有技术中研究者利用钌、铱等贵金属和一些复杂配体作用合成出具有水裂解功能的人工催化剂,但贵金属和复杂配体的使用导致这些催化剂的制备成本高，且易造成环境污染，所以难以被推广应用。如何制备高效、稳定、廉价、环保型的水裂解催化剂尚是一个未解的科学难题。Energy crisis and environmental pollution are two key issues restricting the sustainable development of human society in the 21st century. If the inexhaustible and inexhaustible solar energy can be used to crack the abundant water on the earth, release oxygen, obtain electrons and protons, and generate electric energy or hydrogen energy, it can fundamentally solve the energy crisis and environmental problems faced by human beings. pollution problem. But water is a thermodynamically very stable substance, to achieve its efficient and safe cracking must have a suitable catalyst. Recently, researchers in the prior art synthesized artificial catalysts with water splitting function by using noble metals such as ruthenium and iridium and some complex ligands. pollution, so it is difficult to be popularized and applied. How to prepare efficient, stable, cheap, and environmentally friendly water splitting catalysts is still an unsolved scientific problem.
光合生物的光系统II是自然界唯一能够高效、安全利用廉价金属离子实现水裂解，并获得电子、质子，同时释放出氧气的生物系统。光系统II之所以能够高效、安全裂解水是因为拥有一个独特的[Mn
4CaO
5]异核金属簇合物生物催化剂，其外周由六个羧基、一个咪唑环和四个水分子提供配体。水裂解过程中，生物催化剂经历五种不同状态(S
0,S
1,S
2,S
3,S
4)；其中，S
1态是黑暗稳定状态，四个锰离子的价态对应为(+3，+3，+4，+4)。光合生物水裂解催化中心结构的揭示为发展高效、稳定、廉价、环保型的仿生水裂解催化剂提供了理想的蓝图。
The photosystem II of photosynthetic organisms is the only biological system in nature that can efficiently and safely use cheap metal ions to split water, obtain electrons and protons, and release oxygen at the same time. The reason why Photosystem II can efficiently and safely split water is that it has a unique [Mn 4 CaO 5 ] heteronuclear metal cluster biocatalyst, whose periphery is provided by six carboxyl groups, an imidazole ring and four water molecules to provide ligands . During water splitting, the biocatalyst undergoes five different states (S 0 , S 1 , S 2 , S 3 , S 4 ); among them, the S 1 state is a dark stable state, and the valence states of the four manganese ions correspond to (+ 3, +3, +4, +4). The revelation of the structure of photosynthetic biological water-splitting catalytic center provides an ideal blueprint for the development of efficient, stable, cheap, and environmentally friendly biomimetic water-splitting catalysts.
如何化学合成类似于生物水裂解催化中心是一个重要科学前沿，同时也是极有挑战的科学难题。专利ZL201510065238.7公开了一种含有[Mn
4CaO
4]核心结构的水裂解催化剂，其制备方法及其应用；专利ZL201711059799.1公开了一种含有[Mn
3SrO
4]和[Mn
4SrO
4]核心结构的簇合物及其制备方法和应用。这两个专利分别保护了如下所示的结构式：
How to chemically synthesize a catalytic center similar to biological water splitting is an important scientific frontier and also a very challenging scientific problem. Patent ZL201510065238.7 discloses a water splitting catalyst containing [Mn 4 CaO 4 ] core structure, its preparation method and its application; patent ZL201711059799.1 discloses a catalyst containing [Mn 3 SrO 4 ] and [Mn 4 SrO 4 ] Clusters with core structure and their preparation methods and applications. These two patents respectively protect the structural formula shown below:
式1和式2中，R
1选自H或C
1-8直链或支链烷基；L
1、L
2、L
3、L
4为四个相同或不同配体，各自独立地选自羧酸分子及其衍生物，吡啶、咪唑、吡嗪、喹啉、异喹啉及它们的衍生物，或者是水分子、醇分子、酮类、腈类(如乙腈)、酯类等可以交换的小分子。
In formula 1 and formula 2, R 1 is selected from H or C 1-8 linear or branched chain alkyl; L 1 , L 2 , L 3 , L 4 are four identical or different ligands, each independently selected from Carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their derivatives, or water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters, etc. can be exchanged of small molecules.
上述两种含碱土金属离子的合成[Mn
4CaO
4]和[Mn
4SrO
4]簇合物是迄今为止与生物水裂解催化中心最为类似的仿生簇合物，但仿生簇合物的稳定性有待进一步提升。
The above two synthetic [Mn 4 CaO 4 ] and [Mn 4 SrO 4 ] clusters containing alkaline earth metal ions are biomimetic clusters most similar to biological water splitting catalytic centers so far, but the stability of biomimetic clusters To be further improved.
发明内容Contents of the invention
为了改善上述技术问题，本发明将稀土离子X(例如选自钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、 铽、镝、钬、铒、铥、镱和镥中的至少一种)引入到合成催化剂中，提供了三类核心结构为[Mn
3XO
2]、[Mn
4XO
4]和[Mn
4XO
5]的稀土锰异核金属簇合物及其制备方法和应用。
In order to improve the above-mentioned technical problems, the present invention uses rare earth ions X (such as selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) At least one of ) is introduced into the synthesis catalyst, providing three types of rare earth manganese heteronuclear metal clusters with core structures of [Mn 3 XO 2 ], [Mn 4 XO 4 ] and [Mn 4 XO 5 ] and their preparation methods and applications.
本发明是通过如下技术方案实现：The present invention is realized through the following technical solutions:
一种稀土锰异核金属簇合物，其具有[Mn
nXO
m]异核金属簇骨架核心，其中，n为3或4；m为2，4或5；X选自稀土元素。
A rare earth manganese heteronuclear metal cluster compound, which has a [Mn n XO m ] heteronuclear metal cluster skeleton core, wherein, n is 3 or 4; m is 2, 4 or 5; X is selected from rare earth elements.
根据本发明的一个具体实施方式，所述稀土锰异核金属簇合物具有下述核心结构中的一种：[Mn
3XO
2]异核金属簇骨架核心、[Mn
4XO
4]异核金属簇骨架核心和[Mn
4XO
5]异核金属簇骨架核心，所述X选自稀土元素。
According to a specific embodiment of the present invention, the rare earth manganese heteronuclear metal cluster has one of the following core structures: [Mn 3 XO 2 ] heteronuclear metal cluster skeleton core, [Mn 4 XO 4 ] heteronuclear Metal cluster skeleton core and [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core, wherein X is selected from rare earth elements.
根据本发明，所述X选自钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥。According to the invention, said X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
根据本发明的一个具体实施方式，所述簇合物的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3，具有如式I所示结构，其含有一个稀土离子X和三个Mn离子，它们通过2个μ
3-O桥连接成[Mn
3XO
2]异核金属簇骨架核心；
According to a specific embodiment of the present invention, the chemical formula of the cluster is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , which has a structure as shown in Formula I, which contains a rare earth ion X and three Mn ions, which are connected by two μ 3 -O bridges to form the [Mn 3 XO 2 ] heteronuclear metal cluster skeleton core;
[Mn
3XO
2]异核金属簇骨架核心的外围配体由九个羧酸根阴离子R
1CO
2
-和三个中性羧酸配体R
1CO
2H提供，其中三个Mn离子的价态分别是+3，+3，+4价，整个簇合物呈电中性；
The peripheral ligands of the [Mn 3 XO 2 ] heteronuclear metal cluster framework core are provided by nine carboxylate anions R 1 CO 2 - and three neutral carboxylic acid ligands R 1 CO 2 H, of which the valence of three Mn ions The states are +3, +3, +4 respectively, and the whole cluster is electrically neutral;
其中，X选自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu；Wherein, X is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
R
1相同或不同、彼此独立地选自H或C
1-8直链或支链烷基。
R 1 are the same or different, independently selected from H or C 1-8 straight or branched chain alkyl.
根据本发明，羧酸根阴离子R
1CO
2
-可以为甲酸根、乙酸根、丙酸根、异丙酸根、丁酸根、异丁酸根、叔丁酸根、戊酸根、异戊酸根、特戊酸根、己酸根等中的至少一种。即，R
1可以为氢(H)、甲基(-CH
3)、乙基(-C
2H
5)、正丙基(-CH
2CH
2CH
3)、异丙基(-CH(CH
3)
2)、正丁基(-(CH
2)
3CH
3)、异丁基(-CH(CH
3)C
2H
5)、叔丁基(-C(CH
3)
3)、正戊基(-(CH
2)
4CH
3)、异戊基(-CH
2CH
2CH(CH
3)
2)、特戊基(-CH
2C(CH
3)
3)或正己基(-(CH
2)
5CH
3)等中的一种。
According to the invention, the carboxylate anion R 1 CO 2 - may be formate, acetate, propionate, isopropionate, butyrate, isobutyrate, tert-butyrate, valerate, isovalerate, pivalate At least one of acid radical, hexanoic acid radical and the like. That is, R 1 can be hydrogen (H), methyl (-CH 3 ), ethyl (-C 2 H 5 ), n-propyl (-CH 2 CH 2 CH 3 ), isopropyl (-CH(CH 3 ) 2 ), n-butyl (-(CH 2 ) 3 CH 3 ), isobutyl (-CH(CH 3 )C 2 H 5 ), tert-butyl (-C(CH 3 ) 3 ), n-pentyl (-(CH 2 ) 4 CH 3 ), isopentyl (-CH 2 CH 2 CH(CH 3 ) 2 ), pentyl (-CH 2 C(CH 3 ) 3 ) or n-hexyl (-(CH 2 ) One of 5 CH 3 ) and the like.
根据本发明，R
1CO
2H可以为甲酸、乙酸、丙酸、异丙酸、丁酸、异丁酸、叔丁酸、戊酸、异戊酸、特戊酸、己酸等中的至少一种。
According to the present invention, R 1 CO 2 H may be at least A sort of.
优选地，具有如式I所示结构的簇合物选自如下簇合物1～簇合物5中的任一簇合物：Preferably, the cluster compound having the structure shown in formula I is selected from any cluster compound in the following cluster compounds 1 to 5:
簇合物1，化学式为Mn
3YO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 1, the chemical formula is Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 = tert-butyl.
优选地，簇合物1为单晶；其结构如式I-1所示：Preferably, the cluster compound 1 is a single crystal; its structure is shown in formula I-1:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.526(3)°，β＝87.004(2)°，γ＝65.818(3)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.526(3)°, β=87.004(2)°, γ=65.818(3)°, Z=2, the volume is
簇合物2，化学式为Mn
3LaO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 2, the chemical formula is Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 = tert-butyl.
优选地，簇合物2为单晶；其结构如式I-2所示：Preferably, the cluster compound 2 is a single crystal; its structure is shown in formula I-2:
其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90°，β＝107.516(4)°，γ＝90°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90°, β=107.516(4)°, γ=90°, Z=4, the volume is
簇合物3，化学式为Mn
3GdO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 3, the chemical formula is Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
优选地，簇合物3为单晶；其结构如式I-3所示：Preferably, the cluster compound 3 is a single crystal; its structure is shown in formula I-3:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.898(2)°，β＝87.087(2)°，γ＝65.755(2)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.898(2)°, β=87.087(2)°, γ=65.755(2)°, Z=2, the volume is
簇合物4，化学式为Mn
3DyO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 4, the chemical formula is Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
优选地，簇合物4为单晶；其结构如式I-4所示：Preferably, the cluster compound 4 is a single crystal; its structure is shown in formula I-4:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.790(2)°，β＝86.995(2)°，γ＝65.678(2)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.790(2)°, β=86.995(2)°, γ=65.678(2)°, Z=2, the volume is
簇合物5，化学式为Mn
3LuO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 5, the chemical formula is Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
优选地，簇合物5为单晶；其结构如式I-5所示：Preferably, the cluster compound 5 is a single crystal; its structure is shown in formula I-5:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.450(3)°，β＝87.291(3)°，γ＝65.954(3)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.450(3)°, β=87.291(3)°, γ=65.954(3)°, Z=2, the volume is
根据本发明的一个具体实施方式，所述簇合物的化学式为Mn
4XO
4(R
1CO
2)
8(L
1)(L
2)(L
3)，具有如式II所示结构，其含有四个Mn离子和一个稀土离子X，它们通过四个μ-O桥连接成[Mn
4XO
4]异核金属簇骨架核心；
According to a specific embodiment of the present invention, the chemical formula of the cluster is Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), which has a structure as shown in formula II, which Containing four Mn ions and one rare earth ion X, they are connected into [Mn 4 XO 4 ] heteronuclear metal cluster skeleton core through four μ-O bridges;
[Mn
4XO
4]异核金属簇骨架核心的外围配体由八个羧酸根阴离子R
1CO
2
-和三个配体L
1、L
2和L
3提供；其中四个Mn离子的价态分别是+3，+3，+4，+4。
The peripheral ligands of the [Mn 4 XO 4 ] heteronuclear metal cluster framework core are provided by eight carboxylate anions R 1 CO 2 - and three ligands L 1 , L 2 and L 3 ; the valence states of four Mn ions They are +3, +3, +4, +4 respectively.
式II中，稀土离子X、R
1具有如上含义；
In formula II, the rare earth ion X, R have the above meanings;
L
1、L
2相同或不同，各自独立地选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物，或者L
1和L
2连接为一个双齿螯合配体；
L 1 and L 2 are the same or different, each independently selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, Ethers, ketones, nitriles, esters, amides and their respective derivatives, or L1 and L2 are connected as a bidentate chelating ligand;
L
3选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物。
L3 is selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters , amides and their respective derivatives.
根据本发明，式II中，L
1和L
2优选连接为特戊酸根，L
3优选为异喹啉。
According to the present invention, in formula II, L 1 and L 2 are preferably connected as pivalate, and L 3 is preferably isoquinoline.
根据本发明，所述腈类例如可以为乙腈。所述酯类例如为乙酸乙酯；所述酰胺类例如为N-甲基甲酰胺、N-甲基乙酰胺、N,N-二甲基甲酰胺和N，N-二甲基乙酰胺中的一种。According to the present invention, the nitriles may be, for example, acetonitrile. The esters are, for example, ethyl acetate; the amides are, for example, N-methylformamide, N-methylacetamide, N,N-dimethylformamide and N,N-dimethylacetamide kind of.
根据本发明，具有式II所示结构的簇合物选自如下簇合物6～簇合物8中的任一簇合物：According to the present invention, the cluster compound having the structure shown in formula II is selected from any cluster compound in the following cluster compounds 6 to 8:
簇合物6，化学式为Mn
4YO
4(R
1CO
2)
8(L
1)(L
2)(L
3)，其中，R
1＝叔丁基，L
1和L
2连接后为特戊酸根(例如三甲基乙酸根，即式II-1中R
2为叔丁基)，L
3＝异喹啉。
Cluster 6, the chemical formula is Mn 4 YO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, and L 1 and L 2 are connected to be pentyl Acid group (such as trimethyl acetate, ie R 2 in formula II-1 is tert-butyl), L 3 = isoquinoline.
优选地，所述簇合物6为单晶；其结构如式II-1所示：Preferably, the cluster compound 6 is a single crystal; its structure is shown in formula II-1:
其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.6590(10)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.6590(10)°, γ=90.00°, Z=4, the volume is
簇合物7，化学式为Mn
4GdO
4(R
1CO
2)
8(L
1)(L
2)(L
3)，其中，R
1＝叔丁基，L
1和L
2连接后为特戊酸根(例如三甲基乙酸根，即式II-2中R
2为叔丁基)，L
3＝异喹啉。
Cluster 7, the chemical formula is Mn 4 GdO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, and L 1 and L 2 are connected to be pentyl Acid group (such as trimethyl acetate, ie R 2 in formula II-2 is tert-butyl), L 3 = isoquinoline.
优选地，所述簇合物7为单晶；其结构如式II-2所示：Preferably, the cluster compound 7 is a single crystal; its structure is shown in formula II-2:
其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.799(2)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.799(2)°, γ=90.00°, Z=4, the volume is
簇合物8，化学式为Mn
4LuO
4(R
1CO
2)
8(L
1)(L
2)(L
3)，其中，R
1＝叔丁基，L
1和L
2连接后为特戊酸根(例如三甲基乙酸根，即式II-3中R
2为叔丁基)，L
3＝异喹啉。
Cluster 8, the chemical formula is Mn 4 LuO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, L 1 and L 2 are connected to be pentyl Acid group (such as trimethyl acetate, ie R 2 in formula II-3 is tert-butyl), L 3 = isoquinoline.
优选地，所述簇合物8为单晶；其结构如式II-3所示：Preferably, the cluster compound 8 is a single crystal; its structure is shown in formula II-3:
其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.7670(10)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.7670(10)°, γ=90.00°, Z=4, the volume is
根据本发明的一个具体实施方式，所述簇合物的化学式为Mn
4XO
5H(R
1CO
2)
8(L
4)(L
5)，具有式III所示结构，其含有四个Mn离子和一个稀土离子，它们通过五个μ-O连接成[Mn
4XO
5]异核金属簇骨架核心；[Mn
4XO
5]异核金属簇骨架核心的外围配体由八个羧酸根阴离子R
1CO
2
-和两个配体L
4和L
5提供；[Mn
4XO
5]异核金属簇骨架核心存在一个μ
2-O桥；四个锰离子的价态为+3，+3，+4，+4；
According to a specific embodiment of the present invention, the chemical formula of the cluster is Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), which has a structure shown in formula III, which contains four Mn ions and a rare earth ion, they are connected by five μ-O to form the [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core; the peripheral ligands of the [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core are composed of eight carboxylate anions Provided by R 1 CO 2 - and two ligands L 4 and L 5 ; [Mn 4 XO 5 ] there is a μ 2 -O bridge in the core of the heteronuclear metal cluster framework; the valence states of the four manganese ions are +3, +3 , +4, +4;
式III中，稀土离子X、R
1具有如上含义；L
4和L
5相同或不同，彼此独立地选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物，或者L
4和L
5连接为一个双齿螯合配体。
In formula III, the rare earth ion X and R have the above meanings; L and L are the same or different, and are independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and Their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and their respective derivatives, or L4 and L5 linked as a bidentate chelating ligand .
根据本发明，式III中，L
4、L
5相同或不同、彼此独立地选自N,N-二甲基乙酰胺，N,N-二甲基甲酰胺，N-甲基甲酰胺中的一种。
According to the present invention, in formula III, L 4 and L 5 are the same or different, independently selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methylformamide A sort of.
优选地，具有式III所示结构的簇合物选自如下簇合物9～簇合物11中任一簇合物：Preferably, the cluster compound having the structure shown in formula III is selected from any one of the following cluster compounds 9 to 11:
簇合物9，化学式为Mn
4YO
5H(RCO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 9, the chemical formula is Mn 4 YO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
优选地，所述簇合物9为单晶；其结构如式III-1所示：Preferably, the cluster compound 9 is a single crystal; its structure is shown in formula III-1:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
簇合物10，化学式为Mn
4DyO
5H(RCO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 10, the chemical formula is Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
优选地，所述簇合物10为单晶；其结构如式III-2所示：Preferably, the cluster compound 10 is a single crystal; its structure is shown in formula III-2:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
簇合物11，化学式为Mn
4LuO
5H(RCO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 11, the chemical formula is Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
优选地，所述簇合物11为单晶；其结构如式III-3所示：Preferably, the cluster compound 11 is a single crystal; its structure is shown in formula III-3:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
本发明还提供一种所述稀土锰异核金属簇合物的制备方法，所述方法包括如下步骤：将高锰酸根阴离子型氧化剂、稀土盐和配体，任选地加入水或二价锰盐，在溶液中反应，制备得到所述簇合物。The present invention also provides a method for preparing the rare earth manganese heteronuclear metal cluster, the method comprising the following steps: adding permanganate anion oxidant, rare earth salt and ligand, optionally adding water or divalent manganese salt, and react in solution to prepare the cluster.
在一个具体实施方式中，本发明提供一种具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物的制备方法，所述方法包括如下步骤：
In a specific embodiment, the present invention provides a method for preparing a cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I, said The method includes the following steps:
将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐，任选地加入水或二价锰盐，在乙腈溶液中反应，制备得到所述簇合物。
The cluster compound is prepared by reacting organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt, optionally adding water or divalent manganese salt in an acetonitrile solution.
根据本发明，所述方法具体包括：将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐和水，在乙腈溶液中反应，制备得到具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物。
According to the present invention, the method specifically includes: reacting organic carboxylic acid R 1 COOH, permanganate anion-type oxidizing agent, rare earth salt and water in an acetonitrile solution to prepare the chemical formula Mn 3 XO having the structure shown in formula I 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 clusters.
根据本发明，所述方法具体包括：将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐和二价锰盐，在乙腈溶液中反应，制备得到具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物。
According to the present invention, the method specifically includes: reacting organic carboxylic acid R 1 COOH, permanganate anion-type oxidizing agent, rare earth salt and divalent manganese salt in an acetonitrile solution to prepare a chemical formula having the structure shown in formula I: Clusters of Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 .
根据本发明，所述有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐、水或二价锰盐的摩尔比为(10～120):(1～10):1:(0～5)；优选为(20～120):(2～8):1:(1～2)。
According to the present invention, the molar ratio of the organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt, water or divalent manganese salt is (10～120):(1～10):1:(0～ 5); preferably (20-120):(2-8):1:(1-2).
根据本发明，所述有机羧酸R
1COOH例如选自甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、特戊酸、己酸等羧酸及其衍生物中的至少一种，优选为异丁酸或特戊酸。
According to the present invention, the organic carboxylic acid R 1 COOH is, for example, selected from carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and their derivatives At least one of, preferably isobutyric acid or pivalic acid.
根据本发明，所述高锰酸根阴离子型氧化剂例如为四丁基高锰酸铵((C
4H
9)
4N·MnO
4)。
According to the present invention, the permanganate anionic oxidizing agent is, for example, tetrabutylammonium permanganate ((C 4 H 9 ) 4 N·MnO 4 ).
根据本发明，所述稀土盐可以是稀土离子的三氟甲磺酸盐、硝酸盐、高氯酸盐和羧酸盐等中的至少一种，或者所述稀土盐中还包含有结晶水；其中稀土离子的羧酸盐中含有羧酸根阴离子(R
1CO
2
-)，羧酸根阴离子具有前述的定义。
According to the present invention, the rare earth salt can be at least one of trifluoromethanesulfonate, nitrate, perchlorate and carboxylate of rare earth ions, or the rare earth salt also contains crystal water; The carboxylate of the rare earth ion contains carboxylate anion (R 1 CO 2 - ), and the carboxylate anion has the aforementioned definition.
根据本发明，所述二价锰盐具有如下结构式：MnA
2·tH
2O；其中，A选自羧酸根阴离子(R
1CO
2
-)、氯离子、ClO
4
-、NO
3
-、CF
3SO
3
-、乙酰丙酮根，羧酸根阴离子具有如前所述的含义；t为0～6，优选为1～5，更优选为2～4。
According to the present invention, the divalent manganese salt has the following structural formula: MnA 2 ·tH 2 O; wherein, A is selected from carboxylate anion (R 1 CO 2 - ), chloride ion, ClO 4 - , NO 3 - , CF 3 SO 3 − , acetylacetonate, and carboxylate anions have the meanings described above; t is 0-6, preferably 1-5, and more preferably 2-4.
例如，所述二价锰盐选自Mn(ClO
4)
2，MnCl
2，Mn(NO
3)
2，Mn(CF
3SO
3)
2、乙酰丙酮锰、或者其各自的含有结晶水的锰盐中的至少一种。
For example, the divalent manganese salt is selected from Mn(ClO 4 ) 2 , MnCl 2 , Mn(NO 3 ) 2 , Mn(CF 3 SO 3 ) 2 , manganese acetylacetonate, or their respective manganese salts containing water of crystallization at least one of the
根据本发明，每毫摩尔稀土盐用乙腈为60～100毫升。According to the present invention, 60-100 milliliters of acetonitrile is used for every millimole of rare earth salt.
本发明人发现，具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物的制备方法只能在乙腈溶剂中进行，在醇或其它有机溶剂中均无法获得目标簇合物。
The present inventors found that the preparation method of the cluster compound with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I can only be carried out in acetonitrile solvent, and in alcohol Or other organic solvents can not obtain the target clusters.
根据本发明，所述反应温度为60℃～90℃。例如可以为60℃、70℃、80℃、90℃。According to the present invention, the reaction temperature is 60°C to 90°C. For example, it may be 60°C, 70°C, 80°C, or 90°C.
根据本发明，所述反应时间可以为10～60分钟。According to the present invention, the reaction time may be 10-60 minutes.
根据本发明，所述反应还包括后处理步骤：将反应产物过滤除去沉淀，静止液体后，得到纯化的具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物。
According to the present invention, the reaction further includes a post-treatment step: filter the reaction product to remove the precipitate, and after the liquid is static, the purified chemical formula with the structure shown in formula I is obtained as Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 Clusters of CO 2 H) 3 .
示例性地，静止时间例如为1～7天。Exemplarily, the resting time is, for example, 1 to 7 days.
作为本发明的一种优选实施方案，所述具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物的制备方法具体步骤为：
As a preferred embodiment of the present invention, the specific steps of the preparation method of the cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I are as follows: :
将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐和水，按照摩尔比为(10～120):(1～10):1:(0～5)在乙腈溶液中反应10～60分钟，得到棕色溶液，过滤除去沉淀；静置1～7天得到黑色晶体，即为具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物。
The organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt and water are reacted in the acetonitrile solution for 10~ After 60 minutes, a brown solution was obtained, and the precipitate was removed by filtration; standing for 1 to 7 days to obtain a black crystal, that is, the chemical formula having the structure shown in formula I was Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 clusters.
作为本发明的一种优选实施方案，所述具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物的制备方法具体步骤为：
As a preferred embodiment of the present invention, the specific steps of the preparation method of the cluster with the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 having the structure shown in formula I are as follows: :
将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、稀土盐和二价锰盐，按照摩尔比为(10～120):(1～10):1:(0～5)在乙腈溶液中反应10～60分钟，得到棕色溶液，过滤除去沉淀；静置得到黑色晶体，即为具有式I所示结构的化学式为Mn
3XO
2(R
1CO
2)
9(R
1CO
2H)
3的簇合物。
Put organic carboxylic acid R 1 COOH, permanganate anion oxidant, rare earth salt and divalent manganese salt in the acetonitrile solution according to the molar ratio of (10~120):(1~10):1:(0~5) React for 10-60 minutes to obtain a brown solution, filter to remove the precipitate; stand still to obtain black crystals, that is, the chemical formula with the structure shown in Formula I is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 of clusters.
根据本发明的优选技术方案，簇合物1的分子式为C
60H
111Mn
3O
26Y，化学式为Mn
3YO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of cluster 1 is C 60 H 111 Mn 3 O 26 Y, and the chemical formula is Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl.
簇合物1为单晶；其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.526(3)°，β＝87.004(2)°，γ＝65.818(3)°，Z＝2，体积为
其结构如式I-1所示，晶体结构见图1，单晶参数如表1所示。
Cluster 1 is a single crystal; the single crystal belongs to the triclinic system, the space group is P-1, and the unit cell parameters are α=77.526(3)°, β=87.004(2)°, γ=65.818(3)°, Z=2, the volume is Its structure is shown in Formula I-1, the crystal structure is shown in Figure 1, and the single crystal parameters are shown in Table 1.
表1：簇合物1的单晶参数Table 1: Single crystal parameters of cluster 1
根据本发明的优选技术方案，簇合物2的分子式为C
60H
111LaMn
3O
26，化学式为Mn
3LaO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 2 is C 60 H 111 LaMn 3 O 26 , and the chemical formula is Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl.
簇合物2为单晶；其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90°，β＝107.516(4)°，γ＝90°，Z＝4，体积为
其结构如式I-2所示，晶体结构见图2，单晶参数如表2所示。
Cluster 2 is a single crystal; the single crystal belongs to the monoclinic system, the space group is P2 1 /n, and the unit cell parameters are α=90°, β=107.516(4)°, γ=90°, Z=4, the volume is Its structure is shown in Formula I-2, the crystal structure is shown in Figure 2, and the single crystal parameters are shown in Table 2.
表2：簇合物2的单晶参数Table 2: Single crystal parameters of cluster 2
根据本发明的优选技术方案，簇合物3的分子式为C
60H
111GdMn
3O
26，化学式为Mn
3GdO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 3 is C 60 H 111 GdMn 3 O 26 , and the chemical formula is Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl.
簇合物3为单晶；其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.898(2)°，β＝87.087(2)°，γ＝65.755(2)°，Z＝2，体积为
其结构如式I-3所示，晶体结构见图3，单晶参数如表3所示。
Cluster 3 is a single crystal; the single crystal belongs to the triclinic system, the space group is P-1, and the unit cell parameters are α=77.898(2)°, β=87.087(2)°, γ=65.755(2)°, Z=2, the volume is Its structure is shown in Formula I-3, the crystal structure is shown in Figure 3, and the single crystal parameters are shown in Table 3.
表3：簇合物3的单晶参数Table 3: Single crystal parameters of cluster 3
根据本发明的优选技术方案，簇合物4的分子式为C
60H
111DyMn
3O
26，化学式为Mn
3DyO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 4 is C 60 H 111 DyMn 3 O 26 , and the chemical formula is Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl.
簇合物4为单晶；其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.790(2)°，β＝86.995(2)°，γ＝65.678(2)°，Z＝2，体积为
其结构如式I-4所示，晶体结构见图4，单晶参数如表4所示。
Cluster 4 is a single crystal; the single crystal belongs to the triclinic system, the space group is P-1, and the unit cell parameters are α=77.790(2)°, β=86.995(2)°, γ=65.678(2)°, Z=2, the volume is Its structure is shown in Formula I-4, the crystal structure is shown in Figure 4, and the single crystal parameters are shown in Table 4.
表4：簇合物4的单晶参数Table 4: Single crystal parameters of cluster 4
根据本发明的优选技术方案，簇合物5的分子式为C
60H
111LuMn
3O
26，化学式为Mn
3LuO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 5 is C 60 H 111 LuMn 3 O 26 , and the chemical formula is Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl.
簇合物5为单晶；其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.450(3)°，β＝87.291(3)°，γ＝65.954(3)°，Z＝2，体积为
其结构如式I-5所示，晶体结构见图5，单晶参数如表5所示。
Cluster 5 is a single crystal; the single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.450(3)°, β=87.291(3)°, γ=65.954(3)°, Z=2, the volume is Its structure is shown in Formula I-5, the crystal structure is shown in Figure 5, and the single crystal parameters are shown in Table 5.
表5：簇合物5的单晶参数Table 5: Single crystal parameters of cluster 5
在一个具体实施方式中，本发明还提供一种具有式II所示结构的化学式为Mn
4XO
4(R
1CO
2)
8(L
1)(L
2)(L
3)的簇合物的制备方法，所述方法具体包括如下步骤：
In a specific embodiment, the present invention also provides a cluster compound having the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) having the structure shown in formula II Preparation method, described method specifically comprises the following steps:
(1)将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、二价锰盐和稀土盐，在乙腈溶液中反应，制备中间体；
(1) react organic carboxylic acid R 1 COOH, permanganate anionic oxidizing agent, divalent manganese salt and rare earth salt in acetonitrile solution to prepare intermediate;
(2)将步骤(1)中中间体与配体L
3反应，任选地与配体L
1和/或L
2反应，制备得到具有式II所示结构的化学式为Mn
4XO
4(R
1CO
2)
8(L
1)(L
2)(L
3)的簇合物；
(2) Reaction of the intermediate in step (1) with the ligand L 3 , optionally with the ligand L 1 and/or L 2 to prepare the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) clusters;
其中，所述有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、二价锰盐、稀土盐以及L
1、L
2和L
3具有如上含义。
Wherein, the organic carboxylic acid R 1 COOH, permanganate anion oxidant, divalent manganese salt, rare earth salt, and L 1 , L 2 and L 3 have the above meanings.
根据本发明，所述有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、二价锰盐和稀土盐的摩尔比为(10～120):(1～10):1:1，优选为(20～100):(2～8):1:1。
According to the present invention, the molar ratio of the organic carboxylic acid R 1 COOH, permanganate anion oxidant, divalent manganese salt and rare earth salt is (10-120):(1-10):1:1, preferably ( 20～100):(2～8):1:1.
本方法中，每毫摩尔稀土盐采用乙腈的含量大约为60～100毫升。该反应只能在乙腈溶剂进行，在醇或其它有机溶剂中均无法获得目标簇合物。In this method, the content of acetonitrile per millimole of rare earth salt is about 60-100 milliliters. This reaction can only be carried out in acetonitrile solvent, and the target cluster cannot be obtained in alcohol or other organic solvents.
根据本发明，步骤(2)中，先将中间体溶于卤代烃有机溶剂与腈类溶剂中，再与配体反应。According to the present invention, in step (2), the intermediate is firstly dissolved in a halogenated hydrocarbon organic solvent and a nitrile solvent, and then reacted with a ligand.
根据本发明，步骤(2)中，卤代烃有机溶剂可以是二氯甲烷、二氯乙烷或氯仿及其衍生物中的一种；所述腈类溶剂可以是乙腈、丙腈或丁腈及其衍生物中的一种。According to the present invention, in step (2), halogenated hydrocarbon organic solvent can be a kind of in methylene dichloride, dichloroethane or chloroform and derivative thereof; Described nitrile solvent can be acetonitrile, propionitrile or butyronitrile and one of its derivatives.
根据本发明，步骤(2)中，配体占溶剂总体积的0.1-3％。According to the present invention, in step (2), the ligand accounts for 0.1-3% of the total volume of the solvent.
根据本发明，步骤(1)中，还包括后处理步骤：将中间体过滤除去沉淀，0℃静止液体后，析出固体即为纯化的中间体。According to the present invention, in step (1), a post-processing step is also included: the intermediate is filtered to remove the precipitate, and after the liquid is static at 0° C., the precipitated solid is the purified intermediate.
根据本发明，步骤(2)中，还包括后处理步骤：将反应产物过滤除去沉淀，静止液体后，析出晶体，洗涤干燥，得到纯化的具有式II所示结构的化学式为Mn
4XO
4(R
1CO
2)
8(L
1)(L
2)(L
3)的簇合物。
According to the present invention, in step (2), a post-processing step is also included: the reaction product is filtered to remove the precipitate, and after the liquid is still, crystals are precipitated, washed and dried to obtain the purified chemical formula Mn 4 XO 4 ( Clusters of R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ).
示例性地，静止时间例如为1～7天。Exemplarily, the resting time is, for example, 1 to 7 days.
根据本发明，所述反应温度为60℃～90℃。According to the present invention, the reaction temperature is 60°C to 90°C.
根据本发明，所述反应时间可以为10～60分钟。According to the present invention, the reaction time may be 10-60 minutes.
根据本发明的一种优选方案，所述制备方法具体为：According to a preferred solution of the present invention, the preparation method is specifically:
第一步：将有机羧酸R
1COOH、高锰酸根阴离子型氧化剂、二价锰盐和稀土盐，按照摩尔比为(10～120):(1～10):1:1，在乙腈溶液中加热反应10～60分钟，得到棕色溶液，过滤除去沉淀；在0℃静置1～6天得到棕色晶体，即中间体；
The first step: the organic carboxylic acid R 1 COOH, permanganate anionic oxidant, divalent manganese salt and rare earth salt, according to the molar ratio of (10 ~ 120): (1 ~ 10): 1: 1, in the acetonitrile solution Heating and reacting in medium temperature for 10-60 minutes, a brown solution was obtained, and the precipitate was removed by filtration; standing at 0°C for 1-6 days to obtain a brown crystal, that is, an intermediate;
第二步：将合成中间体溶于卤代烃有机溶剂和腈类的混合溶剂，加入配体L
3，进一步反应，任选地与配体L
1和/或L
2反应，结晶得到具有式(II)所示结构的簇合物。
The second step: dissolve the synthetic intermediate in a mixed solvent of halogenated hydrocarbon organic solvent and nitrile, add ligand L 3 , further react, optionally react with ligand L 1 and/or L 2 , and crystallize to obtain the formula (II) The cluster compound of the structure shown.
根据本发明的优选方案，簇合物6的分子式为C
54H
88Mn
4NO
22Y，化学式为Mn
4YO
4(R
1CO
2)
9(C
9H
7N)， 其中，R
1＝叔丁基。
According to a preferred solution of the present invention, the molecular formula of the cluster compound 6 is C 54 H 88 Mn 4 NO 22 Y, and the chemical formula is Mn 4 YO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein, R 1 = tert-butyl.
簇合物6为单晶；其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.6590(10)°，γ＝90.00°，Z＝4，体积为
其结构如式II-1所示，晶体结构见图6，单晶参数如表6所示。
Cluster 6 is a single crystal; the single crystal belongs to the monoclinic system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.6590(10)°, γ=90.00°, Z=4, the volume is Its structure is shown in Formula II-1, the crystal structure is shown in Figure 6, and the single crystal parameters are shown in Table 6.
表6：簇合物6的单晶参数Table 6: Single crystal parameters of cluster 6
根据本发明的优选技术方案，簇合物7的分子式为C
54H
88GdMn
4NO
22，化学式为Mn
4GdO
4(R
1CO
2)
9(C
9H
7N)，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 7 is C 54 H 88 GdMn 4 NO 22 , and the chemical formula is Mn 4 GdO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein, R 1 = tert-butyl.
簇合物7为单晶。其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.799(2)°，γ＝90.00°，Z＝4，体积为
其结构如式II-2 所示，晶体结构见图7，单晶参数如表7所示。
Cluster 7 is a single crystal. Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.799(2)°, γ=90.00°, Z=4, the volume is Its structure is shown in Formula II-2, the crystal structure is shown in Figure 7, and the single crystal parameters are shown in Table 7.
表7：簇合物7的单晶参数Table 7: Single crystal parameters of cluster 7
根据本发明的优选技术方案，簇合物8的分子式为C
54H
88LuMn
4NO
22，化学式为Mn
4LuO
4(R
1CO
2)
9(C
9H
7N)，其中，R
1＝叔丁基。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 8 is C 54 H 88 LuMn 4 NO 22 , and the chemical formula is Mn 4 LuO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein, R 1 = tert-butyl.
簇合物8为单晶；其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.7670(10)°，γ＝90.00°，Z＝4，体积为
其结构如式II-3所示，晶体结构见图8，单晶参数如表8所示。
Cluster 8 is a single crystal; the single crystal belongs to the monoclinic system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.7670(10)°, γ=90.00°, Z=4, the volume is Its structure is shown in Formula II-3, the crystal structure is shown in Figure 8, and the single crystal parameters are shown in Table 8.
表8：簇合物8的单晶参数Table 8: Single crystal parameters of cluster 8
在一个具体实施方式中，本发明还提供一种具有式III所示结构的化学式为Mn
4XO
5H(R
1CO
2)
8(L
4)(L
5)的簇合物的制备方法，所述方法包括：
In a specific embodiment, the present invention also provides a method for preparing a cluster with the chemical formula Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) having the structure shown in formula III, The methods include:
将具有式II所示结构的簇合物溶于卤代烃和/或酯类溶剂中，加入水，任选地加入或不加入配体L
4和配体L
5，反应，得到具有III所示结构的簇合物。
Dissolving the cluster compound having the structure shown in formula II in halogenated hydrocarbon and/or ester solvent, adding water, optionally adding or not adding ligand L 4 and ligand L 5 , and reacting to obtain Clusters of the shown structure.
根据本发明，所述酯类溶剂可以是乙酸甲酯、乙酸乙酯等中的一种。According to the present invention, the ester solvent may be one of methyl acetate, ethyl acetate and the like.
其中，卤代烃、配体L
4、L
5具有如上含义。
Wherein, halogenated hydrocarbons, ligands L 4 , and L 5 have the above meanings.
根据本发明，所述制备方法还包括后处理步骤：将反应产物过滤，除去少数沉淀后，反应液静止，将析出晶体采用正己烷洗涤，干燥，制备纯化的具有式III所示结构的化学式为Mn
4XO
5H(R
1CO
2)
8(L
4)(L
5)的簇合物。
According to the present invention, the preparation method also includes a post-processing step: filter the reaction product, remove a small amount of precipitate, the reaction solution is still, wash the precipitated crystals with n-hexane, and dry to prepare the purified chemical formula with the structure shown in formula III: Clusters of Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ).
根据本发明，所述反应温度为20℃～60℃。According to the present invention, the reaction temperature is 20°C to 60°C.
根据本发明，所述反应时间可以为1～15分钟。According to the present invention, the reaction time may be 1-15 minutes.
根据本发明的优选技术方案，簇合物9的分子式为C
48H
91Mn
4N
2O
23Y，化学式为Mn
4YO
5H(R
1CO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 9 is C 48 H 91 Mn 4 N 2 O 23 Y, the chemical formula is Mn 4 YO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), Wherein, R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylacetamide.
簇合物9为单晶；其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
其结构如式III-1所示，晶体结构见图9，单晶参数如表9所示。
Cluster 9 is a single crystal; its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is Its structure is shown in formula III-1, the crystal structure is shown in Figure 9, and the single crystal parameters are shown in Table 9.
表9：簇合物9的单晶参数Table 9: Single crystal parameters of cluster 9
根据本发明的优选技术方案，簇合物10的分子式为C
48H
91DyMn
4N
2O
23，化学式为 Mn
4DyO
5H(R
1CO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
According to the preferred technical solution of the present invention, the molecular formula of the cluster compound 10 is C 48 H 91 DyMn 4 N 2 O 23 , and the chemical formula is Mn 4 DyO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), wherein , R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylacetamide.
簇合物10为单晶。其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
其结构如式III-2所示，晶体结构见图10，单晶参数如表10所示。
Cluster 10 is a single crystal. Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is Its structure is shown in formula III-2, the crystal structure is shown in Figure 10, and the single crystal parameters are shown in Table 10.
表10：簇合物10的单晶参数Table 10: Single crystal parameters of cluster 10
根据本发明的优选技术方案，簇合物11的分子式为C
48H
91Mn
4N
2O
23Lu，化学式为Mn
4LuO
5H(R
1CO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
According to the preferred technical solution of the present invention, the molecular formula of the cluster 11 is C 48 H 91 Mn 4 N 2 O 23 Lu, the chemical formula is Mn 4 LuO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), Wherein, R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylacetamide.
簇合物11为单晶；其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
其结构如式III-3所示，晶 体结构见图11，单晶参数如表11所示。
Cluster 11 is a single crystal; the single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is Its structure is shown in formula III-3, the crystal structure is shown in Figure 11, and the single crystal parameters are shown in Table 11.
表11：簇合物11的单晶参数Table 11: Single crystal parameters of cluster 11
本发明还提供了一种仿生水裂解催化剂，所述催化剂含有上述的稀土锰异核金属簇合物。The present invention also provides a biomimetic water splitting catalyst, which contains the above-mentioned rare earth manganese heteronuclear metal clusters.
本发明还提供了上述仿生水裂解催化剂的应用，应用于催化水的裂解。The present invention also provides the application of the above biomimetic water splitting catalyst, which is used to catalyze the splitting of water.
根据本发明，所述催化过程在电极表面进行，或在氧化剂存在下进行。According to the invention, the catalytic process takes place on the surface of the electrodes, or in the presence of an oxidizing agent.
本发明的有益效果：Beneficial effects of the present invention:
本发明引入配位能力更强的稀土离子X，合成了一系列具有[Mn
nXO
m]异核金属簇骨架核心的簇合物，例如核心结构为[Mn
3XO
2]、[Mn
4XO
4]和[Mn
4XO
5]的簇合物。该系列簇合物是一种新型仿生水裂解催化剂。特别是核心结构为[Mn
4XO
4]和[Mn
4XO
5]的簇合物，其几何结构和Mn离子价态均与生物水裂解催化中心十 分相似。这一系列含稀土的新型仿生簇合物，突破了传统观念束缚，不再局限于与生物完全相同的碱土金属，稀土金属离子的引入使其稳定性大大提升，在电极表面，或有氧化剂存在(可以是稳定的氧化剂，也可以是光诱导产生的瞬态氧化剂)驱动水的催化裂解。此外，结合簇合物中四价Mn离子和一些稀土元素独特磁学特征，在磁性材料方面有重要的应用价值，同时结合谱学跟踪表征等可能为今后机理研究奠定了重要的基础。
The present invention introduces rare earth ions X with stronger coordination ability, and synthesizes a series of clusters with [Mn n XO m ] heteronuclear metal cluster skeleton core, for example, the core structure is [Mn 3 XO 2 ], [Mn 4 XO 4 ] and [Mn 4 XO 5 ] clusters. This series of clusters is a new type of biomimetic water splitting catalyst. Especially the clusters whose core structures are [Mn 4 XO 4 ] and [Mn 4 XO 5 ], their geometric structure and Mn ion valence are very similar to the catalytic center of biological water splitting. This series of new biomimetic clusters containing rare earth breaks through the shackles of traditional concepts, and is no longer limited to alkaline earth metals that are exactly the same as living things. The introduction of rare earth metal ions greatly improves the stability. On the electrode surface, there may be oxidants (either a stable oxidant or a light-induced transient oxidant) drives the catalytic splitting of water. In addition, combining the unique magnetic characteristics of tetravalent Mn ions in clusters and some rare earth elements has important application value in magnetic materials, and combined with spectroscopy tracking and characterization may lay an important foundation for future mechanism research.
(1)本发明中，在结构上，所述含三价稀土离子X的[Mn
3XO
2]、[Mn
4XO
4]、[Mn
4XO
5]簇合物与含二价碱土金属离子的[Mn
4CaO
4]、[Mn
4SrO
4]簇合物相比，三价稀土离子的引入使簇合物的稳定性明显增加，同时能更稳定地进行催化水裂解。此外，由于碱土或稀土离子均处于簇合物的核心，没有任何可能让它们进行互换而不破坏整体结构。而碱土和稀土金属离子的电荷和水合离子pKa值等均存在明显不同，这些差异都会导致最终产物结构和性能的巨大差异。
(1) In the present invention, structurally, the [Mn 3 XO 2 ], [Mn 4 XO 4 ], [Mn 4 XO 5 ] clusters containing trivalent rare earth ions X and the divalent alkaline earth metal ions Compared with the [Mn 4 CaO 4 ] and [Mn 4 SrO 4 ] clusters, the introduction of trivalent rare earth ions significantly increases the stability of the clusters, and at the same time can catalyze water splitting more stably. Furthermore, since both alkaline earth or rare earth ions are at the core of the clusters, there is no possibility for them to be interchanged without disrupting the overall structure. However, there are obvious differences in charge and hydrated ion pKa values of alkaline earth and rare earth metal ions, and these differences will lead to huge differences in the structure and properties of the final product.
(2)本申请采用稀土离子、锰离子、羧酸为原料，以高锰酸根阴离子为氧化剂，合成得到核心结构为[Mn
3XO
2]、[Mn
4XO
4]和[Mn
4XO
5]的簇合物，这些簇合物的锰离子价态为+3或+4价，在磁性材料方面有着重要的价值。此外，本发明得到的核心结构为[Mn
4XO
4]和[Mn
4XO
5]的簇合物可作为人工水裂解催化剂，用于在电极表面，或由氧化剂(可以是稳定的氧化剂，也可以是光诱导产生的瞬态氧化剂)驱动水的催化裂解。
(2) This application uses rare earth ions, manganese ions, and carboxylic acids as raw materials, and uses permanganate anion as an oxidant to synthesize the core structures as [Mn 3 XO 2 ], [Mn 4 XO 4 ], and [Mn 4 XO 5 ] The clusters of these clusters have a manganese ion valence of +3 or +4 and are of great value in magnetic materials. In addition, the clusters whose core structures are [Mn 4 XO 4 ] and [Mn 4 XO 5 ] obtained in the present invention can be used as artificial water splitting catalysts on the surface of electrodes, or by oxidants (which can be stable oxidants or can be a photoinduced transient oxidant) drives the catalytic splitting of water.
具体的，specific,
1)本发明利用稀土离子、水或二价锰盐、高锰酸盐和简单有机羧酸作为起始原料，合成得到核心结构为[Mn
3XO
2]的簇合物，该簇合物外围由九个羧酸根阴离子和三个中性羧酸分子提供配体，其中三个锰离子的价态分别为+3,+3,+4价。这种含混合价态、完全由羧酸提供配体的[Mn
3XO
2]簇合物以前没有报道过。
1) The present invention uses rare earth ions, water or divalent manganese salts, permanganate and simple organic carboxylic acids as starting materials to synthesize a cluster with a core structure of [Mn 3 XO 2 ]. The ligands are provided by nine carboxylate anions and three neutral carboxylic acid molecules, among which the valence states of the three manganese ions are +3, +3, +4 respectively. Such [Mn 3 XO 2 ] clusters containing mixed valence states and ligands provided entirely by carboxylic acids have not been reported before.
2)本发明利用稀土离子、高锰酸盐、二价锰离子(Mn
2+)和简单有机羧酸作为起始原料，成功实现利用简单金属离子(Mn
2+,X
3+离子)、简单有机羧酸和MnO
4
-作为起始原料，通过多步合成得到仿生核心结构为[Mn
4XO
4]的簇合物。在该[Mn
4XO
4]簇合物中，[Mn
3XO
4]立方烷和外侧一个Mn离子通过一个μ-O桥连，构成一个[Mn
4XO
4]核心结构，外围配体由八个羧酸根阴离子R
1CO
2
-、配体L
1和L
2以及一个可交换配体L
3组成。其中四个锰离子的价态分别是+3，+3，+4，+4。
2) The present invention uses rare earth ions, permanganate, divalent manganese ions (Mn 2+ ) and simple organic carboxylic acids as starting materials to successfully realize the use of simple metal ions (Mn 2+ , X 3+ ions), simple Organic carboxylic acid and MnO 4 - were used as starting materials, and the biomimetic core structure [Mn 4 XO 4 ] clusters were obtained through multi-step synthesis. In the [Mn 4 XO 4 ] cluster, [Mn 3 XO 4 ] cubane and an outer Mn ion are connected by a μ-O bridge to form a [Mn 4 XO 4 ] core structure, and the peripheral ligands are composed of eight A carboxylate anion R 1 CO 2 - , ligands L 1 and L 2 and an exchangeable ligand L 3 . The valence states of the four manganese ions are +3, +3, +4, +4 respectively.
3)本发明采用上述具有式II结构的簇合物与水进一步反应，在核心中成功引入μ
2-O桥，即二配位的氧桥，得到一种仿生核心结构为[Mn
4XO
5]的簇合物。它的外围配体由八个羧酸根阴离子和两个可交换配体组成。其中四个锰离子的价态分别是+3，+3，+4，+4。这类簇合物不仅成功模拟了生物OEC的十原子核心骨架和配位环境，而且也模拟了生物OEC的氧化-还原特性。特别地，该类簇合物能作为催化剂稳定地进行催化水裂解反应，释放出氧气。
3) The present invention adopts the above-mentioned cluster compound having the structure of formula II to further react with water, successfully introduces μ 2 -O bridges into the core, that is, two-coordinated oxygen bridges, and obtains a bionic core structure [Mn 4 XO 5 ] of clusters. Its peripheral ligands consist of eight carboxylate anions and two exchangeable ligands. The valence states of the four manganese ions are +3, +3, +4, +4 respectively. This kind of clusters not only successfully simulated the ten-atom core framework and coordination environment of biological OECs, but also simulated the oxidation-reduction characteristics of biological OECs. In particular, such clusters can be used as catalysts to stably catalyze water splitting reactions and release oxygen.
图1为本发明实施例1所制备的簇合物1的晶体结构图。Fig. 1 is a diagram of the crystal structure of cluster compound 1 prepared in Example 1 of the present invention.
图2为本发明实施例2所制备的簇合物2的晶体结构图。Fig. 2 is a diagram of the crystal structure of cluster compound 2 prepared in Example 2 of the present invention.
图3为本发明实施例3所制备的簇合物3的晶体结构图。Fig. 3 is a crystal structure diagram of cluster compound 3 prepared in Example 3 of the present invention.
图4为本发明实施例4所制备的簇合物4的晶体结构图。Fig. 4 is a crystal structure diagram of cluster compound 4 prepared in Example 4 of the present invention.
图5为本发明实施例5所制备的簇合物5的晶体结构图。Fig. 5 is a crystal structure diagram of cluster compound 5 prepared in Example 5 of the present invention.
图6为本发明实施例6所制备的簇合物6的晶体结构图。Fig. 6 is a crystal structure diagram of cluster compound 6 prepared in Example 6 of the present invention.
图7为本发明实施例7所制备的簇合物7的晶体结构图。Fig. 7 is a crystal structure diagram of cluster compound 7 prepared in Example 7 of the present invention.
图8为本发明实施例8所制备的簇合物8的晶体结构图。Fig. 8 is a crystal structure diagram of cluster compound 8 prepared in Example 8 of the present invention.
图9为本发明实施例9所制备的簇合物9的晶体结构图。Fig. 9 is a crystal structure diagram of cluster compound 9 prepared in Example 9 of the present invention.
图10为本发明实施例10所制备的簇合物10的晶体结构图。FIG. 10 is a diagram of the crystal structure of the cluster compound 10 prepared in Example 10 of the present invention.
图11为本发明实施例11所制备的簇合物11的晶体结构图。Fig. 11 is a crystal structure diagram of cluster compound 11 prepared in Example 11 of the present invention.
图12为本发明实施例12，对应的簇合物1、2、3、4和5在1,2-二氯乙烷的紫外-可见吸收光谱。Fig. 12 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 1, 2, 3, 4 and 5 in 1,2-dichloroethane.
图13为本发明实施例12，对应的簇合物6和8在1,2-二氯乙烷的紫外-可见吸收光谱。Fig. 13 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 6 and 8 in 1,2-dichloroethane.
图14为本发明实施例12，对应的簇合物9和11在1,2-二氯乙烷的紫外-可见吸收光谱。Fig. 14 is Example 12 of the present invention, the ultraviolet-visible absorption spectra of the corresponding clusters 9 and 11 in 1,2-dichloroethane.
图15为实施例13中吸附簇合物6工作电极产生的催化水裂解电流曲线图。Fig. 15 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 6 in Example 13.
图16为实施例13中吸附簇合物8工作电极产生的催化水裂解电流曲线图。Fig. 16 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 8 in Example 13.
图17为实施例13中吸附簇合物9工作电极产生的催化水裂解电流曲线图。Fig. 17 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 9 in Example 13.
图18为实施例13中吸附簇合物11工作电极产生的催化水裂解电流曲线图。Fig. 18 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 11 in Example 13.
图19为实施例13中簇合物9催化稳定性测试图。Fig. 19 is a graph showing the catalytic stability test of cluster compound 9 in Example 13.
图20为实施例13中簇合物9催化水裂解的氧气测试图。Fig. 20 is an oxygen test graph of cluster 9 in Example 13 catalyzed water splitting.
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies realized based on the above contents of the present invention are covered within the scope of protection intended by the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1-11中，为了使簇合物1-11的结构式清晰，核心骨架和配体分别以球棒和线条形式显示，氢原子均已省略。In Examples 1-11, in order to make the structural formulas of clusters 1-11 clear, the core skeleton and ligands are shown in the form of ball sticks and lines, respectively, and hydrogen atoms have been omitted.
实施例1：簇合物1，Mn
3YO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3
Example 1: Cluster 1, Mn 3 YO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
制备方法选自如下任意一种：The preparation method is selected from any one of the following:
方案1：向250ml的圆底烧瓶中加入四丁基铵高锰酸(Bu
n
4NMnO
4，8mmol)、三氟甲磺酸钇(Y(CF
3SO
3)
3，2mmol)、水(2mmol)和特戊酸(Bu
tCO
2H,80mmol)在80℃乙腈中持续反应25分钟后，停止反应，过滤除去少量沉淀，将所得棕色母液静置于2℃。数天后，析出黑色晶体。收集所得的晶体，用乙腈洗涤，真空干燥，产率约为15％(依据Y离子的摩尔数)。
Scheme 1: Add tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 8 mmol), yttrium trifluoromethanesulfonate (Y(CF 3 SO 3 ) 3 , 2 mmol), water (2 mmol) into a 250 ml round bottom flask ) and pivalic acid ( But CO 2 H, 80 mmol) were continuously reacted in acetonitrile at 80°C for 25 minutes, then the reaction was stopped, a small amount of precipitate was removed by filtration, and the obtained brown mother liquor was left standing at 2°C. After several days, black crystals precipitated out. The resulting crystals were collected, washed with acetonitrile, and dried in vacuo with a yield of about 15% (based on the moles of Y ions).
方案2：向250ml的圆底烧瓶中加入四丁基铵高锰酸(Bu
n
4NMnO
4，8mmol)、三氟甲磺酸钇(Y(CF
3SO
3)
3，2mmol)、乙酰丙酮锰(II)(2mmol)和特戊酸(Bu
tCO
2H,80mmol)在80℃乙腈中持续反应25分钟后，停止反应，过滤除去少量沉淀，将所得棕色母液静置于2℃。数天后，析出黑色晶体。收集所得的晶体，用乙腈洗涤，真空干燥，产率约为58％(依据Y离子的摩尔数)。
Scheme 2: Add tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 8 mmol), yttrium trifluoromethanesulfonate (Y(CF 3 SO 3 ) 3 , 2 mmol), manganese acetylacetonate to a 250 ml round bottom flask (II) (2 mmol) and pivalic acid ( But CO 2 H, 80 mmol) were continuously reacted in acetonitrile at 80°C for 25 minutes, then the reaction was stopped, a small amount of precipitate was removed by filtration, and the resulting brown mother liquor was left standing at 2°C. After several days, black crystals precipitated out. The resulting crystals were collected, washed with acetonitrile, and dried in vacuo with a yield of about 58% (based on the moles of Y ions).
簇合物1，化学式为Mn
3YO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 1, the chemical formula is Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 = tert-butyl.
即簇合物1，化学式为Mn
3YO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3，分子式：C
60H
111Mn
3O
26Y。元素分析理论值(％):C,47.97；H,7.45；实验值(％):C,47.83；H,7.42。其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.526(3)°，β＝87.004(2)°，γ＝65.818(3)°，Z＝2，体积为
Namely cluster compound 1, the chemical formula is Mn 3 YO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 , and the molecular formula is: C 60 H 111 Mn 3 O 26 Y. Elemental analysis theoretical value (%): C, 47.97; H, 7.45; experimental value (%): C, 47.83; H, 7.42. Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.526(3)°, β=87.004(2)°, γ=65.818(3)°, Z=2, the volume is
簇合物1的化学结构如下式I-1，其单晶测定具体参数见表1，其晶体空间结构见图1。The chemical structure of cluster 1 is shown in the following formula I-1, the specific parameters of its single crystal determination are shown in Table 1, and its crystal spatial structure is shown in Figure 1.
实施例2：簇合物2，Mn
3LaO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3
Example 2: Cluster 2, Mn 3 LaO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
实施例2的制备方法与实施例1中方法2相同，区别在于，采用三氟甲磺酸镧替换三氟甲磺酸钇。产率约为31％(依据La离子的摩尔数)。The preparation method of Example 2 is the same as that of Method 2 in Example 1, except that lanthanum trifluoromethanesulfonate is used instead of yttrium trifluoromethanesulfonate. The yield was about 31% (based on the moles of La ions).
簇合物2，化学式为Mn
3LaO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 2, the chemical formula is Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 = tert-butyl.
即簇合物2，化学式为Mn
3LaO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3，分子式：C
60H
111LaMn
3O
26。元素分析理论值(％):C,46.43；H,7.21；实验值(％):C,46.38；H,7.14。其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90°，β＝107.516(4)°，γ＝90°，Z＝4，体积为
That is, cluster 2, the chemical formula is Mn 3 LaO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 , and the molecular formula is: C 60 H 111 LaMn 3 O 26 . Elemental analysis theoretical value (%): C, 46.43; H, 7.21; experimental value (%): C, 46.38; H, 7.14. Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90°, β=107.516(4)°, γ=90°, Z=4, the volume is
簇合物2的化学结构如下式I-2，其单晶测定具体参数见表2，其晶体空间结构见图2。The chemical structure of cluster 2 is shown in the following formula I-2, the specific parameters of its single crystal determination are shown in Table 2, and its crystal spatial structure is shown in Figure 2.
实施例3：簇合物3，Mn
3GdO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3
Example 3: Cluster 3, Mn 3 GdO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
实施例3的制备方法与实施例1中方法2相同，区别在于，采用三氟甲磺酸钆(Gd(CF
3SO
3)
3)替换三氟甲磺酸钇。产率约为48％(依据Gd离子的摩尔数)。
The preparation method of Example 3 is the same as that of Method 2 in Example 1, except that gadolinium trifluoromethanesulfonate (Gd(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate. The yield was about 48% (based on moles of Gd ions).
簇合物3，化学式为Mn
3GdO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 3, the chemical formula is Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
即簇合物3，化学式为Mn
3GdO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3，分子式：C
60H
111GdMn
3O
26。元素分析理论值(％):C,45.88；H,7.12；实验值(％):C,45.66；H,7.23。其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.898(2)°，β＝87.087(2)°，γ＝65.755(2)°，Z＝2，体积为
Namely cluster compound 3, the chemical formula is Mn 3 GdO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 , and the molecular formula is: C 60 H 111 GdMn 3 O 26 . Elemental analysis theoretical value (%): C, 45.88; H, 7.12; experimental value (%): C, 45.66; H, 7.23. Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.898(2)°, β=87.087(2)°, γ=65.755(2)°, Z=2, the volume is
簇合物3的化学结构如下式I-3，其单晶测定具体参数见表3，其晶体空间结构见图3。The chemical structure of the cluster compound 3 is shown in the following formula I-3, the specific parameters of its single crystal determination are shown in Table 3, and its crystal spatial structure is shown in Figure 3.
实施例4：簇合物4，Mn
3DyO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3
Example 4: Cluster 4, Mn 3 DyO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
实施例4的制备方法与实施例1中方法2相同，区别在于，采用三氟甲磺酸镝(Dy(CF
3SO
3)
3)替换三氟甲磺酸钇。产率约为43％(依据Dy离子的摩尔数)。
The preparation method of Example 4 is the same as that of Method 2 in Example 1, except that dysprosium trifluoromethanesulfonate (Dy(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate. The yield was about 43% (based on moles of Dy ions).
簇合物4，化学式为Mn
3DyO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 4, the chemical formula is Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
即簇合物4，化学式为Mn
3DyO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3，分子式：C
60H
111DyMn
3O
26。元素分析理论值:C,45.73；H,7.10；实验值:C,45.76；H,6.98。其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.790(2)°，β＝86.995(2)°，γ＝65.678(2)°，Z＝2，体积为
Namely cluster 4, the chemical formula is Mn 3 DyO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 , and the molecular formula is: C 60 H 111 DyMn 3 O 26 . Elemental analysis theoretical value: C, 45.73; H, 7.10; experimental value: C, 45.76; H, 6.98. Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.790(2)°, β=86.995(2)°, γ=65.678(2)°, Z=2, the volume is
簇合物4的化学结构如下式I-4，其单晶测定具体参数见表4，其晶体空间结构见图4。The chemical structure of cluster 4 is shown in the following formula I-4, the specific parameters of its single crystal determination are shown in Table 4, and its crystal spatial structure is shown in Figure 4.
实施例5：簇合物5，Mn
3LuO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3
Example 5: Cluster 5, Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
实施例5的制备方法与实施例1中方法2相同，区别在于，采用三氟甲磺酸镥(Lu(CF
3SO
3)
3)替换三氟甲磺酸钇。产率约为48％(依据Lu离子的摩尔数)。
The preparation method of Example 5 is the same as that of Method 2 in Example 1, except that lutetium trifluoromethanesulfonate (Lu(CF 3 SO 3 ) 3 ) is used instead of yttrium trifluoromethanesulfonate. The yield was about 48% (based on the moles of Lu ions).
簇合物5，化学式为Mn
3LuO
2(R
1CO
2)
9(R
1CO
2H)
3，其中，R
1＝叔丁基。
Cluster 5, the chemical formula is Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein R 1 =tert-butyl.
即簇合物5，化学式为Mn
3LuO
2(C
5H
9O
2)
9(C
5H
9O
2H)
3，分子式：C
60H
111LuMn
3O
26。其单晶属于三斜晶系，空间群为P-1，晶胞参数为
α＝77.450(3)°，β＝87.291(3)°，γ＝65.954(3)°，Z＝2，体积为
Namely cluster 5, the chemical formula is Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 , and the molecular formula is: C 60 H 111 LuMn 3 O 26 . Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are α=77.450(3)°, β=87.291(3)°, γ=65.954(3)°, Z=2, the volume is
簇合物5的化学结构如下式I-5，其单晶测定具体参数见表5，其晶体空间结构见图5。The chemical structure of cluster 5 is shown in the following formula I-5, the specific parameters of its single crystal determination are shown in Table 5, and its crystal spatial structure is shown in Figure 5.
实施例6：簇合物6，Mn
4YO
4(C
5H
9O
2)
9(C
9H
7N)
Example 6: Cluster 6, Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
制备方法如下：The preparation method is as follows:
第一步，向100ml的圆底烧瓶中加入四丁基高锰酸铵(Bu
n
4NMnO
4，4mmol)、三氟甲磺酸钇(Y(CF
3SO
3)
3，1mmol)，乙酰丙酮锰(Mn(acac)
2),1mmol)和特戊酸((CH
3)
3CCO
2H,40mmol)在80℃乙腈中持续反应25分钟后，停止反应，过滤除去少量沉淀，所得棕色母液静置于2℃，数天后，析出棕色的合成中间体。
In the first step, tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 4 mmol), yttrium trifluoromethanesulfonate (Y(CF 3 SO 3 ) 3 , 1 mmol), acetylacetone was added to a 100 ml round bottom flask. Manganese (Mn(acac) 2 ), 1 mmol) and pivalic acid ((CH 3 ) 3 CCO 2 H, 40 mmol) were continuously reacted in acetonitrile at 80°C for 25 minutes, then the reaction was stopped, and a small amount of precipitate was removed by filtration, and the obtained brown mother liquor was static After several days at 2°C, a brown synthetic intermediate was precipitated.
第二步，将得到的中间体溶于二氯甲烷和乙腈(体积比是1:2)，再加入占总体积为1％的异喹啉，数天后析出棕色晶体。收集所得的晶体，用正己烷洗涤，真空干燥，产率为～19％(依据Y离子的摩尔数)。In the second step, the obtained intermediate was dissolved in dichloromethane and acetonitrile (1:2 volume ratio), and then 1% isoquinoline was added to the total volume, and brown crystals were precipitated after a few days. The resulting crystals were collected, washed with n-hexane, and dried in vacuo in ~19% yield (based on moles of Y ions).
簇合物6，化学式为Mn
4YO
4(R
1CO
2)
9(L
3)，其中，R
1＝叔丁基，L
3＝异喹啉。
Cluster 6 has the chemical formula Mn 4 YO 4 (R 1 CO 2 ) 9 (L 3 ), wherein R 1 = tert-butyl, L 3 = isoquinoline.
即簇合物6，化学式为Mn
4YO
4(C
5H
9O
2)
9(C
9H
7N)，分子式：C
54H
88Mn
4NO
22Y。元素分析理论值(％):C,45.94；H,6.28；N,0.99；实验值(％):C,46.19；H,6.27；N,1.01。其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.6590(10)°，γ＝90.00°，Z＝4，体积为
That is, cluster 6, the chemical formula is Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), and the molecular formula is: C 54 H 88 Mn 4 NO 22 Y. Elemental Analysis Theoretical value (%): C, 45.94; H, 6.28; N, 0.99; Experimental value (%): C, 46.19; H, 6.27; N, 1.01. Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.6590(10)°, γ=90.00°, Z=4, the volume is
簇合物6的化学结构如下式II-1，其单晶测定具体参数见表6，其晶体空间结构见图6。The chemical structure of cluster compound 6 is shown in the following formula II-1, the specific parameters of its single crystal determination are shown in Table 6, and its crystal spatial structure is shown in Figure 6.
实施例7：簇合物7，Mn
4GdO
4(C
5H
9O
2)
9(C
9H
7N)
Example 7: Cluster 7, Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
制备方法如下：The preparation method is as follows:
第一步，向100ml的圆底烧瓶中加入四丁基高锰酸铵(Bu
n
4NMnO
4，8mmol)、三氟甲磺酸钆(Gd(CF
3SO
3)
3，2mmol)，乙酰丙酮锰(II)(Mn(acac)
2),2mmol)和特戊酸((CH
3)
3CCO
2H,80mmol)在80℃乙腈中持续反应25分钟后，停止反应，过滤除去少量沉淀，所得棕色母液静置于2℃，数天后，析出棕色的合成中间体。
In the first step, tetrabutylammonium permanganate (Bu n 4 NMnO 4 , 8 mmol), gadolinium trifluoromethanesulfonate (Gd(CF 3 SO 3 ) 3 , 2 mmol), acetylacetonate were added to a 100 ml round bottom flask. Manganese (II) (Mn(acac) 2 ), 2mmol) and pivalic acid ((CH 3 ) 3 CCO 2 H, 80mmol) were continuously reacted in acetonitrile at 80°C for 25 minutes, then the reaction was stopped, a small amount of precipitate was removed by filtration, and the obtained The brown mother liquor was left standing at 2°C, and after a few days, a brown synthetic intermediate was precipitated.
第二步，将得到的中间体溶于二氯甲烷和乙腈(体积比是1:2)，再加入体积比～1％的异喹啉，数天后析出棕色晶体。In the second step, the obtained intermediate was dissolved in dichloromethane and acetonitrile (volume ratio 1:2), and then 1% isoquinoline by volume ratio was added, and brown crystals were precipitated after a few days.
簇合物7，化学式为Mn
4GdO
4(R
1CO
2)
9(L
3)，其中，R
1＝叔丁基，L
3＝异喹啉。
Cluster 7, the chemical formula is Mn 4 GdO 4 (R 1 CO 2 ) 9 (L 3 ), where R 1 = tert-butyl, L 3 = isoquinoline.
即簇合物7，化学式为Mn
4GdO
4(C
5H
9O
2)
9(C
9H
7N)，分子式：C
54H
88GdMn
4NO
22。其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.799(2)°，γ＝90.00°，Z＝4，体积为
That is, cluster 7, the chemical formula is Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), and the molecular formula is: C 54 H 88 GdMn 4 NO 22 . Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.799(2)°, γ=90.00°, Z=4, the volume is
簇合物7的化学结构如下式II-2，其单晶测定具体参数见表7，其晶体空间结构见图7。The chemical structure of cluster 7 is shown in the following formula II-2, the specific parameters of its single crystal determination are shown in Table 7, and its crystal spatial structure is shown in Figure 7.
实施例8：簇合物8，Mn
4LuO
4(C
5H
9O
2)
9(C
9H
7N)
Example 8: Cluster 8, Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
实施例8中簇合物8的制备方法与实施例6相同，区别在于，采用三氟甲磺酸镥(Lu(CF
3SO
3))替换实施例6中的三氟甲磺酸钇。
The preparation method of cluster 8 in Example 8 is the same as that in Example 6, except that lutetium trifluoromethanesulfonate (Lu(CF 3 SO 3 )) is used instead of yttrium trifluoromethanesulfonate in Example 6.
簇合物8，化学式为Mn
4LuO
4(R
1CO
2)
9(L
3)，其中，R
1＝叔丁基，L
3＝异喹啉。
Cluster 8, the chemical formula is Mn 4 LuO 4 (R 1 CO 2 ) 9 (L 3 ), wherein, R 1 = tert-butyl, L 3 = isoquinoline.
即簇合物8，化学式为Mn
4LuO
4(C
5H
9O
2)
9(C
9H
7N)，分子式：C
54H
88LuMn
4NO
22。元素分析理论值(％):C,43.30；H,5.92；N,0.94；实验值(％):C,43.69；H,5.96；N,0.90。其单晶属于单斜晶系，空间群为P2
1/n，晶胞参数为
α＝90.00°，β＝101.7670(10)°，γ＝90.00°，Z＝4，体积为
That is, cluster 8, the chemical formula is Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), and the molecular formula is: C 54 H 88 LuMn 4 NO 22 . Elemental analysis Theoretical value (%): C, 43.30; H, 5.92; N, 0.94; Experimental value (%): C, 43.69; H, 5.96; N, 0.90. Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are α=90.00°, β=101.7670(10)°, γ=90.00°, Z=4, the volume is
簇合物8的化学结构如下式II-3，其单晶测定具体参数见表8，其晶体空间结构见图8。The chemical structure of cluster 8 is shown in the following formula II-3, the specific parameters of its single crystal determination are shown in Table 8, and its crystal spatial structure is shown in Figure 8.
实施例9：簇合物9，Mn
4YO
5H(C
5H
9O
2)
8(C
4H
9NO)
2
Example 9: Cluster 9, Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
制备方法如下：The preparation method is as follows:
将如式II-1所示的Mn
4YO
4(C
5H
9O
2)
9(C
9H
7N)溶于二氯甲烷和乙酸乙酯(体积比是3:1)，再加入5％的N,N-二甲基乙酰胺(体积比)和水(水与Mn
4YO
4(C
5H
9O
2)
9(C
9H
7N)摩尔比为2:1)，在40℃反应5min，将反应产物过滤，除去少数沉淀后，反应液静止，数天后析出棕色晶体。收集所得的晶体，用正己烷洗涤，真空干燥，产率约为52％(依据Y离子的摩尔数)。
Dissolve Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N) shown in formula II-1 in dichloromethane and ethyl acetate (volume ratio is 3:1), and then add 5 % of N,N-dimethylacetamide (volume ratio) and water (the molar ratio of water to Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N) is 2:1), at 40 After reacting at ℃ for 5 minutes, the reaction product was filtered to remove a small amount of precipitate, the reaction solution was still, and brown crystals were precipitated after a few days. The resulting crystals were collected, washed with n-hexane, and dried in vacuo. The yield was about 52% (based on the moles of Y ions).
簇合物9，化学式为[Mn
4YO
5]H(RCO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 9, the chemical formula is [Mn 4 YO 5 ]H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethyl Acetamide.
即簇合物9，化学式为Mn
4YO
5H(C
5H
9O
2)
8(C
4H
9NO)
2，分子式：H
91C
48N
2O
23Mn
4Y。元素分析理论值(％):C,39.97；H,6.41；N,2.33；实验值(％):C,40.08；H,6.39；N,2.33。其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Namely cluster compound 9, the chemical formula is Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 , and the molecular formula is: H 91 C 48 N 2 O 23 Mn 4 Y. Elemental Analysis Theoretical value (%): C, 39.97; H, 6.41; N, 2.33; Experimental value (%): C, 40.08; H, 6.39; N, 2.33. Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
簇合物9的化学结构如下式III-1，其单晶测定具体参数见表9，其晶体空间结构见图9。The chemical structure of cluster 9 is shown in the following formula III-1, the specific parameters of its single crystal determination are shown in Table 9, and its crystal spatial structure is shown in Figure 9.
实施例10：簇合物10，Mn
4DyO
5H(C
5H
9O
2)
8(C
4H
9NO)
2
Example 10: Cluster 10, Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
制备方法如下：The preparation method is as follows:
Mn
4DyO
5H(C
5H
9O
2)
8(C
4H
9NO)
2的合成方案与Mn
4YO
5H(C
5H
9O
2)
8(C
4H
9NO)
2类似，仅需将合成原料中三氟甲磺酸钇替换为三氟甲磺酸镝(Dy(CF
3SO
3)
3)。
The synthesis scheme of Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 is similar to that of Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 , It is only necessary to replace yttrium trifluoromethanesulfonate in the synthetic raw materials with dysprosium trifluoromethanesulfonate (Dy(CF 3 SO 3 ) 3 ).
簇合物10，化学式为Mn
4DyO
5H(RCO
2)
8(L
4)(L
5)，其中，R
1＝叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 10, the chemical formula is Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
即簇合物10，化学式为Mn
4DyO
5H(C
5H
9O
2)
8(C
4H
9NO)
2。其单晶为正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Namely cluster 10, the chemical formula is Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 . The single crystal is orthorhombic, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
簇合物10的化学结构如下式III-2，其单晶测定具体参数见表10，其晶体空间结构见图10。The chemical structure of the cluster compound 10 is shown in the following formula III-2, the specific parameters of its single crystal determination are shown in Table 10, and its crystal spatial structure is shown in Figure 10.
实施例11：簇合物11，Mn
4LuO
5H(C
5H
9O
2)
8(C
4H
9NO)
2
Example 11: Cluster 11, Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
制备方法如下：The preparation method is as follows:
Mn
4LuO
5H(C
5H
9O
2)
8(C
4H
9NO)
2的合成方案与Mn
4YO
5H(C
5H
9O
2)
8(C
4H
9NO)
2类似，仅需将原料中的三氟甲磺酸钇替换为三氟甲磺酸镥。数天后析出棕色晶体。收集所得的晶体，用正己烷洗涤，真空干燥，产率为～39％(依据Lu离子的摩尔数)。
The synthesis scheme of Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 is similar to that of Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 , It is only necessary to replace the yttrium triflate in the starting material with lutetium triflate. Brown crystals precipitated out after a few days. The resulting crystals were collected, washed with n-hexane, and dried in vacuo in ~39% yield (based on moles of Lu ions).
簇合物11，化学式为Mn
4LuO
5H(RCO
2)
8(L
4)(L
5)，其中，R
1为叔丁基；L
4、L
5均为N,N-二甲基乙酰胺。
Cluster 11, the chemical formula is Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 is tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides.
即簇合物11，化学式为Mn
4LuO
5H(C
5H
9O
2)
8(C
4H
9NO)
2·(C
2H
5NO)
0.5(注:存在N,N-二甲基乙酰胺溶剂分子)，分子式：H
95.5C
50N
2.5O
23.5Mn
4Lu。元素分析理论值(％):C,39.99；H,6.41；N,2.33；实验值(％):C,40.08；H,6.39；N,2.33。其单晶为正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
That is, cluster 11, the chemical formula is Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 ·(C 2 H 5 NO) 0.5 (Note: N,N-dimethyl acetamide solvent molecule), molecular formula: H 95.5 C 50 N 2.5 O 23.5 Mn 4 Lu. Elemental Analysis Theoretical value (%): C, 39.99; H, 6.41; N, 2.33; Experimental value (%): C, 40.08; H, 6.39; N, 2.33. The single crystal is orthorhombic, the space group is Pbca, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=8, the volume is
簇合物11的化学结构如式III-3，其单晶测定具体参数见表11，其晶体空间结构见图11。The chemical structure of cluster 11 is shown in formula III-3, the specific parameters of its single crystal determination are shown in Table 11, and its crystal spatial structure is shown in Figure 11.
实验例12：簇合物1、2、3、4、5、6、8、9和11的紫外-可见吸收光谱Experimental example 12: UV-Vis absorption spectra of clusters 1, 2, 3, 4, 5, 6, 8, 9 and 11
向10mm光径石英比色皿中加入20μM对应簇合物的1,2-二氯乙烷溶液，以纯1,2-二氯乙烷作为参比，在Hitachi U-3900紫外-可见光谱仪测得对应簇合物的吸收光谱(如图12、13和14所示)。Add 20 μM 1,2-dichloroethane solution of the corresponding cluster to a 10mm optical diameter quartz cuvette, and use pure 1,2-dichloroethane as a reference, and measure it on a Hitachi U-3900 UV-visible spectrometer The absorption spectra of the corresponding clusters (as shown in Figures 12, 13 and 14).
实施案例13：簇合物6、8、9和11在电极表面催化水裂解释放氧气的测定Example 13: Determination of oxygen release by catalytic water splitting of clusters 6, 8, 9 and 11 on the electrode surface
利用Princeton Applied Research VersaSTAT 3电化学工作站分别对簇合物6、8、9和11在电极表面催化水裂解进行跟踪。测试采用三电极装置，其中工作电极为吸附簇合物的ITO-nanoITO电极，对电极为铂网电极，参比电极为银/硝酸银电极(参比液为10mM AgNO
3和100mM LiClO
4的乙腈溶液)。电解液为含100mM LiClO
4和1.2M水(H
2O)的碳酸丙烯酯溶液。扫描速度为10mV/s。图15、16、17和18分别对应吸附簇合物6、8、9和11工作电极所产生的催化水裂解电流，而在未吸附上述簇合物则未观察到明显催化电流。
Using Princeton Applied Research VersaSTAT 3 electrochemical workstation, clusters 6, 8, 9 and 11 were followed to catalyze water splitting on the electrode surface. The test adopts a three-electrode device, wherein the working electrode is an ITO-nanoITO electrode that adsorbs clusters, the counter electrode is a platinum mesh electrode, and the reference electrode is a silver/silver nitrate electrode (the reference solution is 10mM AgNO 3 and 100mM LiClO 4 acetonitrile solution). The electrolyte was a propylene carbonate solution containing 100 mM LiClO 4 and 1.2 M water (H 2 O). The scanning speed is 10mV/s. Figures 15, 16, 17, and 18 correspond to the catalytic water splitting currents generated by the working electrodes of adsorbed clusters 6, 8, 9, and 11, respectively, while no significant catalytic current was observed in the unadsorbed clusters.
对簇合物进行恒电位测试。所用电解池为H型电解池，两腔室之间用阴离子交换膜隔开。工作电极和参比电极置于含100mM LiClO
4和1.2M H
2O的碳酸丙烯酯溶液中，对电极置于含10mM Li
2CO
3/HClO
4和100mM LiClO
4的水溶液(pH＝6～7)中。测得电流-时间曲线如图19所示，表明实施案例9中所制备的核心结构为[Mn
4YO
5]的簇合物可在上述电解液中稳定催化10小时以上，具有优异的催化稳定性。同时，利用Ocean Optics NeoFOX-GT oxygen sensing system探测到该过程伴有明显的氧气释放，如图20。上述测定实验表明核心结构为[Mn
4XO
4]和[Mn
4XO
5]的两种簇合物具有显著的催化水裂解放氧气的功能。
Potentiostatic tests were performed on the clusters. The electrolytic cell used is an H-type electrolytic cell, and the two chambers are separated by an anion exchange membrane. The working electrode and the reference electrode are placed in a propylene carbonate solution containing 100mM LiClO 4 and 1.2M H 2 O, and the counter electrode is placed in an aqueous solution containing 10mM Li 2 CO 3 /HClO 4 and 100mM LiClO 4 (pH=6~7) middle. The measured current-time curve is shown in Figure 19, indicating that the cluster compound with the core structure [Mn 4 YO 5 ] prepared in Example 9 can be stably catalyzed in the above electrolyte for more than 10 hours, and has excellent catalytic stability sex. At the same time, the Ocean Optics NeoFOX-GT oxygen sensing system was used to detect the process accompanied by obvious oxygen release, as shown in Figure 20. The above determination experiments show that the two clusters with the core structures of [Mn 4 XO 4 ] and [Mn 4 XO 5 ] have a significant function of catalyzing water splitting to liberate oxygen.
以上，对本发明的实施方式进行了示例性的说明。但是，本发明的保护范围不拘囿于上述实施方式。凡在本发明的精神和原则之内，本领域技术人员所作出的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described as examples above. However, the protection scope of the present invention is not limited to the above-mentioned embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
Claims (10)
- 一种稀土锰异核金属簇合物，其特征在于，所述簇合物具有[Mn nXO m]异核金属簇骨架核心，其中，n为3或4；m为2，4或5；X选自稀土元素。 A rare earth manganese heteronuclear metal cluster compound, characterized in that the cluster compound has a [Mn n XO m ] heteronuclear metal cluster skeleton core, wherein n is 3 or 4; m is 2, 4 or 5; X is selected from rare earth elements.
- 根据权利要求1所述的稀土锰异核金属簇合物，其特征在于，所述稀土锰异核金属簇合物具有下述核心结构中的一种：[Mn 3XO 2]异核金属簇骨架核心、[Mn 4XO 4]异核金属簇骨架核心和[Mn 4XO 5]异核金属簇骨架核心，所述X选自稀土元素； The rare earth manganese heteronuclear metal cluster according to claim 1, wherein the rare earth manganese heteronuclear metal cluster has one of the following core structures: [Mn 3 XO 2 ] heteronuclear metal cluster framework core, [Mn 4 XO 4 ] heteronuclear metal cluster framework core and [Mn 4 XO 5 ] heteronuclear metal cluster framework core, wherein X is selected from rare earth elements;所述X选自钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥。Said X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
- 根据权利要求1所述的稀土锰异核金属簇合物，其特征在于，所述簇合物的化学式为Mn 3XO 2(R 1CO 2) 9(R 1CO 2H) 3化合物，具有如式I所示结构，其含有一个稀土离子X和三个Mn离子，它们通过2个μ 3-O桥连接成的[Mn 3XO 2]异核金属簇骨架核心； The rare earth manganese heteronuclear metal cluster compound according to claim 1, characterized in that, the chemical formula of the cluster compound is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 compound, having The structure shown in formula I, which contains a rare earth ion X and three Mn ions, which are connected by two μ 3 -O bridges to form a [Mn 3 XO 2 ] heteronuclear metal cluster skeleton core;[Mn 3XO 2]异核金属簇骨架核心的外围配体由九个羧酸根阴离子R 1CO 2 -和三个中性羧酸配体R 1CO 2H提供，其中三个Mn离子的价态分别是+3，+3，+4价，整个簇合物呈电中性； The peripheral ligands of the [Mn 3 XO 2 ] heteronuclear metal cluster framework core are provided by nine carboxylate anions R 1 CO 2 - and three neutral carboxylic acid ligands R 1 CO 2 H, of which the valence of three Mn ions The states are +3, +3, +4 respectively, and the whole cluster is electrically neutral;
其中，X选自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu；Wherein, X is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;R 1相同或不同、彼此独立地选自H或C 1-8直链或支链烷基； R 1 are the same or different, independently selected from H or C 1-8 straight chain or branched chain alkyl;或者，所述簇合物的化学式为Mn 4XO 4(R 1CO 2) 8(L 1)(L 2)(L 3)，具有如式II所示结构，其含有四个Mn离子和一个稀土离子X，它们通过四个μ-O桥连接成[Mn 4XO 4]异核金属簇骨架核心； Alternatively, the chemical formula of the cluster is Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), which has a structure as shown in formula II, which contains four Mn ions and one Rare earth ions X, which are connected into [Mn 4 XO 4 ] heteronuclear metal cluster skeleton core through four μ-O bridges;[Mn 4XO 4]异核金属簇骨架核心的外围配体由八个羧酸根阴离子R 1CO 2 -和三个配体L 1、L 2和L 3提供；其中四个Mn离子的价态分别是+3，+3，+4，+4； The peripheral ligands of the [Mn 4 XO 4 ] heteronuclear metal cluster framework core are provided by eight carboxylate anions R 1 CO 2 - and three ligands L 1 , L 2 and L 3 ; the valence states of four Mn ions They are +3, +3, +4, +4 respectively;
式II中，稀土离子X、R 1具有如上含义； In formula II, the rare earth ion X, R have the above meanings;L 1、L 2相同或不同，各自独立地选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物，或者L 1和 L 2连接为一个双齿螯合配体； L 1 and L 2 are the same or different, each independently selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, Ethers, ketones, nitriles, esters, amides and their respective derivatives, or L1 and L2 are connected as a bidentate chelating ligand;L 3选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物； L3 is selected from carboxylic acid molecules and their derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters Classes, amides and their respective derivatives;或者，所述簇合物的化学式为Mn 4XO 5H(R 1CO 2) 8(L 4)(L 5)，具有式III所示结构，其含有四个Mn离子和一个稀土离子，它们通过五个μ-O连接成[Mn 4XO 5]异核金属簇骨架核心；[Mn 4XO 5]异核金属簇骨架核心的外围配体由八个羧酸根阴离子R 1CO 2 -和两个配体L 4和L 5提供；[Mn 4XO 5]异核金属簇骨架核心存在一个μ 2-O桥；四个锰离子的价态为+3，+3，+4，+4； Alternatively, the chemical formula of the cluster is Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ), which has the structure shown in formula III, which contains four Mn ions and one rare earth ion, and they The core of [Mn 4 XO 5 ] heteronuclear metal cluster skeleton is connected by five μ-O; the peripheral ligands of [Mn 4 XO 5 ] heteronuclear metal cluster skeleton core consist of eight carboxylate anions R 1 CO 2 - Provided by two ligands L 4 and L 5 ; [Mn 4 XO 5 ] there is a μ 2 -O bridge in the core of the heteronuclear metal cluster framework; the valence states of the four manganese ions are +3, +3, +4, +4;
式III中，稀土离子X、R 1具有如上含义；L 4和L 5相同或不同，彼此独立地选自羧酸分子及其衍生物、吡啶、咪唑、吡嗪、喹啉、异喹啉及其各自的衍生物，或者是水分子、醇分子、醚类、酮类、腈类、酯类、酰胺类及其各自的衍生物，或者L 4和L 5连接为一个双齿螯合配体。 In formula III, the rare earth ion X and R have the above meanings; L and L are the same or different, and are independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and Their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and their respective derivatives, or L4 and L5 linked as a bidentate chelating ligand . - 根据权利要求3所述的稀土锰异核金属簇合物，其特征在于，具有如式I所示结构的簇合物选自如下簇合物1～簇合物5中的任一簇合物：The rare earth manganese heteronuclear metal cluster compound according to claim 3, characterized in that the cluster compound having the structure shown in formula I is selected from any cluster compound in the following cluster compounds 1 to 5 :簇合物1，化学式为Mn 3YO 2(R 1CO 2) 9(R 1CO 2H) 3，其中，R 1＝叔丁基； Cluster 1, the chemical formula is Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , where R 1 = tert-butyl;簇合物1为单晶；其结构如式I-1所示：Cluster 1 is a single crystal; its structure is shown in formula I-1:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为α＝77.526(3)°，β＝87.004(2)°，γ＝65.818(3)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are
α=77.526(3)°, β=87.004(2)°, γ=65.818(3)°, Z=2, the volume is簇合物2，化学式为Mn 3LaO 2(R 1CO 2) 9(R 1CO 2H) 3，其中，R 1＝叔丁基； Cluster 2, the chemical formula is Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , where R 1 = tert-butyl;簇合物2为单晶；其结构如式I-2所示：Cluster 2 is a single crystal; its structure is shown in formula I-2:
其单晶属于单斜晶系，空间群为P2 1/n，晶胞参数为
α＝90°，β＝107.516(4)°，γ＝90°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
α=90°, β=107.516(4)°, γ=90°, Z=4, the volume is簇合物3，化学式为Mn 3GdO 2(R 1CO 2) 9(R 1CO 2H) 3，其中，R 1＝叔丁基； Cluster 3, the chemical formula is Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , where R 1 = tert-butyl;簇合物3为单晶；其结构如式I-3所示：Cluster 3 is a single crystal; its structure is shown in formula I-3:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为α＝77.898(2)°，β＝87.087(2)°，γ＝65.755(2)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are
α=77.898(2)°, β=87.087(2)°, γ=65.755(2)°, Z=2, the volume is簇合物4，化学式为Mn 3DyO 2(R 1CO 2) 9(R 1CO 2H) 3，其中，R 1＝叔丁基； Cluster 4, the chemical formula is Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , wherein, R 1 = tert-butyl;簇合物4为单晶；其结构如式I-4所示：Cluster 4 is a single crystal; its structure is shown in formula I-4:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为α＝77.790(2)°，β＝86.995(2)°，γ＝65.678(2)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are
α=77.790(2)°, β=86.995(2)°, γ=65.678(2)°, Z=2, the volume is簇合物5，化学式为Mn 3LuO 2(R 1CO 2) 9(R 1CO 2H) 3，其中，R 1＝叔丁基； Cluster 5, the chemical formula is Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 , where R 1 = tert-butyl;簇合物5为单晶；其结构如式I-5所示：Cluster 5 is a single crystal; its structure is shown in formula I-5:
其单晶属于三斜晶系，空间群为P-1，晶胞参数为α＝77.450(3)°，β＝87.291(3)°，γ＝65.954(3)°，Z＝2，体积为
Its single crystal belongs to the triclinic crystal system, the space group is P-1, and the unit cell parameters are
α=77.450(3)°, β=87.291(3)°, γ=65.954(3)°, Z=2, the volume is - 根据权利要求3所述的稀土锰异核金属簇合物，其特征在于，具有式II所示结构的簇合物选自如下簇合物6～簇合物8中的任一簇合物：The rare earth manganese heteronuclear metal cluster compound according to claim 3, wherein the cluster compound having the structure shown in formula II is selected from any cluster compound in the following cluster compounds 6 to 8:簇合物6，化学式为Mn 4YO 4(R 1CO 2) 8(L 1)(L 2)(L 3)，其中，R 1＝叔丁基，L 1和L 2连接后为特戊酸根(例如三甲基乙酸根，即式II-1中R 2为叔丁基)，L 3＝异喹啉； Cluster 6, the chemical formula is Mn 4 YO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, and L 1 and L 2 are connected to be pentyl Acid group (such as trimethyl acetate, that is, R 2 in formula II-1 is a tert-butyl group), L 3 = isoquinoline;所述簇合物6为单晶；其结构如式II-1所示：The cluster compound 6 is a single crystal; its structure is shown in formula II-1:
其单晶属于单斜晶系，空间群为P2 1/n，晶胞参数为
α＝90.00°，β＝101.6590(10)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
α=90.00°, β=101.6590(10)°, γ=90.00°, Z=4, the volume is簇合物7，化学式为Mn 4GdO 4(R 1CO 2) 8(L 1)(L 2)(L 3)，其中，R 1＝叔丁基，L 1和L 2连接后为特戊酸根，即式II-2中R 2为叔丁基，L 3＝异喹啉； Cluster 7, the chemical formula is Mn 4 GdO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, and L 1 and L 2 are connected to be pentyl Acid radical, that is, in formula II-2, R 2 is tert-butyl, L 3 = isoquinoline;所述簇合物7为单晶；其结构如式II-2所示：The cluster compound 7 is a single crystal; its structure is shown in formula II-2:
其单晶属于单斜晶系，空间群为P2 1/n，晶胞参数为
α＝90.00°，β＝101.799(2)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
α=90.00°, β=101.799(2)°, γ=90.00°, Z=4, the volume is簇合物8，化学式为Mn 4LuO 4(R 1CO 2) 8(L 1)(L 2)(L 3)，其中，R 1＝叔丁基，L 1和L 2连接后为特戊酸根，即式II-3中R 2为叔丁基，L 3＝异喹啉； Cluster 8, the chemical formula is Mn 4 LuO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ), wherein, R 1 = tert-butyl, L 1 and L 2 are connected to be pentyl Acid radical, that is, in formula II-3, R 2 is tert-butyl, L 3 = isoquinoline;所述簇合物8为单晶；其结构如式II-3所示：The cluster compound 8 is a single crystal; its structure is shown in formula II-3:
其单晶属于单斜晶系，空间群为P2 1/n，晶胞参数为
α＝90.00°，β＝101.7670(10)°，γ＝90.00°，Z＝4，体积为
Its single crystal belongs to the monoclinic crystal system, the space group is P2 1 /n, and the unit cell parameters are
α=90.00°, β=101.7670(10)°, γ=90.00°, Z=4, the volume is - 根据权利要求3所述的稀土锰异核金属簇合物，其特征在于，具有式III所示结构的簇合物选自如下簇合物9～簇合物11中任一簇合物：The rare earth manganese heteronuclear metal cluster compound according to claim 3, wherein the cluster compound having the structure shown in formula III is selected from any cluster compound in the following cluster compounds 9 to 11:簇合物9，化学式为Mn 4YO 5H(RCO 2) 8(L 4)(L 5)，其中，R 1＝叔丁基；L 4、L 5均为N,N-二甲基乙酰胺； Cluster 9, the chemical formula is Mn 4 YO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides;所述簇合物9为单晶；其结构如式III-1所示：The cluster compound 9 is a single crystal; its structure is shown in formula III-1:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are
α=90°, β=90°, γ=90°, Z=8, the volume is簇合物10，化学式为Mn 4DyO 5H(RCO 2) 8(L 4)(L 5)，其中，R 1＝叔丁基；L 4、L 5均为N,N-二甲基乙酰胺； Cluster 10, the chemical formula is Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides;所述簇合物10为单晶；其结构如式III-2所示：The cluster compound 10 is a single crystal; its structure is shown in formula III-2:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are
α=90°, β=90°, γ=90°, Z=8, the volume is簇合物11，化学式为Mn 4LuO 5H(RCO 2) 8(L 4)(L 5)，其中，R 1＝叔丁基；L 4、L 5均为N,N-二甲基乙酰胺； Cluster 11, the chemical formula is Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ), where R 1 = tert-butyl; L 4 and L 5 are both N,N-dimethylethyl amides;所述簇合物11为单晶；其结构如式III-3所示：The cluster compound 11 is a single crystal; its structure is shown in formula III-3:
其单晶属于正交晶系，空间群为Pbca，晶胞参数为
α＝90°，β＝90°，γ＝90°，Z＝8，体积为
Its single crystal belongs to the orthorhombic crystal system, the space group is Pbca, and the unit cell parameters are
α=90°, β=90°, γ=90°, Z=8, the volume is - 根据权利要求1-6任一项所述的稀土锰异核金属簇合物的制备方法，其特征在于，所述方法包括如下步骤：将高锰酸根阴离子型氧化剂、稀土盐和配体，任选地加入水或二价锰盐，在溶液中反应，制备得到所述簇合物。According to the preparation method of the rare earth manganese heteronuclear metal cluster described in any one of claims 1-6, it is characterized in that the method comprises the following steps: permanganate anionic oxidant, rare earth salt and ligand, any Optionally add water or divalent manganese salt and react in solution to prepare the cluster compound.
- 根据权利要求7所述的稀土锰异核金属簇合物的制备方法，其特征在于，具有式I所示结构的化学式为Mn 3XO 2(R 1CO 2) 9(R 1CO 2H) 3的簇合物的制备方法包括如下步骤：将有机羧酸R 1COOH、高锰酸根阴离子型氧化剂、稀土盐，任选地加入水或二价锰盐，在乙腈溶液中反应，制备得到所述簇合物； The preparation method of rare earth manganese heteronuclear metal clusters according to claim 7, characterized in that the chemical formula having the structure shown in formula I is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) The preparation method of the cluster compound of 3 comprises the following steps: react organic carboxylic acid R 1 COOH, permanganate anion oxidizing agent, rare earth salt, optionally adding water or divalent manganese salt in acetonitrile solution to prepare the obtained said clusters;或者，具有式II所示结构的化学式为Mn 4XO 4(R 1CO 2) 8(L 1)(L 2)(L 3)的簇合物的制备方法包括如下步骤： Or, the preparation method of the cluster with the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) having the structure shown in formula II comprises the following steps:(1)将有机羧酸R 1COOH、高锰酸根阴离子型氧化剂、二价锰盐和稀土盐，在乙腈溶液中反应，制备中间体； (1) react organic carboxylic acid R 1 COOH, permanganate anionic oxidizing agent, divalent manganese salt and rare earth salt in acetonitrile solution to prepare intermediate;(2)将步骤(1)中中间体与配体L 3反应，任选地与配体L 1和/或L 2反应，制备得到具有式II所示结构的化学式为Mn 4XO 4(R 1CO 2) 8(L 1)(L 2)(L 3)的簇合物； (2) Reaction of the intermediate in step (1) with the ligand L 3 , optionally with the ligand L 1 and/or L 2 to prepare the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) clusters;或者，具有式III所示结构的化学式为Mn 4XO 5H(R 1CO 2) 8(L 4)(L 5)的簇合物的制备方法包括：将具有式II所示结构的簇合物溶于卤代烃和/或酯类溶剂中，加入水，任选地加入或不加入配体L 4和配体L 5，反应，得到具有III所示结构的簇合物。 Alternatively, the preparation method of the cluster compound having the structure shown in formula III as Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) comprises: combining the cluster compound having the structure shown in formula II The compound is dissolved in halogenated hydrocarbon and/or ester solvent, added with water, optionally with or without ligand L 4 and ligand L 5 , and reacted to obtain a cluster compound with the structure shown in III.
- 一种仿生水裂解催化剂，其特征在于，所述催化剂含有权利要求1-6任一项所述的簇合物。A biomimetic water splitting catalyst, characterized in that the catalyst contains the cluster compound according to any one of claims 1-6.
- 权利要求9所述仿生水裂解催化剂的应用，其特征在于，所述催化剂应用于催化水的裂解；所述催化过程在电极表面进行，或在氧化剂存在下进行。The application of the biomimetic water splitting catalyst according to claim 9, characterized in that the catalyst is used to catalyze the splitting of water; the catalytic process is carried out on the surface of an electrode, or in the presence of an oxidizing agent.
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