CN109748939B - Containing [ Mn3SrO4]And [ Mn4SrO4]Cluster compound with core structure and preparation method and application thereof - Google Patents

Containing [ Mn3SrO4]And [ Mn4SrO4]Cluster compound with core structure and preparation method and application thereof Download PDF

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CN109748939B
CN109748939B CN201711059799.1A CN201711059799A CN109748939B CN 109748939 B CN109748939 B CN 109748939B CN 201711059799 A CN201711059799 A CN 201711059799A CN 109748939 B CN109748939 B CN 109748939B
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张纯喜
陈长辉
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Abstract

The invention discloses a catalyst containing [ Mn3SrO4]And [ Mn4SrO4]A cluster compound with a core structure, a preparation method and application thereof. The present inventors have found that simple and inexpensive Mn is used2+、Sr2+Inorganic compound and carboxylic acid are used as raw materials, high manganese acid anion is used as an oxidant, and [ Mn ] is obtained by one-step synthesis3SrO4]Cluster compound, and further realize asymmetric bionic water cracking catalyst [ Mn ] in the presence of water4SrO4]Synthesis of Cluster Compound, [ Mn ]4SrO4]The clusters are capable of catalyzing the cracking of water and the release of oxygen in the presence of an oxidizing agent. Neutral [ Mn ] obtained by the invention3SrO4](R1CO2)6(R1CO2H)3The cluster compound is used as a precursor for synthesizing the bionic water cracking catalyst and can be used for synthesizing different types of bionic water cracking catalysts. [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4) The cluster compound can be used as an artificial water cracking catalyst for catalytic cracking of water on the surface of an electrode or driven by an oxidant (which can be a stable oxidant or a transient oxidant generated by light induction). Such [ Mn ]3SrO4]Cluster compound and [ Mn4SrO4]No related literature reports on the bionic water cracking catalyst exist at present.

Description

Containing [ Mn3SrO4]And [ Mn4SrO4]Cluster compound with core structure and preparation method and application thereof
Technical Field
The invention relates to a bionic water cracking catalyst containing a manganese-strontium cluster compound. In particular, the invention relates to compositions containing [ Mn3SrO4]And [ Mn4SrO4]Two kinds of cluster compounds with core structures, and preparation method and application thereof, wherein [ Mn4SrO4]The cluster compound can be directly used as an artificial catalyst for catalyzing water cracking, and [ Mn ]3SrO4]The cluster compound can be used as a precursor for synthesizing the bionic water cracking catalyst.
Background
The problems of energy crisis and environmental pollution are two key problems restricting the continuous development of human society in the twenty-first century. If abundant water on the earth can be cracked by using inexhaustible solar energy, oxygen is released, electrons and protons are obtained, and electric energy or hydrogen energy is generated, the problems of energy crisis and environmental pollution of human beings can be fundamentally solved. However, water is a thermodynamically very stable substance and a suitable catalyst is necessary to achieve its efficient and safe cracking. In recent years, many research groups internationally synthesize artificial catalysts with water splitting function by using noble metals such as ruthenium, iridium and the like and some complex ligands, but the use of the noble metals and the complex ligands causes high preparation cost of the catalysts and easily causes environmental pollution, so the catalysts are difficult to popularize and apply. How to prepare the high-efficiency, cheap and environment-friendly water cracking catalyst is an unsolved scientific problem.
The photosystem II of the photosynthetic organisms is the only biological system which can efficiently and safely utilize cheap metal ions (Mn and Ca) to realize water splitting, obtain electrons and protons and release oxygen in the nature. Photosystem II is capable of efficiently and safely splitting water because it possesses a unique [ Mn ]4Ca]Cluster catalytic centers. The recent three-dimensional crystal structure research of photosystem II with high resolution reveals that the biological water cracking catalytic center consists of [ Mn3CaO4]Cubic alkane and one Mn ion pass through O2-The bridge connection constituting an asymmetry [ Mn ]4CaOn](the value of n depends on the redox state of the catalyst, which may be 4 or 5) heteronuclear metal clusters, the periphery of which is provided with ligands by six carboxyl groups, one imidazole ring and four water molecules.
The inventor filed an invention named "a Mn-containing solution on day 2/6 of 20154CaO4Chinese patent CN 104761591B of chinese invention patent CN 104761591B of core structure, its preparation method and its application, the entire content of which is incorporated herein by reference. Wherein the patent protects the structural formula shown below:
Figure BDA0001454524240000021
wherein the content of the first and second substances,
R1is selected from H or C1-8A linear or branched alkyl group;
L1，L2,L3the three ligands are the same or different and are respectively and independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and derivatives thereof, or exchangeable neutral small molecules such as water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and the like.
How to chemically synthesize and prepare a catalytic center similar to biological water cracking is an important scientific frontier and is a very challenging scientific problem. The artificial Mn with the structure and the performance similar to those of a biological water cracking catalytic center is successfully prepared internationally in the earlier stage for the first time4Ca]Clusters, but which are sensitive to the environment, in particular Ca among them2+Ions are subject to dissociation, resulting in loss of catalytic performance of the artificial catalyst.
Biological research shows that calcium ions in the biological water cracking catalytic center can be replaced by strontium ions to generate [ Mn4Sr]Clusters, both steric structure and catalytic function of which are associated with biological [ Mn4Ca]Clusters are similar, but biological [ Mn4Sr]The stability of cluster water splitting catalytic centers is significantly increased (F.H.M.Koua, Y.Umena, K.Kawakami and J.R.Shen, Proc.Natl.Acad.Sci.USA, 2013,110, 3889-. During the water splitting process, the biocatalyst undergoes five different states (S)0,S1,S2,S3,S4). Wherein the dark steady state (S)1State) the valence of the four manganese ions is (+3, +3, +4, + 4). The disclosure of the water cracking catalysis center structure of the photosynthetic organisms provides an ideal blueprint for developing a low-cost, high-efficiency and environment-friendly bionic water cracking catalyst.
Disclosure of Invention
The invention provides [ Mn3SrO4]And][Mn4SrO4]two novel clusters and preparation methods thereof: first, using a cheap metal ion (Mn)2+,Sr2+Ionic), simple organic carboxylic acids and permanganate anionsIon MnO4 -(as an oxide) as a starting material, synthesized in one step to contain [ Mn3SrO4][ Mn ] of cubane3SrO4]A cluster, the periphery of which is provided with ligands by six carboxyl anions and three neutral carboxylic acid molecules, wherein the valence states of the three manganese ions are all +4, and the [ Mn ] of the ligands is completely provided by the carboxylic acid3SrO4]Cluster compounds, the synthesis and isolation of which is to prepare biomimetics [ Mn ], have not been reported before4Sr]The catalyst provides important basis, and simultaneously, the [ Mn ] is used3SrO4]The unpaired electrons of the three + 4-valent manganese ions in the cluster compound are in a high-spin state, and the magnetic material has important application value.
In the synthesis of [ Mn3SrO4]Based on the cluster compound, the method successfully realizes the utilization of cheap metal ions (Mn)2+,Sr2+Ionic), simple organic carboxylic acids and MnO4 -As starting material. Through extensive experiments, we found that this novel cluster can be formed in situ in the presence of water [ Mn4SrO4]Core, reacting with pyridine, and synthesizing to obtain stable [ Mn ]4SrO4]Cluster bionic water cracking catalyst. In this new form, [ Mn ]4SrO4]In the cluster, [ Mn ]3SrO4]Cubic alkane and one Mn ion through one O2-Bridging to form an asymmetric [ Mn ]4SrO4]Core structure, [ Mn ]4SrO4]Consists of eight carboxyl anions and four exchangeable neutral ligands. Wherein the valence states of the four manganese ions are (+3, + 4). This novel cluster and organism [ Mn ]4Sr]The catalytic center of water cracking is very similar to the [ Mn ] synthesized by the inventor in the previous period4Ca]The structure and properties of the clusters are similar. Prophase of [ Mn4Ca]The synthesis of the cluster compound does not require the presence of water, since the addition of water leads to failure of the synthesis reaction. This time [ Mn ]4Sr]The synthesis of clusters must be in the presence of water or else results in the formation of completely different compounds (c.chen, c.zhang, h.dong and j.zhao, chem.commun.,2014,50,9263-9265)。[Mn4SrO4]Cluster compound and [ Mn4CaO4]Cluster compound of Sr2+The stability of the cluster compound is obviously increased due to the introduction of ions, and due to Sr2+Having three neutral ligands (Ca) on the ion2+Only two neutral ligands on the ion) such that [ Mn4SrO4]The cluster compound is more suitable for being modified into different types of artificial water cracking catalysts, so that the requirements of future practical application are more likely to be met. Such [ Mn ]4SrO4]The cluster compound can catalyze the water cracking reaction in the presence of an oxidant to release oxygen. The cluster compound and the derivative of the modified structure can be used as an artificial catalyst for bionic water splitting.
It is an object of the present invention to provide a catalyst containing [ Mn3SrO4]And [ Mn4SrO4]A cluster compound with a core structure, a preparation method and application thereof.
It is another object of the present invention to provide a catalyst containing [ Mn4SrO4]A bionic water cracking catalyst with a core structure, a preparation method and application thereof.
The invention also aims to provide a compound and a preparation method and application thereof.
The invention is realized by the following technical scheme:
(1) [ Mn ] shown as formula I3SrO4](R1CO2)6(R1CO2H)3A compound, characterized in that: the compound contains three Mn ions and one Sr2+Ions passing through four O2-Ionically bonded to form [ Mn3SrO4]Heteronuclear metal cluster framework cores;
[Mn3SrO4]the peripheral ligand of the cluster is composed of six carboxylic acid anions (R)1CO2 -) And three neutral carboxylic acid ligands (R)1CO2H) Wherein the valence states of three Mn ions are +4, and the whole cluster compound is electrically neutral.
Figure BDA0001454524240000041
Wherein R is1Is selected from H or C1-8Straight or branched chain alkyl.
According to a preferred embodiment of the invention, the carboxylic acid anion (R)1CO2 -) Examples of the anion include carboxylic acid anions such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid. Namely, R1Can be hydrogen (H) or methyl (-CH)3) Ethyl (-C)2H5) N-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (- (CH)2)3CH3) Isobutyl (-CH (CH)3)C2H5) T-butyl (-C (CH))3)3) N-pentyl (- (CH)2)4CH3) Isopentyl (-CH)2CH2CH(CH3)2And the like.
Particularly preferably, the compound of formula I is selected from:
compound 1, [ Mn3SrO4](R1CO2)6(R1CO2H)3Wherein R is1Tert-butyl.
Preferably, compound 1 is single crystalline. The single crystal is a trigonal system, the space group is R-3c, and the cell parameter is
Figure BDA0001454524240000042
Figure BDA0001454524240000043
α 90.00 degrees, β 90.00 degrees, gamma 120.00 degrees, Z6 degrees, and the volume is
Figure BDA0001454524240000044
The structure is shown as formula I-1:
Figure BDA0001454524240000051
(2) [ Mn ] shown as formula II4SrO4](R1CO2)8(L1)(L2)(L3)(L4) A compound, characterized in that: the compound contains four Mn ions and one Sr2+Ions passing through four O2-Ionic linkage into asymmetric [ Mn ]4SrO4]Heteronuclear metal cluster skeleton core.
[Mn4SrO4]The peripheral ligand of the cluster is composed of eight carboxylic acid anions (R)1CO2 -) And four neutral ligands (L)1、L2、L3、 L4) Provided is a method. The valence states of the four Mn ions are (+3, +3, +4, +4), respectively, and the whole cluster is electrically neutral.
Figure BDA0001454524240000052
Wherein R is1Is selected from H or C1-8A linear or branched alkyl group;
L1、L2、L3、L4the four ligands are the same or different and are respectively and independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline, bipyridine and derivatives thereof, or exchangeable neutral small molecules such as water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and the like.
According to a preferred embodiment of the invention, the carboxylic acid anion (R)1CO2 -) Examples of the anion include carboxylic acid anions such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid. Namely, R1Can be hydrogen (H) or methyl (-CH)3) Ethyl (-C)2H5) N-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (- (CH)2)3CH3) Isobutyl (-CH)2CH(CH3)2) T-butyl (-C (CH))3)3) N-pentyl (- (CH)2)4CH3) Isopentyl (-CH)2CH2CH(CH3)2) And the like.
Particularly preferably, the compound of formula II is selected from:
[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Wherein R is1T-butyl L1L from pyridine2＝L3＝L4Pivalic acid.
Most preferably, the compound of formula II is selected from the following compounds:
compound 2, [ Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Wherein R is1T-butyl L1L from pyridine2＝L3＝L4Pivalic acid (or 2, 2-dimethylpropionic acid, or trimethylacetic acid, corresponding to R1COOH，R1A tert-butyl structure).
Preferably, the compound 2 is a single crystal. The single crystal is an orthorhombic system, the space group is Pna21, and the unit cell parameter is
Figure BDA0001454524240000064
Figure BDA0001454524240000062
α 90.00 degrees, β 90.00 degrees, gamma 90.00 degrees, Z4 degrees, and the volume is
Figure BDA0001454524240000063
The structure of compound 2 is shown in formula II-1 below:
Figure BDA0001454524240000061
(3) the invention also provides a complex, wherein the complex is formed by the association of two or more compounds of formula II:
Figure BDA0001454524240000071
wherein each substituent group is defined as shown in formula II.
Particularly preferably, the complex is selected from the following:
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate;
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]wherein R is1T-butyl L1L from Arthroquine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
Most preferably, the complex is selected from any of the following complexes:
complex 3, [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
Preferably, the compound 3 is a single crystal. The single crystal is monoclinic system, and the space group is P121C1, unit cell parameter of
Figure BDA0001454524240000074
Figure BDA0001454524240000072
90.00 degrees, β 92.6590(10 degrees), γ 90.00 degrees, Z4 degrees, and volume
Figure BDA0001454524240000073
In the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]Part of the structure is similar to the formula II-1, wherein [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]In part represented by formula II-2:
Figure BDA0001454524240000081
complex 4, [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from Arthroquine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
Preferably, the composite 4 is a single crystal. The single crystal is a triclinic system, the space group is P-1, and the unit cell parameters are
Figure BDA0001454524240000083
Figure BDA0001454524240000082
α is 76.547(5) °, β is 87.559(6) °, γ is 73.153(6) °, and Z is 2, and the volume is 76.547(5) °
Figure BDA0001454524240000084
In the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]Part is shown as formula II-3-1; in the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]The moiety is represented by the following formula II-3-2:
Figure BDA0001454524240000091
(4) [ Mn ] as shown in formula I3SrO4](R1CO2)6(R1CO2H)3A method for preparing a compound, the method comprising:
mixing acid (preferably organic carboxylic acid), oxidant, Mn2+Salt, Sr2+Heating and reacting a salt in an acetonitrile solution at a molar ratio of x: y:1:1(x is 10-120, y is 1-10; preferably x is 20-100, and y is 2-8) for 10-60 minutes to obtain a solution, and filtering to remove precipitates; standing for 1-6 days to obtain crystals.
According to the invention, the reagents used are as follows: manganese (II) salt Mn2+Can be various Mn-containing2+A carboxylic acid salt of (1). Wherein the carboxylic acid anion (R)1CO2 -) As mentioned above, the carboxyl group may be, for example, formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate, or a derivative thereof (preferably, acetate, pivalate); it may also be Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2And divalent manganese salts. These salts may be derivatives containing different numbers of water of crystallization (number n of water of crystallization is 0 to 6, preferably 1 to 5, or 2 to 4).
Sr2+The salts may be various strontium carboxylates. Wherein the carboxylic acid anion (R)1CO2 -) As mentioned above, the carboxyl group may be, for example, formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate, or a derivative thereof (preferably, acetate, pivalate); or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2And the like. These salts may be derivatives thereof containing different numbers of water of crystallization (the number n of water of crystallization is 0 to 6, preferably 0 to 5, or 2 to 4).
The oxidant is preferably an anionic permanganate oxidant, more preferably ammonium tetrabutylpermanganate ((C)4H9)4N·MnO4)。
The acid is preferably an organic carboxylic acid. Such as: carboxyl groups such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid, and derivatives thereof (preferably isobutyric acid and pivalic acid).
The volume of acetonitrile solvent is about 60-100 ml acetonitrile per millimole strontium salt.
The present inventors have found that the above reaction can be carried out only in an acetonitrile solvent, and that the target compound cannot be obtained in any of alcohols and other organic solvents.
According to the invention, the reaction temperature is 60 to 90 ℃, for example 70 to 80 ℃.
According to the invention, the reaction time may be 10 to 60 minutes, for example 20 to 50 minutes.
(5) The invention also provides compounds of formula I [ Mn3SrO4](R1CO2)6(R1CO2H)3As synthetic biomimetics [ Mn4SrO4]Use of a precursor of a water-splitting catalyst.
Preferably, the compounds of formula I according to the invention are used for the conversion of [ Mn ] in the presence of water3SrO4]Formation of Cluster Compound [ Mn4SrO4]A cluster compound.
Preferably, the compounds of formula I according to the invention are used for the conversion of [ Mn ] in the presence of water3SrO4]Formation of Cluster Compound [ Mn4SrO4]The cluster compounds, in turn, catalyze the oxygen evolution reaction.
According to a preferred embodiment of the invention, the compound 1 according to the invention has the formula C45H84Mn3O22Sr, its structure is [ Mn3SrO4](R1CO2)6(R1CO2H)3Wherein R is1Tert-butyl.
Compound 1 is a single crystal. The single crystal is a trigonal system, the space group is R-3c, and the unit cell parameter is
Figure BDA0001454524240000101
Figure BDA0001454524240000102
α 90.00 degrees, β 90.00 degrees, gamma 120.00 degrees, Z6 degrees, and the volume is
Figure BDA0001454524240000103
Figure BDA0001454524240000112
The structure is shown as formula I: the crystal structure is shown in FIG. 1, and the single crystal parameters are shown in Table 1.
Table 1: single Crystal parameter of Compound 1
Figure BDA0001454524240000111
(6) [ Mn ] as shown in formula II4SrO4](R1CO2)8(L1)(L2)(L3)(L4) A method for preparing a compound, the method comprising:
the first step is as follows: mixing acid (preferably organic carboxylic acid), oxidant, Mn2+Salt, Sr2+Heating salt and water in a molar ratio of x to y to 1 to z (x is 10-120, y is 1-10, z is 0-20, preferably x is 20-100, y is 2-8, and z is 0-10) in an acetonitrile solution for 10-60 minutes to obtain a solution, and filtering to remove precipitates; obtaining crystals, preferably crystallizing the solution at 0 ℃ to obtain crystals;
secondly, dissolving the crystal obtained in the first step in an ester solvent, and adding an organic ligand L1,L2,L3,L4Crystallization gives the product.
Wherein the product obtained in the second step can be further treated (e.g. recrystallized) with alkanes, cycloalkanes or halogenated hydrocarbons to obtain the final product.
According to the invention, the reagents used are as follows: the divalent manganese salt can be various Mn-containing salts2+A carboxylic acid salt of (1). Wherein the carboxylic acid anion (R)1CO2 -) As mentioned above, the carboxyl group may be, for example, formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate, or a derivative thereof (preferably, acetate, pivalate); it may also be Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2And divalent manganese salts. These salts may be derivatives containing different numbers of water of crystallization (number n of water of crystallization is 0 to 6, preferably 1 to 5, or 2 to 4).
Sr2+The salts may be various strontium carboxylates. Wherein the carboxylic acid anion (R)1CO2 -) As mentioned above, the carboxyl group may be, for example, formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate, or a derivative thereof (preferably, acetate, pivalate); or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2And the like. These salts may be derivatives thereof containing different numbers of water of crystallization (the number n of water of crystallization is 0 to 6, preferably 0 to 5, or 2 to 4).
The oxidant is preferably an anionic permanganate oxidant, more preferably ammonium tetrabutylpermanganate ((C)4H9)4N·MnO4)。
The acid is preferably an organic carboxylic acid. Such as: carboxyl groups such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid, and derivatives thereof (preferably acetic acid and pivalic acid).
The volume of acetonitrile solvent in the first step is about 60-100 ml per millimole of strontium salt. The reaction can only be carried out in acetonitrile solvent, and the target compound can not be obtained in alcohol and other organic solvents.
According to the present invention, the ester organic solvent in the second reaction step may be an ester such as ethyl acetate, methyl acetate, propyl propionate, etc. The organic solvent for recrystallization of the product can be normal hexane, isooctane, dichloroethane, dichloromethane and other straight-chain or branched alkanes, halogenated hydrocarbons and derivatives thereof.
The organic ligands are the same or different and are respectively and independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, bipyridine, isoquinoline and derivatives thereof, or exchangeable neutral small molecules such as water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and the like.
According to the invention, the reaction temperature is 60 to 90 ℃, for example 70 to 80 ℃.
According to the invention, the reaction time may be 10 to 60 minutes, for example 20 to 50 minutes.
(7) The invention also provides a preparation method of the compound, which is characterized by comprising the following steps:
the first step is as follows: mixing acid (preferably organic carboxylic acid), oxidant, Mn2+Salt, Sr2+Heating salt and water in a molar ratio of x to y to 1 to z (x is 10-120, y is 1-10, z is 0-20, preferably x is 20-100, y is 2-8, and z is 0-10) in an acetonitrile solution for 10-60 minutes to obtain a solution, and filtering to remove precipitates; obtaining crystals, preferably crystallizing the solution at 0 ℃ to obtain crystals;
secondly, dissolving the crystal obtained in the first step in an ester solvent, and adding an organic ligand L1,L2,L3,L4Crystallizing to obtain a primary product;
the third step: the product obtained in the second step is optionally further processed (for example by rinsing or recrystallisation with alkanes, cycloalkanes or halohydrocarbons) to give the final product. Preferably, the product is dissolved in an ester solvent prior to further processing.
According to the invention, the reagents used are as follows: the divalent manganese salt can be various Mn-containing salts2+A carboxylic acid salt of (1). Wherein the carboxylic acid anion (R)1CO2 -) As beforeExamples of the carboxyl group include a carboxyl group such as formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, and hexanoate, and derivatives thereof (preferably acetate, pivalate); it may also be Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2And divalent manganese salts. These salts may be derivatives containing different numbers of water of crystallization (number n of water of crystallization is 0 to 6, preferably 1 to 5, or 2 to 4).
Sr2+The salts may be various strontium carboxylates. Wherein the carboxylic acid anion (R)1CO2 -) As mentioned above, the carboxyl group may be, for example, formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate, or a derivative thereof (preferably, acetate, pivalate); or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2And the like. These salts may be derivatives thereof containing different numbers of water of crystallization (the number n of water of crystallization is 0 to 6, preferably 0 to 5, or 2 to 4).
The oxidant is preferably an anionic permanganate oxidant, more preferably ammonium tetrabutylpermanganate ((C)4H9)4N·MnO4)。
The acid is preferably an organic carboxylic acid. Such as: carboxyl groups such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid, and derivatives thereof (preferably acetic acid and pivalic acid).
The volume of acetonitrile solvent in the first step is about 60-100 ml per millimole of strontium salt. The reaction can only be carried out in acetonitrile solvent, and the target compound can not be obtained in alcohol and other organic solvents.
According to the present invention, the ester organic solvent in the second reaction step may be an ester such as ethyl acetate, methyl acetate, propyl propionate, etc. The organic solvent for recrystallization of the product can be normal hexane, isooctane, dichloroethane, dichloromethane and other straight-chain or branched alkanes, halogenated hydrocarbons and derivatives thereof.
The organic ligands are the same or different and are respectively and independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, bipyridine, isoquinoline and derivatives thereof, or exchangeable neutral small molecules such as water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and the like.
According to the invention, the reaction temperature is 60 to 90 ℃, for example 70 to 80 ℃.
According to the invention, the reaction time may be 10 to 60 minutes, for example 20 to 50 minutes.
(8) The invention also provides application of the compound shown in the formula II as a bionic water cracking catalyst.
Preferably, the compound of formula II is used to drive the catalytic cracking of water in the presence of an oxidant (which may be a stable oxidant or a light-induced transient oxidant) to release oxygen.
(9) The invention also provides the application of the compound as a bionic water cracking catalyst.
Preferably, the compound is used to drive the catalytic cracking of water in the presence of an oxidant (which may be a stable oxidant or a light-induced transient oxidant) to release oxygen.
(10) The present invention also provides a water-splitting catalyst characterized by containing [ Mn ] represented by the above formula of the present invention4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Compounds of the class in which the substituents are as defined above; and/or, a complex comprising the above, wherein each substituent is as defined above.
According to the invention, the compound 2 according to the invention has the formula C60H107Mn4NO26Sr, its structure is [ Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Wherein R is1T-butyl L1L from pyridine2＝L3＝L4Pivalic acid.
Compound 2 is a single crystal. The single crystal is an orthorhombic system, and the space group is Pna21Cell parameter of
Figure BDA0001454524240000142
Figure BDA0001454524240000143
α 90.00 degrees, β 90.00 degrees, gamma 90.00 degrees, Z4 degrees, and the volume is
Figure BDA0001454524240000144
Figure BDA0001454524240000145
The crystal structure is shown in FIG. 2, and the single crystal parameters are shown in Table 2.
Table 2: single Crystal parameter of Compound 2
Figure BDA0001454524240000141
Figure BDA0001454524240000151
The molecular formula of the compound 3 of the invention is C119H212Mn8N2O52Sr2The structure of which is [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
The compound 3 is a single crystal which is monoclinic and has a space group of P121C1, unit cell parameter of
Figure BDA0001454524240000153
Figure BDA0001454524240000154
α ═ 90.00 °, β ═ 92.6590(10 °), γ ═ 90.00 °, Z ═ 4, volume
Figure BDA0001454524240000155
The crystal structure is shown in FIG. 3, and the single crystal parameters are shown in Table 3:
table 3: single Crystal parameter of Compound 3
Figure BDA0001454524240000152
Figure BDA0001454524240000161
Inventive Compound 4, [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]The molecular formula is C132H226Mn8N2O54Sr2(ii) a Wherein R is1T-butyl L1L from Arthroquine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
The composite 4 is a single crystal. The single crystal is a triclinic system, the space group is P-1, and the unit cell parameters are
Figure BDA0001454524240000163
Figure BDA0001454524240000164
α is 76.547(5) °, β is 87.559(6) °, γ is 73.153(6) °, and Z is 2, and the volume is 76.547(5) °
Figure BDA0001454524240000165
The crystal structure is shown in FIG. 4, and the single crystal parameters are shown in Table 4:
table 4: single Crystal parameter of Compound 4
Figure BDA0001454524240000162
Figure BDA0001454524240000171
In the present invention, the [ Mn ] is described in the synthetic method3SrO4]And [ Mn4Sr]Cluster compound of [ Mn ]4SrO4]The synthesis of the clusters of the core structure must be in the presence of water, otherwise it leads to the formation of completely different compounds. Structurally, the [ Mn ]4SrO4]Cluster compound and [ Mn4CaO4]Cluster compound of Sr2+The stability of the cluster compound is obviously increased due to the introduction of ions, and due to Sr2+Having three neutral ligands (Ca) on the ion2+Only two neutral ligands on the ion) such that [ Mn4SrO4]The cluster compound is more suitable to be modified, so that the cluster compound is more likely to meet the requirements of practical application in the future. In addition, since both Sr ion and Ca ion are in the core of the cluster compound, there is no possibility of allowing them to exchange without destroying the entire structure. Therefore, the cluster compounds can only be synthesized from the source, and the synthesis of the cluster compounds is extremely sensitive to reaction conditions, and slight changes of the reaction conditions can cause great differences of the structure and the performance of final products.
The invention has the beneficial effects that:
the present inventors have found that simple and inexpensive Mn is used2+、Sr2+Inorganic compound and carboxylic acid are used as raw materials, high manganese acid anion is used as an oxidant, and [ Mn ] is obtained by one-step synthesis3SrO4]Cluster compound, and further realize asymmetric bionic water cracking catalyst [ Mn ] in the presence of water4SrO4]Synthesis of Cluster Compound, [ Mn ]4SrO4]The clusters are capable of catalyzing the cracking of water and the release of oxygen in the presence of an oxidizing agent.
Neutral [ Mn ] obtained by the invention3SrO4](R1CO2)6(R1CO2H)3The cluster compound is used as a precursor for synthesizing the bionic water cracking catalyst and can be used for synthesizing different types of bionic water cracking catalysts.
[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) The cluster compound can be used as an artificial water cracking catalyst for catalytic cracking of water on the surface of an electrode or driven by an oxidant (which can be a stable oxidant or a transient oxidant generated by light induction). Such [ Mn ]3SrO4]Cluster compound and [ Mn4SrO4]No related literature reports on the bionic water cracking catalyst exist at present.
Drawings
FIG. 1 is a crystal structure diagram of Compound 1 prepared in example 1 of the present invention. For clarity of illustration, the hydrogen atom and the methyl group of the t-butyl group and the solvent molecule are omitted.
FIG. 2 is a crystal structure diagram of Compound 2 prepared in example 2 of the present invention. For clarity of illustration, the hydrogen atom and the methyl group of the t-butyl group and the solvent molecule are omitted.
FIG. 3 is a crystal structure diagram of composite 3 prepared in example 3 of the present invention. For clarity of illustration, the hydrogen atom and the methyl group of the t-butyl group and the solvent molecule are omitted. Two of them [ Mn ]4SrO4]Cluster molecules, the difference between which is that one neutral pivalic acid molecule on the strontium ion is replaced by an ethyl acetate molecule.
FIG. 4 is a crystal structure diagram of composite 4 prepared in example 4 of the present invention. For clarity of illustration, the hydrogen atom and the methyl group of the t-butyl group and the solvent molecule are omitted. Two of them [ Mn ]4SrO4]Cluster molecules, the difference between which is that one neutral pivalic acid molecule on the strontium ion is replaced by an ethyl acetate molecule.
FIG. 5 is a trace of the change of UV-visible absorption spectrum of compound 2 in water according to example 5 of the present invention.
FIG. 6 shows the electron paramagnetic signal given by the oxidized compound 2 in example 6 of the present invention, and the data supports the valence states of four Mn ions in the ground-state compound 2 to be (+3, +3, +4, + 4).
FIG. 7 is a graph of example 7 of the present invention, which is a measurement of the ability of Compound 2 to catalyze the release of oxygen in the presence of an oxidizing agent.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
Example 1: compound 1, [ Mn3SrO4](C5H9O2)6(C5H9O2H)3
The preparation method comprises the following steps:
to a 100ml round bottom flask was added tetrabutylammonium permanganate (Bu)n 4N·MnO44mmol), manganese acetate (Mn (CH)3CO2)21mmol), strontium acetate (Sr (CH)3CO2)21mmol) and pivalic acid ((CH)3)3CCO2H, 40mmol) is continuously reacted in acetonitrile at the temperature of 80 ℃ for 25 minutes, the reaction is stopped, a small amount of precipitate is removed by filtration, and the obtained brown mother liquor is placed at the temperature of 0 ℃ for 1-6 days to separate out brown crystals. The resulting crystals were collected, dissolved in n-hexane and dried under vacuum with a yield of-60% (based on moles of Sr ions).
Compound 1, structural formula is [ Mn3SrO4](R1CO2)6(R1CO2H)3Wherein R is1Tert-butyl.
Namely the compound 1 with the structural formula [ Mn3SrO4](C5H9O2)6(C5H9O2H)3The molecular formula is as follows: c45H84Mn3O22Sr. Theory of elemental analysisTheoretical value of C, 43.96; h, 6.89; experimental values of C, 44.01; h, 6.84. The single crystal is a trigonal system, the space group is R-3c, and the cell parameter is
Figure BDA0001454524240000181
α 90.00 degrees, β 90.00 degrees, gamma 120.00 degrees, Z6 degrees, and the volume is
Figure BDA0001454524240000182
The chemical structure of the compound 1 is shown as the following formula I-1, the specific parameters of single crystal measurement are shown in Table 1, and the crystal space structure is shown in figure 1.
Figure BDA0001454524240000191
Example 2: compound 2, [ Mn4SrO4](C5H9O2)8(C5H9O2H)3(C5H5N)
The preparation method comprises the following steps:
the first step is the synthesis of the precursor of compound 2: to a 100ml round bottom flask was added tetrabutylammonium permanganate (Bu)n 4N·MnO44mmol), manganese acetate (Mn (CH)3CO2)21mmol), strontium acetate (Sr (CH)3CO2)21mmol) and pivalic acid ((CH)3)3CCO2H, 40mmol), water (H)2O, 1mmol) is continuously reacted in acetonitrile at the temperature of 80 ℃ for 25 minutes, then the reaction is stopped, a small amount of precipitate is removed by filtration, and the obtained brown mother liquor is placed at the temperature of 0 ℃ for 1-2 weeks to separate out brown crystals.
And the second step is to react with pyridine, wherein crystals obtained in the first step are collected and dissolved by ethyl acetate, 2% pyridine (volume ratio) is added, and brown crystals are separated out after 1-2 weeks. The resulting crystals were collected, dissolved in n-hexane, freed of small amounts of insoluble material, recrystallized, 1 week later brown crystals were precipitated, dried in vacuo, the yield was-12% (based on Sr)2+Moles of ions).
Compound 2, structural formula [ Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Wherein R is1T-butyl L1L from pyridine2＝L3＝L4Pivalic acid.
Namely the compound 2 with the structural formula of [ Mn4SrO4](C5H9O2)8(C5H9O2H)3(C5H5N)·(C6H14)1.5(note: n-hexane is a solvent molecule), molecular formula: c69H128Mn4NO26Sr. Theoretical value of element analysis is C, 48.89; h, 7.61; n,0.83 Experimental value C, 49.00; h, 7.51; n, 0.70. The single crystal of the compound 2 is an orthorhombic system with a space group of Pna21 and a unit cell parameter of
Figure BDA0001454524240000195
Figure BDA0001454524240000192
α 90.00 degrees, β 90.00 degrees, gamma 90.00 degrees, Z4 degrees, and the volume is
Figure BDA0001454524240000194
Figure BDA0001454524240000193
The chemical structure of the compound 2 is shown in the following formula II-1, the specific parameters of the single crystal measurement are shown in Table 2, and the crystal space structure is shown in figure 2.
Figure BDA0001454524240000201
Example 3 composite 3[ [ Mn ]4SrO4](C5H9O2)8(C5H5N)1(C5H9O2H)3]·[[Mn4SrO4](C5H9O2)8(C5H5N)1(C5H9O2H)2(C2H5O2CCH3)1]
The preparation method comprises the following steps:
weighing 0.100 g of compound 2, dissolving in ethyl acetate, standing at room temperature for 1-3 weeks, precipitating a slender brown crystal, leaching with cyclohexane, and vacuum drying to obtain a yield of-70% (based on Sr)2+Moles of ions).
Compound 3, structural formula
[]Mn4SrO4](R1CO2)8](L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8](L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
Namely, the compound 3 has the structural formula
[[Mn4SrO4](C5H9O2)8(C5H5N)1(C5H9O2H)3]·[[Mn4SrO4](C5H9O2)8(C5H5N)1(C5H9O2H)2(C2H5O2CCH3)1]. The molecular formula is as follows: c119H212Mn8N2O52Sr2. Theoretical value of elemental analysis: c, 45.84; h, 6.85; n, 0.90; experimental values: c, 45.82; h, 6.81; n, 1.21. The single crystal of the composite 3 is monoclinic system, and the space group is P121C1, unit cell parameter of
Figure BDA0001454524240000202
α ═ 90.00 °, β ═ 92.6590(10 °), γ ═ 90.00 °, Z ═ 4, volume
Figure BDA0001454524240000203
Chemical structure of Compound 3[ [ Mn ]4SrO4](C5H9O2)8(C5H5N)1(C5H9O2H)2(C2H5O2CCH3)1]The following formula II-2 shows the following formula, and the specific parameters of single crystal measurement of composite 3 are shown in Table 3, and the crystal space structure is shown in FIG. 3.
Figure BDA0001454524240000211
Example 4-the complex 4 was added to the reaction mixture,
[[Mn4SrO4](C5H9O2)8(C9H7N)1(C5H9O2H)3]·[[Mn4SrO4](C5H9O2)8(C9H7N)1(C5H9O2H)2(C2H5O2CCH3)1]。
the preparation method comprises the following steps:
the first step is the synthesis of complex 4 precursor: to a 100ml round bottom flask was added tetrabutylammonium permanganate (Bu)n 4N·MnO44mmol), manganese acetate (Mn (CH)3CO2)21mmol), strontium acetate (Sr (CH)3CO2)21mmol) and pivalic acid ((CH)3)3CCO2H, 40mmol) is continuously reacted in acetonitrile at the temperature of 80 ℃ for 25 minutes, the reaction is stopped, a small amount of precipitate is removed by filtration, and the obtained brown mother liquor is placed at the temperature of 0 ℃ for 1-2 weeks to separate out brown crystals.
The second step is reaction with isoquinoline: collecting the crystals obtained in the first step, dissolving the crystals with ethyl acetate, adding 1% isoquinoline (volume ratio) for recrystallization, collecting black crystals after 1-2 weeks, leaching the black crystals with cyclohexane, and drying the black crystals in vacuum, wherein the yield is 40% (according to Sr)2+Moles of ions).
Compound 4, the structural formula is
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]Wherein R is1T-butyl L1(iii) isoquinoline, L2＝L3＝L4Pivalic acid L4 *Ethyl acetate.
Namely, the compound 4 has the structural formula
[[Mn4SrO4](C5H9O2)8(C9H7N)1(C5H9O2H)3]·[[Mn4SrO4](C5H9O2)8(C9H7N)1(C5H9O2H)2(C2H5O2CCH3)1]The molecular formula is as follows: c132H226Mn8N2O54Sr2. The single crystal of the composite 4 is triclinic, the space group is P-1, and the unit cell parameters are
Figure BDA0001454524240000222
α is 76.547(5) °, β is 87.559(6) °, γ is 73.153(6) °, and Z is 2, and the volume is 76.547(5) °
Figure BDA0001454524240000223
The chemical structure of the complex 4 is shown in the following formulas II-3-1 and II-3-2, the specific single crystal measurement parameters are shown in Table 4, and the crystal space structure is shown in FIG. 4.
Figure BDA0001454524240000221
Experimental example 5: UV-VIS Spectroscopy tracking of Compound 2 with Water
Add 25 μ to cuvetteM Compound 2 in acetonitrile 1M L, with pure acetonitrile 1M L as a reference, measured in a Hitachi U-3900 spectrophotometer type UV-Vis spectrometer (see FIG. 5), which has a maximum absorption at 250 nm, with the addition of water molecules (0%, 0.15%, 0.35%, 0.55%, 1.05% water, respectively), the absorption spectrum undergoes a significant change, with a significant decrease in absorption at 250 nm and an increase in absorption at 400 nm, indicating that water molecules can interact with Compound 2 but with [ Mn [4CaO4]Comparison of Cluster Compound, [ Mn4SrO4]The sensitivity of the cluster to water is significantly reduced. [ Mn ]4SrO4]When the cluster compound exists in 1% of water, the absorption peak at 250 nm is reduced by only 20%, and the corresponding [ Mn ]4CaO4]The absorption peak at 250 nm of the cluster compound is reduced by more than 60% in the presence of 1% water, indicating [ Mn4SrO4]The spectrum of the crystal is not greatly influenced in the presence of a small amount of water, and [ Mn ]4CaO4]The cluster compound has a large influence on the spectrum of the cluster compound in the presence of a small amount of water, belongs to substances which are extremely sensitive to water, and the sensitivity causes the stability of the cluster compound to be reduced, so that the application is limited. The newly synthesized and discovered [ Mn ] of the invention4SrO4]Cluster compound ratio [ Mn4CaO4]The stability of the cluster is much better. Has wide application prospect of the water cracking catalyst.
Experimental example 6: electron paramagnetic resonance of compound 2 probes the valence state of the Mn ion in the compound.
Compound 2(1mM) was dissolved in dichloroethane, and 0.5mM of an oxidizing agent [ Fe (Phen) ]was added3](PF6)3(wherein Phen ═ phenanthroline) was then rapidly frozen to 77K, and its electron paramagnetic signal was detected at 7K using a Bruker E500 electron paramagnetic resonance instrument (see FIG. 6). We can clearly see the multi-peak paramagnetic signal of g-2.0. The appearance of this signal indicates that after the compound is oxidized, the valence states of the four Mn ions are (+3, +4, +4, +4), respectively, and we can deduce that the valence states of the four Mn ions in the ground state (steady state before oxidation) are (+3, +3, +4, + 4).
Experimental example 7: determination of oxygen released by cracking of catalytic water in the presence of oxidant by Compound 2
The oxygen evolution activity of the catalytic water decomposition was measured on a Clark-type oxygen electrode (FIG. 7). In an aqueous solution containing an oxidizing agent (hydrogen peroxide, 0.1M), a rapid oxygen evolution to saturation was observed by adding 500. mu.M of Compound 2, while a reference compound (Mn (ClO)4)2) No significant oxygen formation is seen. In the figure, the arrow indicates the position of the sample application. Figure 7 illustrates that compound 2 has catalytic activity for catalyzing the cleavage of water to release oxygen.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (44)

1. [ Mn ] shown as formula I3SrO4](R1CO2)6(R1CO2H)3A compound, characterized in that: the compound contains three Mn ions and one Sr2+Ions passing through four O2-Ionically bonded to form [ Mn3SrO4]Heteronuclear metal cluster framework cores;
[Mn3SrO4]the peripheral ligand of the cluster compound is formed by six carboxylic acid anions R1CO2 -And three neutral carboxylic acid ligands R1CO2H, wherein the valence states of three Mn ions are +4, and the whole cluster compound is electrically neutral;
Figure FDA0002458684920000011
wherein R is1Is selected from H or C1-8Straight or branched chain alkyl.
2. The compound of claim 1, wherein the carboxylate anion R1CO2 -Is formate, acetate, propionate, butyrate, isobutyrate, valerateIsovalerate, pivalate, hexanoate.
3. The compound of claim 1, wherein R1Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl.
4. The compound of claim 1, wherein the compound of formula I is selected from:
compound 1, [ Mn3SrO4](R1CO2)6(R1CO2H)3Wherein R is1A single crystal of t-butyl, which is trigonal, the space group is R-3c, and the unit cell parameters are
Figure FDA0002458684920000012
α 90.00 degrees, β 90.00 degrees, gamma 120.00 degrees, Z6 degrees, and the volume is
Figure FDA0002458684920000013
The structure is shown as formula I-1:
Figure FDA0002458684920000021
wherein R is1Is tert-butyl
Formula I-1.
5. [ Mn ] shown as formula II4SrO4](R1CO2)8(L1)(L2)(L3)(L4) A compound, characterized in that: the compound contains four Mn ions and one Sr2+Ions passing through four O2-Ionic linkage into asymmetric [ Mn ]4SrO4]Heteronuclear metal cluster framework cores;
[Mn4SrO4]the peripheral ligand of the cluster is composed of eight carboxylic anions R1CO2 -And four neutral ligands L1、L2、L3、L4Providing; the valence states of the four Mn ions are +3, +3, +4, +4 respectively, and the whole cluster compound is electrically neutral;
Figure FDA0002458684920000031
wherein R is1Is selected from H or C1-8A linear or branched alkyl group;
L1、L2、L3、L4the four ligands are the same or different and are respectively and independently selected from carboxylic acid molecules, pyridine, imidazole, pyrazine, quinoline, isoquinoline and bipyridine, or water molecules, alcohol molecules, ketones, nitriles and esters.
6. A compound according to claim 5, wherein the carboxylate anion R1CO2 -Is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate or hexanoate.
7. The compound of claim 5, wherein R1Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl.
8. The compound of claim 5, wherein the compound of formula II is selected from:
compound 2, [ Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) Wherein R is1T-butyl L1L from pyridine2＝L3＝L4Pivalic acid.
9. The compound according to claim 8, wherein the compound 2 is a single crystal, the single crystal is an orthorhombic system, space group is Pna21, and unit cell parameter is Pna21
Figure FDA0002458684920000032
α 90.00 degrees, β 90.00 degrees, gamma 90.00 degrees, Z4 degrees, and the volume is
Figure FDA0002458684920000033
The structure is shown as the following formula II-1:
Figure FDA0002458684920000041
wherein R is1Is tert-butyl
Formula II-1.
10. A complex formed by the association of two or more compounds of formula II:
Figure FDA0002458684920000042
wherein R is1Is selected from H or C1-8A linear or branched alkyl group;
L1、L2、L3、L4the four ligands are the same or different and are respectively and independently selected from carboxylic acid molecules, pyridine, imidazole, pyrazine, quinoline, isoquinoline and bipyridine, or water molecules, alcohol molecules, ketones, nitriles and esters.
11. A complex according to claim 10, wherein the carboxylate anion R1CO2 -Is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate or hexanoate.
12. The complex of claim 10, wherein R1Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl.
13. The compound of claim 10, wherein the compound is selected from the group consisting of:
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate;
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]wherein R is1T-butyl L1L from Arthroquine2＝L3＝L4L from pivalic acid4 *Ethyl acetate.
14. The compound of claim 13, wherein the compound is selected from any one of the following compounds:
complex 3, [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from pyridine2＝L3＝L4L from pivalic acid4 *Ethyl acetate; the single crystal is monoclinic system, and the space group is P121C1, unit cell parameter of
Figure FDA0002458684920000051
α ═ 90.00 °, β ═ 92.6590(10 °), γ ═ 90.00 °, Z ═ 4, volume
Figure FDA0002458684920000052
In the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]In part, as shown in formula II-1:
Figure FDA0002458684920000053
wherein R is1Is tert-butyl
Formula II-1;
in the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]In part represented by formula II-2:
Figure FDA0002458684920000061
wherein R is1Is tert-butyl
Formula II-2;
complex 4, [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]·[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]Wherein R is1T-butyl L1L from Arthroquine2＝L3＝L4L from pivalic acid4 *Ethyl acetate, the single crystal of the compound is a triclinic system, the space group is P-1, and the unit cell parameters are
Figure FDA0002458684920000062
α is 76.547(5) °, β is 87.559(6) °, γ is 73.153(6) °, and Z is 2, and the volume is 76.547(5) °
Figure FDA0002458684920000063
In the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4)]Part is shown as formula II-3-1; in the structure of [ [ Mn ]4SrO4](R1CO2)8(L1)(L2)(L3)(L4 *)]The moiety is represented by the following formula II-3-2:
Figure FDA0002458684920000071
wherein R is1Is tert-butyl
Formula II-3-1;
Figure FDA0002458684920000072
wherein R is1Is tert-butyl
Formula II-3-2.
15. [ Mn ] of the formula I according to any one of claims 1 to 43SrO4](R1CO2)6(R1CO2H)3The preparation method of the compound is characterized by comprising the following steps: the method comprises the following steps:
reacting an acid R1CO2H. Oxidant, Mn2+Salt, Sr2+Heating salt in an acetonitrile solution according to a molar ratio of x: y:1:1 for 10-60 minutes to react to obtain a solution, and filtering to remove precipitates; standing for 1-6 days to obtain crystals, wherein x is 10-120, and y is 1-10.
16. The method according to claim 15, wherein x is 20 to 100 and y is 2 to 8.
17. The method according to claim 15, wherein the manganese salt Mn is2+Is containing Mn2+Wherein the carboxylate anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; orThat is Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2。
18. The production method according to claim 15, wherein Sr2+The salts are strontium carboxylates wherein the carboxylic anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2。
19. The method of claim 15, wherein the oxidant is a permanganate anion oxidant.
20. The method of claim 19, wherein the oxidizing agent is ammonium tetrabutylpermanganate (C)4H9)4N·MnO4。
21. The method according to claim 15, wherein the acid is formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid.
22. The preparation method according to claim 15, wherein the volume of the acetonitrile solvent is 60-100 ml of acetonitrile for every millimole of strontium salt, the reaction temperature is 60-90 ℃, and the reaction time is 10-60 minutes.
23. A compound of formula I [ Mn ] as claimed in any of claims 1 to 43SrO4](R1CO2)6(R1CO2H)3As synthetic biomimetics [ Mn4SrO4]Use of a precursor of a water-splitting catalyst.
24. Use of a compound of formula I according to any one of claims 1 to 4 for the treatment of waterGeneration of [ Mn ] in time4SrO4]A cluster compound.
25. Use of a compound of formula I as claimed in any of claims 1 to 4 for the production of [ Mn ] in the presence of water4SrO4]The cluster compounds, in turn, catalyze the oxygen evolution reaction.
26. [ Mn ] of the formula II according to any one of claims 5 to 94SrO4](R1CO2)8(L1)(L2)(L3)(L4) A method for preparing the compound, which is characterized in that; the method comprises the following steps:
the first step is as follows: reacting an acid R1CO2H. Oxidant, Mn2+Salt, Sr2+Heating salt and water in an acetonitrile solution according to a molar ratio of x: y:1:1: z for 10-60 minutes to obtain a solution, and filtering to remove precipitates; crystallizing at 0 ℃ to obtain crystals, wherein x is 10-120, y is 1-10, z is 0-20 and 0 is not included;
secondly, dissolving the crystal obtained in the first step in an ester solvent, and adding an organic ligand L1,L2,L3,L4Crystallizing to obtain initial product, and recrystallizing with alkane and halogenated hydrocarbon to obtain final product.
27. The method according to claim 26, wherein x is 20 to 100, y is 2 to 8, and z is 0 to 10 and does not include 0.
28. The process according to claim 26, wherein the product obtained in the second step is further recrystallized from an alkane, cycloalkane or halohydrocarbon to obtain a final product.
29. The method of claim 26, wherein the manganese salt is Mn-containing2+Wherein the carboxylate anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; or Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2；
Sr2+The salts are strontium carboxylates wherein the carboxylic anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2。
30. The production method according to claim 26, wherein the oxidizing agent is a permanganate anion type oxidizing agent;
the acid is formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid.
31. The preparation method of claim 26, wherein the volume of the acetonitrile solvent in the first step is 60-100 ml per millimole of strontium salt, the ester organic solvent in the second step is ethyl acetate, methyl acetate or propyl propionate, and the organic solvent for recrystallization of the product is n-hexane, isooctane, dichloroethane or dichloromethane.
32. The method according to claim 26, wherein the reaction temperature is 60 to 90 ℃ and the reaction time is 10 to 60 minutes.
33. A method of preparing a composite as claimed in any one of claims 10 to 14, wherein the method comprises:
the first step is as follows: mixing acid, oxidant and Mn2+Salt, Sr2+Heating salt and water in an acetonitrile solution according to a molar ratio of x: y:1:1: z for 10-60 minutes to obtain a solution, and filtering to remove precipitates; crystallizing at 0 ℃ to obtain crystals, wherein x is 10-120, y is 1-10, z is 0-20 and 0 is not included;
secondly, dissolving the crystal obtained in the first step in an ester solvent, and adding an organic ligand L1,L2,L3,L4Crystallizing to obtain a primary product;
the third step: and dissolving the product obtained in the second step in an ester solvent, and then leaching or recrystallizing by using alkane, cycloalkane or halogenated hydrocarbon to obtain the final product.
34. The method of claim 33, wherein x is 20 to 100, y is 2 to 8, and z is 0 to 10, and does not include 0.
35. The method of claim 33, wherein the manganese salt is Mn-containing2+Wherein the carboxylate anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; or Mn (ClO)4)2，MnCl2，MnSO4，Mn(NO3)2，Mn(CF3SO3)2；
Sr2+The salts are strontium carboxylates wherein the carboxylic anion is formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, hexanoate; or Sr (ClO)4)2，Sr(NO3)2，Sr(CF3SO3)2。
36. The method of claim 33, wherein the oxidant is a permanganate anion oxidant.
37. The method according to claim 33, wherein the acid is formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid.
38. The preparation method of claim 33, wherein the volume of the acetonitrile solvent in the first step is 60-100 ml per millimole of strontium salt;
the ester organic solvent in the second step reaction is ethyl acetate, methyl acetate and propyl propionate; the organic solvent for recrystallization of the product is n-hexane, isooctane, dichloroethane, dichloromethane.
39. The method according to claim 33, wherein the reaction temperature is 60 to 90 ℃ and the reaction time is 10 to 60 minutes.
40. Use of a compound of formula II according to any one of claims 5 to 9 as a biomimetic water splitting catalyst.
41. The use as claimed in claim 40, wherein the compound of formula II is used to drive the catalytic cracking of water in the presence of an oxidant, releasing oxygen.
42. Use of a composite according to any one of claims 10 to 14 as a biomimetic water splitting catalyst.
43. The use as claimed in claim 42, wherein the complex is used to drive the catalytic cracking of water in the presence of an oxidant, releasing oxygen.
44. A water-splitting catalyst comprising [ Mn ] according to any one of claims 5 to 94SrO4](R1CO2)8(L1)(L2)(L3)(L4) A compound of the class wherein each substituent is as defined in any one of claims 5 to 9;
and/or, comprising a complex according to any one of claims 10 to 14, wherein each substituent is as defined in any one of claims 10 to 14.
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