US 2020/0290031 A1Published application

Cluster compounds containing [Mn3SrO4] and [Mn4SrO4] core structures, preparation method and application thereof

AssigneeInstitute of Chemistry, Chinese Academy of Sciences

InventorsChunxi ZHANG, Changhui CHEN

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Abstract

[Mn3SrO4] cluster compounds are synthesized in a single step from raw materials consisting of simple and inexpensive Mn2+, Sr2+ inorganic compounds and carboxylic acids by using permanganate anion as oxidant. This step can be followed by the synthesis of asymmetric biomimetic water splitting catalyst [Mn4SrO4] cluster compounds in the presence of water. The [Mn4SrO4] cluster compound can catalyze the splitting of water in the presence of an oxidant to release oxygen gas. The neutral [Mn3SrO4](R1CO2)6(R1CO2H)3 cluster compound can serve as precursors for the synthesis of biomimetic water splitting catalysts, and can be utilized in the synthesis of different types of biomimetic water splitting catalysts. [Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) cluster compounds can serve as artificial water splitting catalysts, can be utilized on the surface of an electrode or in the catalyzed splitting of water driven by an anoxidant.

Claims11

Dependent claims

A [Mn3SrO4](R1CO2)6(R1CO2H)3 compound represented by Formula I, characterized in that the compound comprises three Mn ions and one Sr2− ion linked via four O2− ions to form a [Mn3SrO4] heteronuclear metal cluster skeleton core;

the [Mn3SrO4] cluster compound has six carboxylate anions (R1CO2−) and three neutral carboxylic acid ligands (R1CO2H) as the peripheral ligands;
the three Mn ions all have a valence state of +4, and the whole cluster compound is electrically neutral;
wherein, R1 is selected from the group consisting of H and C1-8 linear or branched alkyl.
Preferably, the carboxylate anion (R1CO2−) may be the anion of a carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid and hexanoic acid.
Preferably, R1 may be hydrogen (H), methyl (—CH3), ethyl (—C2H5), n-propyl (—CH2CH2CH3), isopropyl (—CH(CH3)2), n-butyl (—(CH2)3CH3), isobutyl (—CH(CH3)C2H5), tert-butyl (—C(CH3)3), n-pentyl (—(CH2)4CH3), isopentyl (—CH2CH2CH(CH3)2), and the like.
Preferably, the compound of Formula I is selected from the group consisting of:
compound 1, [Mn3SrO4](R1CO2)6(R1CO2H)3, wherein R1=tert-butyl. Compound 1 is a single crystal of trigonal system with space group of R-3c, cell parameters of a=10.6575(15) Å, b=10.6575(15) Å, c=87.917(18) Å, α=90.00°, β=90.00°, and γ=120.00°, Z=6, and volume of 8648(3) Å3. Compound 1 has the structure as shown in the following Formula I-1:
wherein R1 is tert-butyl;

5 more elements

A [Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4) compound represented by Formula II, characterized in that the compound comprises four Mn ions and one Sr2+ ion via four O2− ions to form an asymmetric [Mn4SrO4] heteronuclear metal cluster skeleton core;

the [Mn4SrO4] cluster compound has eight carboxylate anions (R1CO2−) and four neutral ligands (L1, L2, L3, L4) as the peripheral ligands;
the four Mn ions have valence states of +3, +3, +4 and +4, respectively, and the whole cluster compounds is electrically neutral;
wherein, R1 is selected from the group consisting of H and C1-8 linear or branched alkyl;
the four ligands L1, L2, L3 and L4 are the same or different and are each independently selected from the group consisting of carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline, bipyridine and derivatives thereof, or water molecule, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and other exchangeable neutral small molecules.
Preferably, the carboxylate anion (R1CO2−) may be the anion of a carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid and hexanoic acid.
Preferably, R1 may be hydrogen (H), methyl (—CH3), ethyl (—C2H5), n-propyl (—CH2CH2CH3), isopropyl (—CH(CH3)2), n-butyl (—(CH2)3CH3), isobutyl (—CH(CH3)C2H5), tert-butyl (—C(CH3)3), n-pentyl (—(CH2)4CH3), isopentyl (—CH2CH2CH(CH3)2), and the like.
Preferably, the compound of Formula II is selected from the group consisting of:
[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4), wherein R1=tert-butyl, L1=pyridine, and L2=L3=L4=pivalic acid.
Preferably, the compound of Formula II is selected from the following compound:
compound 2, [Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4), wherein R1=tert-butyl, L1=pyridine, L2=L3=L4=pivalic acid (or 2,2-dimethylpropionic acid, or trimethyl acetic acid, corresponding to R1COOH, wherein R1 is tert-butyl).
Preferably, compound 2 is a single crystal of orthogonal system with space group of Pna21, cell parameters of a=19.059(3) Å, b=23.711(4) Å, c=19.416(4) Å, α=90.00°, β=90.00°, and γ=90.00°, Z=4, and volume of 8774(3) Å3;
and compound 2 has the structure as shown in the following Formula II-1:
wherein R1 is tert-butyl;

10 more elements

A complex, characterized in that the complex is formed by the combination of two or more compounds of Formula II:

wherein, R1 is selected from the group consisting of H and C1-8 linear or branched alkyl;
the four ligands L1, L2, L3 and L4 are the same or different and are each independently selected from the group consisting of carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline, bipyridine and derivatives thereof, or water molecule, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and other exchangeable neutral small molecules.
Preferably, the carboxylate anion (R1CO2−) may be the anion of a carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid and hexanoic acid.
Preferably, R1 may be hydrogen (H), methyl (—CH3), ethyl (—C2H5), n-propyl (—CH2CH2CH3), isopropyl (—CH(CH3)2), n-butyl (—(CH2)3CH3), isobutyl (—CH(CH3)C2H5), tert-butyl (—C(CH3)3), n-pentyl (—(CH2)4CH3), isopentyl (—CH2CH2CH(CH3)2), and the like.
Preferably, the complex is selected from the following ones:
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)].[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)], wherein R1=tert-butyl, L1=pyridine, L2=L3=L4=pivalic acid, and L4*=ethyl acetate;
[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)].[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)], wherein R1=tert-butyl, L1=isoquinoline, L2=L3=L4=pivalic acid, and L4*=ethyl acetate.
Preferably, the complex is selected from any of the following ones:
complex 3, [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)].[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)], wherein R1=tert-butyl, L1=pyridine, L2=L3=L4=pivalic acid, and L4*=ethyl acetate. Complex 3 is a single crystal of monoclinic system with space group of P1 21/c1, cell parameters of a=29.9019(5) Å, b=18.9368(3) Å, c=30.1980(4) Å, α=90.00°, β=92.6590(10)°, and γ=90.00°, Z=4, and volume of 17081.1(5) Å3. The [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)] part of the structure of complex 3 is shown in Formula II-1, and the [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)] part is shown in the following Formula II-2:
wherein R1 is tert-butyl;
complex 4, [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)].[[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)], wherein R1=tert-butyl, L1=isoquinoline, L2=L3=L4=pivalic acid, and L4*=ethyl acetate. The compound is a single crystal of triclinic system with space group of P-1, cell parameters of a=14.676(2) Å, b=25.313(3) Å, c=25.601(4) Å, α=76.547(5)°, β=87.559(6)°, and γ=73.153(6)°, Z=2, and volume of 8850(2) Å3. The [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4)] part of the structure of complex 4 is shown in Formula II-3-1, and the [[Mn4SrO4](R1CO2)8(L1)(L2)(L3)(L4*)] part is shown in the following Formula II-3-2:
wherein R1 is tert-butyl;
wherein R1 is tert-butyl;

10 more elements

Dependencies are inferred from the claim text.