CN114736236B - Polynuclear annular organotin oxygen sulfur cluster compound and preparation method and application thereof - Google Patents

Polynuclear annular organotin oxygen sulfur cluster compound and preparation method and application thereof Download PDF

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CN114736236B
CN114736236B CN202210408028.3A CN202210408028A CN114736236B CN 114736236 B CN114736236 B CN 114736236B CN 202210408028 A CN202210408028 A CN 202210408028A CN 114736236 B CN114736236 B CN 114736236B
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organotin
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oxysulfide
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CN114736236A (en
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林启普
黄山林
赖恒东
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/226—Compounds with one or more Sn-S linkages
    • 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
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C02F2101/40—Organic compounds containing sulfur
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Abstract

The application relates to a polynuclear annular organic tin oxide sulfur cluster compound, a preparation method and application thereof, wherein the cluster compound is formed by constructing a basic construction unit A and a basic construction unit B and has a chemical formula (A) n ‑(B) i Is a ring structure; wherein i=0, 1 or 2; when i=0, n is a natural number of 2 or more; when i=1 or 2, n is a natural number of 1 or more; the basic construction unit A has the structural formula:the basic building unit B has the structural formula:wherein R is selected from C1-C8 alkyl, phenyl, benzyl, p-methylphenyl, or p-ethylphenyl; r' is selected from H or C1-C20 alkyl; r' is selected from H or C1-C20 alkyl. The application takes organic metal tin, sulfur source, organic amine and organic polyol as raw materials, adopts a solvothermal synthesis method to prepare the multi-nuclear ringThe organic tin oxide sulfur cluster compound can be used as a catalyst in the field of dye degradation.

Description

Polynuclear annular organotin oxygen sulfur cluster compound and preparation method and application thereof
Technical Field
The application belongs to the technical field of crystal material preparation, and particularly relates to a polynuclear annular organic tin-oxygen-sulfur cluster compound, and a preparation method and application thereof.
Background
Organotin compounds are important organometallic compounds, which are not only one of the main compounds of research in the chemical disciplines such as metal organic chemistry and coordination chemistry, but also are the subjects of interest in other disciplines such as biochemistry and pharmaceutical chemistry.
In recent years, researches on structural diversity and functional diversity of organotin compounds are receiving increasing attention from researchers. On the one hand, a plurality of organotin compounds show good catalytic activity in organic reactions, and have the characteristics of mild reaction conditions, high yield, high reaction rate, high efficiency, no toxicity, easy separation, better stereoselectivity and regioselectivity and the like, so that the organotin compounds are highly concerned by synthetic chemists. For example, organotin compounds catalyze the addition reaction of isocyanates with alcohols and can produce aminothioformates almost quantitatively. Meanwhile, organotin has rich and diversified coordination modes, and through development of recent decades, organotin-chalcogen cluster compounds and organotin-oxygen cluster compounds with rich types and novel structures and organotin-chalcogen cluster compounds have been synthesizedRelatively little research has been done. For example, CN102093431B discloses an organotin oxy cluster containing ferrocenyl pyrazolyl, a complex of the following chemical formula is prepared from 3-trifluoromethyl-5-ferrocenyl pyrazolyl acetic acid (LCOOH) ligand and monobutyl tin oxide, dibutyl tin oxide and triphenyl tin hydroxide, respectively: [ BuSnO (OOCL)] 6 、[Ph 4 Sn 2 O(OCH 3 )(OOCL)] 2 、[Bu 4 Sn 2 O(OOCL) 2 ] 2 The organotin oxygen cluster compound can be applied to the preparation of antitumor drugs. CN104327112B discloses a dumbbell-shaped methyl cup [4 ]]An arene organic tin-oxygen cluster complex and a preparation method thereof belong to the technical field of chemistry, and the complex has the following chemical formula: [ (Bu) 2 Sn) 2 (μ 3 -O)(L)(EtO)] 2 2EtOH in which L-is deprotonated methyl cup [4 ]]Aromatic carboxylic acid anionic ligands. Heating and refluxing n-BuSn (O) OH, ligand HL and mixed solution of toluene and ethanol in a dean-Stark device for 8 hours, removing water generated in the reaction through azeotropic distillation, then distilling the solution under reduced pressure to obtain white solid, and recrystallizing the white solid at room temperature by using mixed solution of chloroform and ethanol to obtain the complex, wherein the complex has fluorescent property and can be used as a fluorescent material in the field of material science.
However, elemental sulfur and elemental oxygen differ in atomic radius and electronegativity, and organotin-oxygen clusters and organotin-sulfur clusters differ greatly in structure and properties. Therefore, a new method is needed to be searched for to introduce the two into the structure at the same time so as to obtain the organotin cluster compound with novel structure and stable performance.
Disclosure of Invention
Therefore, it is necessary to provide a polynuclear annular organic tin oxide sulfur cluster compound which has novel structure, stable performance and better catalytic activity, and can be widely applied to catalytic degradation of dyes; meanwhile, a preparation method of the polynuclear annular organic tin oxide sulfur cluster compound needs to be provided, the method is simple in requirement, low in requirement on raw material purity, easy to obtain raw materials, low in cost, convenient for large-scale production, simple and feasible in post-treatment, and a pure-phase crystalline product can be obtained only through simple separation and purification treatment.
In order to achieve the above purpose, the main technical scheme adopted by the application comprises the following steps:
in a first aspect, the present application provides a polynuclear cyclic organotin oxysulfide cluster compound having the chemical formula (A) formed by a basic building block A and a basic building block B n -(B) i Is a ring structure;
wherein i=0, 1 or 2;
when i=0, n is a natural number of 2 or more;
when i=1 or 2, n is a natural number of 1 or more;
the basic construction unit A has the structural formula:
the basic building unit B has the structural formula:
wherein R is selected from C1-C8 alkyl, phenyl, benzyl, p-methylphenyl, or p-ethylphenyl; r' is selected from H or C1-C20 alkyl; r' is selected from H or C1-C20 alkyl.
In a second aspect, the present application provides a method for preparing a polynuclear cyclic organotin oxysulfide cluster, comprising the steps of;
s1: adding organic metal tin, a sulfur source and organic amine into organic polyol, and uniformly mixing to obtain a mixed solution;
s2: heating the mixed solution for reaction, and cooling to room temperature to obtain a reaction product;
s3: and (3) separating and purifying the reaction product to obtain the cluster compound.
As a further embodiment of the present application, in step S1, the organometallic tin is one of methyl tin, ethyl tin, propyl tin, butyl tin, amyl tin, hexyl tin, octyl tin, phenyl tin, benzyl tin, p-methylphenyl tin, and p-ethylphenyl tin.
As a further embodiment of the present application, in step S1, the sulfur source is one or a mixture of two of elemental sulfur powder, inorganic sulfide, and organic sulfide.
As a further embodiment of the present application, in the step S1, the organic amine is ethylenediamine, N, N '-dimethylethylenediamine, tetramethylethylenediamine, piperidine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, methylpiperidine, methylpiperazine, dimethylpiperazine, dimethylpiperidine, pentamethyldiethylenetriamine, N, N, N' -triethylethylenediamine, tetraethylethylenediamine, 1-methylpiperazine, 2-methylpiperazine, 1, 4-dimethylpiperazine, 1, 4-diethylpiperazine, 1, 2-dimethylpiperazine, N, N, N ', N' -tetraethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N, N ', N' -tetrabutyldiethylenetriamine, hexamethyltriethyltriethylenetetramine, heptamethyltetraethylenepentamine, 1, 4-diethylpiperazine, 3-methyl-1-phenylpiperazine, 1-butylpiperazine, 1-phenethylpiperazine, 3-propylpiperidine, N, N-Dimethylformamide (DMF), N-methylformamide (NMF), N, N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF).
As a further embodiment of the present application, in step S1, the organic polyol is one or a mixture of two of vicinal diols having 1 to 40 carbon atoms.
As a further embodiment of the present application, the molar ratio of the organometallic tin, the sulfur source, the organic amine, and the organic polyol is 1: (2-10): (10-100): (50-150).
In a further embodiment of the present application, in step S2, the reaction temperature of the heating reaction is 80 to 180 ℃ and the reaction time is 76 to 480 hours.
As a further embodiment of the present application, the reaction temperature is 100 to 140℃and the reaction time is 120 to 340 hours.
As a further embodiment of the present application, in step S2, an auxiliary agent is further added to the heating reaction, wherein the auxiliary agent is selected from one or more of tin dichloride, zinc chloride, zinc acetate, cadmium chloride, cadmium acetate, ferrocene, cerium nitrate hydrate, 2, 6-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, and 3, 5-dihydroxybenzoic acid.
As a further embodiment of the present application, in step S3, the separation and purification includes:
separating from the reaction product to obtain a solid crystalline substance, and cleaning and purifying the solid crystalline substance by adopting an alcohol solvent to obtain the cluster compound.
In a further embodiment of the present application, the alcohol solvent is one or a mixture of two of a monohydric alcohol or a dihydric alcohol having 1 to 40 carbon atoms.
In a third aspect, the application provides the use of polynuclear cyclic organotin oxysulfide cluster compounds as catalysts in the field of catalytic degradation of dyes.
Compared with the prior art, the technical scheme has the following beneficial effects:
(1) The polynuclear annular organic tin-oxygen-sulfur cluster compound disclosed by the application has the advantages that sulfur element and oxygen element are simultaneously introduced into the structure, so that the polynuclear annular organic tin-oxygen-sulfur cluster compound has better catalytic activity and stability, provides a new choice for a catalyst for catalytic degradation of dye, and simultaneously widens the application range of the organic tin cluster compound.
(2) The application discloses a preparation method of a polynuclear annular organic tin oxide sulfur cluster compound, which has simple process requirements, lower requirements on raw material purity, easy and cheap raw material acquisition, convenient mass production, simple and easy post-treatment, and can obtain a pure-phase crystalline product only through simple separation and purification treatment; in addition, the pollution in the process of synthesis is less, the environment-friendly requirement is met, the yield can reach more than 50%, and a new thought is provided for synthesizing the organotin oxygen sulfur cluster compound with stable performance.
(3) The polynuclear annular organotin oxygen sulfur cluster compound disclosed by the application has catalytic activity and stability, can be used as a catalyst in the field of catalytic dye degradation, and can realize rapid decomposition of dye.
The foregoing summary is provided to enable one of ordinary skill in the art to make and use the application, and is intended to provide an overview of the application, as it is claimed, and is intended to provide an overview of the application as it is claimed.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic diagram of the crystal structure of a 9-core cyclic organotin oxysulfide cluster prepared in example 1;
FIG. 2 is an X-ray powder diffraction pattern of a 9-core cyclic organotin-oxysulfide cluster prepared in example 1;
FIG. 3 is an infrared spectrum of a 9-core cyclic organotin oxysulfide cluster prepared in example 1;
FIG. 4 is an X-ray Energy Dispersive Spectrometry (EDS) of the 9-core cyclic organotin-oxysulfide cluster prepared in example 1;
FIG. 5 is a schematic view of the crystal structure of the 11-core cyclic organotin-oxysulfide cluster prepared in example 4;
FIG. 6 is an X-ray powder diffraction pattern of the 11-core cyclic organotin-oxysulfide cluster prepared in example 4;
FIG. 7 is an infrared spectrum of the 11-nucleus cyclic organotin-oxygen-sulfur cluster compound prepared in example 4;
FIG. 8 is an X-ray Energy Dispersive Spectrometry (EDS) of the 11-core cyclic organotin-oxysulfide cluster prepared in example 4;
FIG. 9 is a schematic diagram showing the crystal structure of a 12-core cyclic organotin-oxysulfide cluster compound prepared in example 6;
FIG. 10 is an X-ray powder diffraction pattern of a 12-core cyclic organotin-oxysulfide cluster prepared in example 6;
FIG. 11 is an infrared spectrum of a 12-core cyclic organotin oxysulfide cluster compound prepared in example 6;
FIG. 12 is an X-ray Energy Dispersive Spectrometry (EDS) of a 12-core cyclic organotin-oxysulfide cluster prepared in example 6;
FIG. 13 is a schematic view showing the crystal structure of a 12-core cyclic organotin-oxysulfide cluster compound prepared in example 8;
FIG. 14 is an X-ray powder diffraction pattern of a 12-core cyclic organotin-oxysulfide cluster prepared in example 8;
FIG. 15 is an infrared spectrum of a 12-core cyclic organotin oxysulfide cluster compound prepared in example 8;
FIG. 16 is an X-ray Energy Dispersive Spectrometry (EDS) of a 12-core cyclic organotin-oxysulfide cluster prepared in example 8;
FIG. 17 is a graph of ultraviolet absorption spectrum of the test sample in example 9, wherein the curves from top to bottom in the arrow direction correspond to the data measured for 0, 20, 40, 60, 80, 100, 120 min;
FIG. 18 is a graph of ultraviolet absorption spectrum of a hollow white sample in example 9, wherein curves from top to bottom in the arrow direction correspond to data measured at 0, 20, 40, 60, 80, 100, 120 min;
FIG. 19 is a graph comparing the relative concentration changes of methyl blue dye in the test and blank samples of example 9.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in connection with the specific embodiments in conjunction with the accompanying drawings. The present embodiment is implemented on the premise of the technical scheme of the present application, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present application is not limited to the following embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
First, the polynuclear cyclic organotin oxysulfide cluster provided by the first aspect of the present application is explained.
A polynuclear annular organotin oxysulfide cluster compound has a chemical formula (A) formed by a basic building unit A and a basic building unit B n -(B) i Is a ring structure;
wherein i=0, 1 or 2;
when i=0, n is a natural number of 2 or more;
when i=1 or 2, n is a natural number of 1 or more;
the basic construction unit A has the structural formula:
the basic building unit B has the structural formula:
wherein R is selected from C1-C8 alkyl, phenyl, benzyl, p-methylphenyl, or p-ethylphenyl; r' is selected from H or C1-C20 alkyl; r' is selected from H or C1-C20 alkyl. Wherein R 'and R' may be the same or different.
The polynuclear annular organic tin oxide sulfur cluster compound provided by the technical scheme is a pure-phase colorless polyhedral crystal, is a zero-dimensional cluster with an annular structure, can have different structural stacking parameters, has different nuclear numbers, has adjustable organic functional groups, has good catalytic activity, and can be used as a catalyst for catalytic degradation of dyes.
The specific structure of the cyclic organotin-oxygen-sulfur cluster is exemplified by the cyclic organotin-oxygen-sulfur cluster having 5 to 15 cores, but the scope of the present application is not limited thereto.
5-nucleus cyclic organotin oxysulfide cluster (A) 1 -B 1 ) Is of the formula:
6-nucleus cyclic organotin oxysulfide cluster (A) 2 -B 0 ) Is of the formula:
7-nucleus cyclic organotin oxysulfide cluster (A) 1 -B 2 ) Is of the formula:
8-nucleus cyclic organotin oxysulfide cluster (A) 2 -B 1 ) Is of the formula:
9-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 0 ) Is of the formula:
10-nucleus cyclic organotin oxysulfide cluster (A) 2 -B 2 ) Is of the formula:
11-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 1 ) Is of the formula:
12-nucleus cyclic organotin oxysulfide cluster (A) 4 -B 0 ) Is of the formula:
13-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 2 ) Is of the formula:
14-nucleus cyclic organotin oxysulfide cluster (A) 4 -B 1 ) Is of the formula:
15-nucleus cyclic organotin oxysulfide cluster (A) 5 -B 0 ) Is of the formula:
in the above formulas (1) to (11), R is selected from C1-C8 alkyl, phenyl, benzyl, p-methylphenyl, or p-ethylphenyl; r' is selected from H or C1-C20 alkyl; r' is selected from H or C1-C20 alkyl. Wherein R 'and R' may be the same or different.
Next, a method for preparing the polynuclear cyclic organotin-oxygen-sulfur cluster according to the first aspect of the present application is described.
The preparation method of the polynuclear annular organotin oxysulfide cluster compound comprises the following steps of;
s1: adding organic metal tin, a sulfur source and organic amine into organic polyol, and uniformly mixing to obtain a mixed solution;
s2: heating the mixed solution for reaction, and cooling to room temperature to obtain a reaction product;
s3: and (3) separating and purifying the reaction product to obtain the cluster compound.
According to the technical scheme, the polynuclear annular organotin oxygen sulfur cluster compound is prepared by taking organic metal tin, a sulfur source, organic amine and organic polyol as raw materials and adopting a solvothermal synthesis method. The preparation method has the advantages of simple process, easy repetition, low raw material cost and convenient production. The solvothermal synthesis method refers to heating reaction in a solvent.
The reaction mechanism of the technical scheme is as follows: organic tin cations in the organic metal tin react with sulfur sources and anions formed after hydroxyl dehydrogenation on organic polyol, and meanwhile, in the reaction process, organic amine is used as a structure directing agent, a guest molecule filled in a structural space and charge balance ions, so that organic tin oxygen sulfur cluster compounds with different nuclear numbers are generated.
In some embodiments of the application, in step S1, the organometallic tin is one of methyl tin, ethyl tin, propyl tin, butyl tin, amyl tin, hexyl tin, octyl tin, phenyl tin, benzyl tin, p-methylphenyl tin, p-ethylphenyl tin. The organic metal tin participates in the structure of the organic tin oxygen sulfur cluster compound, and different organic metal tin changes the structure. Different organotin groups have different alkyl chain lengths, so that the selection of different organotin groups can change the structural size and molecular formula of the cluster compound, but can not change the structural configuration and the number of metal ions in the structure. For example, when ethyltin is selected as the organotin salt to construct a ring structure having the same number of nuclei, the number of carbon atoms bonded to each metallic tin in the molecular formula of the structure is reduced by two (compared with butyltin "butyltin trichloride" in the example), and the number of nonmetallic carbon atoms in the molecular formula is reduced. Meanwhile, the volume of the alkyl group in the structure is reduced, so that the distance between cluster molecules is shortened, and the stacking parameter of the cluster molecules is reduced (compared with a polymorphous butyl tin structure).
In the description of the present application, the "number of cores", "multi-core", "5-core", "6-core", and the like correspond to the number of "tin" in the organotin oxysulfide cluster.
In some embodiments of the present application, in step S1, the sulfur source is one or a mixture of two of elemental sulfur powder, inorganic sulfide, and organic sulfide. Specifically, elemental sulfur powder includes, but is not limited to, sulfur powder, sulfur; inorganic sulfides include, but are not limited to, sodium sulfide, lithium sulfide, potassium sulfide, zinc sulfide, tin sulfide, ammonium sulfide; organic sulfides include, but are not limited to, thiourea, dimethylthiourea, sodium dimethyldithiocarbamate. The choice of sulfur source also has a promoting effect on the growth of the crystal. For example, in the synthesis of 9-core cyclic clusters, selection of either elemental sulfur powder or organic thiourea can produce higher yields of cluster crystal products; however, when inorganic sodium sulfide is selected as the sulfur source, there is little crystallization.
In some embodiments of the application, in step S1, the organic amine is ethylenediamine, N, N '-dimethylethylenediamine, tetramethylethylenediamine, piperidine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, methylpiperidine, methylpiperazine, dimethylpiperazine, dimethylpiperidine, pentamethyldiethylenetriamine, N, N, N' -triethylethylenediamine, tetraethylethylenediamine, 1-methylpiperazine, 2-methylpiperazine, 1, 4-dimethylpiperazine, 1, 4-diethylpiperazine, 1, 2-dimethylpiperazine, N, N, N ', N' -tetraethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N, N ', N' -tetrabutyldiethylenetriamine, hexamethyltriethyltriethylenetetramine, heptamethyltetraethylenepentamine, 1, 4-diethylpiperazine, 3-methyl-1-phenylpiperazine, 1-butylpiperazine, 1-phenethylpiperazine, 3-propylpiperidine, N, N-Dimethylformamide (DMF), N-methylformamide (NMF), N, N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF).
In the synthesis process, the organic amine plays a vital role in the formation of the cyclic structure and the number of cores of the organotin oxysulfide cluster compound, and is used as a reaction medium, a structure guiding agent generated by the structure, a guest molecule filled in a structural space and a charge balance ion. Thus, organic tin-oxygen-sulfur clusters with different core numbers can be generated by adopting different organic amines as structure directing agents.
For example, in the synthesis of 5-nucleus cyclic organotin oxysulfide cluster (A) 1 -B 1 ) When the organic amine may be a mixture of chain alkylamine and amide. Wherein, the alkylamine can be selected from ethylenediamine, N' -dimethylethylenediamine and tetramethylethylenediamine; the amide may be selected from N, N-Dimethylformamide (DMF), N-methylformamide (NMF), N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of tetramethyl ethylenediamine and N-methyl formamide (NMF).
For example, in the synthesis of 6-nucleus cyclic organotin oxysulfide cluster (A) 2 -B 0 ) In this case, the organic amine may be a mixture of piperidine and its derivatives with tertiary alkyl amines. Wherein the tertiary alkyl amine may be selected from trimethylamine, triethylamine, tripropylamine or triisopropylamine. Preferably, the organic amine is a mixture of piperidine and triethylamine.
For example, in the synthesis of 7-nucleus cyclic organotin oxysulfide cluster (A) 1 -B 2 ) When the organic amine is a mixture of dialkylamine and methylpiperidine. Wherein the dialkylamine can be dimethylamine, diethylamine, dipropylamine, diisopropylamine or dibutylamine. Preferably, the organic amine is a mixture of methylpiperidine and dipropylamine.
For example, in the synthesis of the 8-core cyclic organotin oxysulfide cluster (A2-B1), the organic amine may employ a mixture of an alkyl tertiary amine and an amide. Wherein the tertiary alkyl amine may be selected from trimethylamine, triethylamine, tripropylamine or triisopropylamine; the amide may be selected from N, N-Dimethylformamide (DMF), N-methylformamide (NMF), N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of triethylamine and N, N-Diethylformamide (DEF).
For example, in the synthesis of 9-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 0 ) In this case, the organic amine may be one or a mixture of two of methylpiperidine, methylpiperazine, dimethylpiperazine and dimethylpiperidine, preferably methylpiperidine.
For example, in the synthesis of 10-nucleus cyclic organotin oxysulfide cluster (A) 2 -B 2 ) In the case of organic amines, methylpiperidine, methylpiperazine and polyalkyl groups can be usedMixtures of tertiary amines, wherein the polyalkyl tertiary amine may be selected from trimethylamine, triethylamine, tripropylamine or triisopropylamine. Preferably, the organic amine is a mixture of methylpiperidine and triethylamine.
For example, in the synthesis of 11-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 0 ) When the organic amine may be a mixture of a multi-branched alkyl tertiary amine and an amide. Wherein the multi-branched alkyl tertiary amine is selected from pentamethyl diethylene triamine, N, N, N' -triethyl ethylenediamine or tetraethyl ethylenediamine; the amide is selected from N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMA), N-methylformamide (NMF) or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of pentamethyldiethylenetriamine and N, N-Dimethylformamide (DMF).
For example, in the synthesis of 12-nucleus cyclic organotin oxysulfide cluster (A) 4 -B 0 ) When the organic amine may be a mixture of a cyclic organic amine and an amide. Wherein the cyclic organic amine is selected from methylpiperazine and derivatives thereof, such as, but not limited to, 1-methylpiperazine, 2-methylpiperazine, 1, 4-dimethylpiperazine, 1, 4-diethylpiperazine, 1, 2-dimethylpiperazine; the amide is selected from N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of 1-methylpiperazine and N, N-Dimethylformamide (DMF).
For example, in the synthesis of 13-nucleus cyclic organotin oxysulfide cluster (A) 3 -B 2 ) When the organic amine can be a mixture of a multi-branched alkylamine and a polyalkyl tertiary amine, the alkylamine can be selected from N, N, N ', N' -tetraethyl diethylenetriamine, hexamethyl triethylenetetramine, N, N, N ', N' -tetrabutyl diethylenetriamine or hexaethyltriethyltriethylenetetramine; the polyalkyl tertiary amine may be trimethylamine, triethylamine, tripropylamine or triisopropylamine. Preferably, the organic amine is a mixture of N, N, N ', N' -tetraethyldiethylenetriamine and triethylamine.
For example, in the synthesis of 14-nucleus cyclic organotin oxysulfide cluster (A) 4 -B 1 ) When the organic amine may be a mixture of a multi-branched alkylamine and an amide. Wherein the alkylamine is selected from N, N, N ', N' -tetraethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N,n ', N' -tetrabutyldiethylenetriamine, hexaethyltriethylenetetramine or heptamethyltetraethylenepentamine; the amide is selected from N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMA), N-methylformamide (NMF) or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of hexamethyltriethylenetetramine and N, N-Dimethylacetamide (DMA).
For example, in the synthesis of 15-nucleus cyclic organotin oxysulfide cluster (A) 5 -B 0 ) When the organic amine is a mixture of branched cyclic organic amine and amide. Wherein the cyclic amine may be selected from 1, 4-diethyl piperazine, 3-methyl-1-phenyl piperazine, 1-butyl piperazine, 1-phenethyl piperazine or 3-propyl piperidine; the amide is selected from N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMA), N-methylformamide (NMF), or N, N-Diethylformamide (DEF). Preferably, the organic amine is a mixture of 1-butylpiperazine and N, N-Dimethylacetamide (DMA).
In some embodiments of the application, in step S1, the organic polyol is one or a mixture of two of vicinal diols containing 1 to 40 carbon atoms. In particular, the vicinal diols include, but are not limited to, ethylene glycol, 1, 2-propylene glycol, 1, 2-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 2, 3-pentanediol, 1, 2-hexanediol, and the like. Organic polyols participate in the structure formation of organotin oxysulfide clusters, and different organic polyols change the structure composition. For example, when ethylene glycol is used as the organic polyol, R 'and R' in the structural formulae of the basic building blocks A and B are both H; when 1, 2-propanediol is used as the organic polyol, R 'and R' in the structural formulae of the basic building blocks A and B are independently H, CH, respectively 3 Or R 'and R' are independently CH 3 H, H; when 2, 3-butanediol is used as the organic polyol, R 'and R' in the structural formulae of the basic building blocks A and B are both CH 3 。
In some embodiments of the application, the molar ratio of the organometallic tin, the sulfur source, the organoamine, and the organic polyol is 1: (2-10): (10-100): (50-150). When the molar ratio is within this range, the yield of the crystalline substance is high and the impurities are less. If the proportion of the sulfur source is too small, it may result in a low crystal yield or even difficult crystallization, and if it is too high, it may result in impurities in the final product; too low a molar ratio of organic amine to organic polyol tends to result in impurities in the final crystalline product, while too high a molar ratio results in too low a yield of crystalline product, even without crystallization of crystalline product.
In some embodiments of the present application, in step S2, the reaction temperature of the heating reaction is 80 to 180 ℃ and the reaction time is 76 to 480 hours. Preferably, the reaction temperature is 100-140 ℃, and the reaction time is 120-340 hours. If the reaction temperature is too low, the reaction time will be long and the crystal size will be relatively small.
According to the requirement, an auxiliary agent can be added in the solvothermal reaction process, the crystallization rate of the polynuclear annular organotin oxygen-sulfur cluster compound can be controlled by the auxiliary agent, the crystal growth is promoted, and the yield is improved, so that a crystalline product with larger size and higher yield is obtained. Thus, in some embodiments of the application, in step S2, an adjunct selected from one or more of tin dichloride, zinc chloride, zinc acetate, cadmium chloride, cadmium acetate, ferrocene, cerium nitrate hydrate, 2, 6-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, 3, 5-dihydroxybenzoic acid is also added to the heating reaction.
In some embodiments of the application, in step S3, the separating and purifying includes:
separating from the reaction product to obtain a solid crystalline substance, and cleaning and purifying the solid crystalline substance by adopting an alcohol solvent to obtain the cluster compound.
In some embodiments of the application, the alcoholic solvent is one or a mixture of two of a monohydric alcohol or a dihydric alcohol containing 1 to 40 carbon atoms. Among them, the monohydric alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, etc.; diols include, but are not limited to, ethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 2, 3-pentanediol, 1, 2-hexanediol, and the like. In some embodiments, the alcohol solvent of step S3 for washing the solid crystalline material and the organic polyol of step S1 may be the same alcohol solvent or different alcohol solvents, which is not limited in particular.
Finally, the application of the polynuclear annular organotin oxysulfide cluster compound provided by the third aspect of the application as a catalyst in the field of catalytic degradation of dyes is described. The polynuclear annular organotin oxygen sulfur cluster compound disclosed by the application has catalytic activity and stability, can be used as a catalyst in the field of catalytic dye degradation, and can realize rapid decomposition of dye. Examples of applications are described in detail in the following specific examples.
The above is a core technical scheme of the present application, and the technical scheme of the present application will be described in detail with reference to the following specific examples, but the specific embodiments of the present application are not limited to the following examples.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The experimental methods in the following examples are conventional methods unless otherwise specified.
The single crystal structure analysis of the application uses a MM-007 single crystal diffractometer of Japanese physics; the X-ray powder diffraction pattern uses Mo-K alpha rays as a radiation source.
In particular embodiments of the application, the solvothermal synthesis reaction may be carried out in a glass bottle (oven heated) or polytetrafluoroethylene reactor or other reactor. The following examples are illustrative of only glass bottles (oven heated) as reaction vessels, but are not intended to limit embodiments of the present application.
Example 19 preparation of cyclic organotin oxysulfide Cluster
Sulfur powder (60 mg,1.88 mmol) was weighed, tin dichloride dihydrate (45 mg,0.2 mmol) was put into a 20mL glass bottle, then butyl tin trichloride (80 μl,0.5 mmol), 4-methylpiperidine (2 mL,12.9 mmol) and ethylene glycol (EG, 2mL,35.86 mmol) were added to the glass bottle at one time, stirred at room temperature for 30 minutes, then put into an oven at 100 ℃ for constant temperature reaction for 7 days (168 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed and purified with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide cluster crystalline product, the structural formula of which is shown in formula (I), and the crystal parameters of which are shown in table 1. The yield of the crystalline product prepared in this example was tested to be 70%. The single crystal X-ray structural analysis of the crystalline product prepared in this example is shown in fig. 1, and as can be seen from fig. 1, the organotin oxysulfide-cluster crystalline product prepared in this example has a ring structure. The crystalline product prepared in this example has an X-ray powder diffraction pattern as shown in fig. 2, an infrared spectrum as shown in fig. 3, and an X-ray Energy Dispersive Spectroscopy (EDS) as shown in fig. 4.
Example 2 9 preparation of cyclic organotin oxysulfide Cluster
Sulfur powder (300 mg,9.4 mmol) was weighed, tin dichloride dihydrate (225 mg,1 mmol) was placed in a 50mL glass bottle, then butyl tin trichloride (400 μl,2.5 mmol), 4-methylpiperidine (10 mL,64.5 mmol) and ethylene glycol (EG, 10mL,179.3 mmol) were added to the glass bottle at one time, stirred at room temperature for 30 minutes, then placed in an oven at 100 ℃ for reaction at constant temperature for 10 days (240 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide group crystalline product, the structure and crystal parameters of which were the same as those of the crystalline product in example 1. The yield of the crystalline product prepared in this example was tested to be 70%.
Example 3 9 preparation of cyclic organotin oxysulfide Cluster
Thiourea (155.4 mg,2.04 mmol) was weighed, ferrocene (34.5 mg,0.18 mmol) was put into a 20mL glass bottle, then butyl tin trichloride (80. Mu.L, 0.5 mmol), 4-methylpiperidine (2 mL,12.9 mmol) and ethylene glycol (EG, 2mL,35.86 mmol) were added to the glass bottle at one time, stirred at room temperature for 30 minutes, then put into an oven at 100 ℃ for reaction at constant temperature for 7 days (168 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide group crystalline product having the same structural formula as the crystalline product in example 1, and the crystal parameters are shown in Table 1. The yield of the crystalline product prepared in this example was tested to be 70%.
EXAMPLE 4 preparation of Nuclear cyclic organotin oxysulfide Cluster
Thiourea (133.6 mg,1.75 mmol), 2, 6-dihydroxybenzoic acid (107.2 mg,0.7 mmol) were weighed into a 20mL glass bottle, then ethylene glycol (EG, 1.5mL,26.89 mmol), butyltin trichloride (80. Mu.L, 0.5 mmol), N, N-dimethylformamide (DMF, 1.5mL,19.37 mmol) and pentamethyldiethylenetriamine (2 mL,9.58 mmol) were added to the glass bottle at one time, stirred at room temperature for 30 minutes, then placed in an oven at 120 ℃ for reaction at constant temperature for 7 days (168 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide crystalline product, the structural formula of which is shown in formula (II), and the crystal parameters of which are shown in Table 1. The yield of the crystalline product prepared in this example was 50% as tested. As shown in FIG. 5, the crystalline product of the organotin oxysulfide group prepared in this example has a ring structure as can be seen from FIG. 5. The crystalline product prepared in this example has an X-ray powder diffraction pattern as shown in fig. 6, an infrared spectrum as shown in fig. 7, and an X-ray Energy Dispersive Spectroscopy (EDS) as shown in fig. 8.
EXAMPLE 5 preparation of Nuclear cyclic organotin oxysulfide Cluster
Thiourea (1.07 g,14 mmol) and 2, 6-dihydroxybenzoic acid (534 mg,3.5 mmol) were weighed into a 100mL glass bottle, then ethylene glycol (EG, 9mL,161.34 mmol), butyltin trichloride (480. Mu.L, 3 mmol), N, N-dimethylformamide (DMF, 9mL,116.22 mmol) and pentamethyldiethylenetriamine (12 mL,57.48 mmol) were added to the glass bottle at a time, stirred at room temperature for 30 minutes, then placed in an oven at 120 ℃ for constant temperature reaction for 7 days (168 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide cluster crystalline product, the structure and crystal parameters of which are the same as those of the crystalline product in example 4. The yield of the crystalline product prepared in this example was 50% as tested.
EXAMPLE 6 preparation of 12 Nuclear cyclic organotin oxysulfide Cluster
Thiourea (132.8 mg,1.74 mmol) was weighed into a 20mL glass bottle, then ethylene glycol (EG, 3mL,53.78 mmol) was added to the glass bottle at one time, butyltin trichloride (90. Mu.L, 0.56 mmol), N, N-dimethylformamide (DMF, 1.5mL,19.37 mmol) and 1-methylpiperazine (3 mL,27.09 mmol) were stirred at room temperature for 30 minutes, then placed in an oven at 100 ℃ for constant temperature reaction for 7 days (168 hours), taken out, naturally cooled to room temperature, separated to obtain a solid crystalline substance, and the solid crystalline substance was washed with ethanol to obtain a colorless polyhedral cyclic organotin oxysulfide group crystalline product, the structural formula of which is shown in formula (III), and the crystal parameters of which are shown in Table 1. The yield of the crystalline product prepared in this example was tested to be 60%. As shown in FIG. 9, the crystalline product of the organotin oxysulfide group prepared in this example has a ring structure as can be seen from FIG. 9. The crystalline product prepared in this example has an X-ray powder diffraction pattern as shown in fig. 10, an infrared spectrum as shown in fig. 11, and an X-ray Energy Dispersive Spectroscopy (EDS) as shown in fig. 12.
EXAMPLE 7 preparation of 12 Nuclear Cyclic organotin oxysulfide Cluster
Thiourea (664 mg,8.7 mmol) was weighed into a 50mL glass bottle, then ethylene glycol (EG, 9mL,161.34 mmol) was added to the glass bottle at a time, butyltin trichloride (480. Mu.L, 3 mmol), N, N-dimethylformamide (DMF, 4.5mL,58.11 mmol) and 1-methylpiperazine (9 mL,81.27 mmol) were stirred at room temperature for 30 minutes, then the mixture was placed in an oven at 100℃for a constant temperature reaction for 7 days (168 hours), taken out, naturally cooled to room temperature, and the solid phase crystalline substance was obtained by separation and washed with ethanol, and the structure and the crystal parameters of the obtained colorless polyhedral crystalline product of cyclic organotin oxysulfide group were the same as those of the crystalline product in example 6. The yield of the crystalline product prepared in this example was tested to be 60%.
EXAMPLE 8 preparation of 12 Nuclear cyclic organotin oxysulfide Cluster
Sodium sulfide (160 mg,1.67 mmol) and cerium nitrate hydrate (90.1 mg,0.41 mmol) are weighed into a 20mL glass bottle, 1, 2-propanediol (PG, 2mL,27.23 mmol) and butyltin trichloride (90 mu L,0.56 mmol) are added into the glass bottle at one time, N, N-dimethylformamide (DMF, 1mL,12.86 mmol) and 1-methylpiperazine (2 mL,18.06 mmol) are stirred at room temperature for 30 minutes, then the mixture is placed into a baking oven at 100 ℃ for constant temperature reaction for 7 days (168 hours), the mixture is taken out, naturally cooled to room temperature, solid phase crystalline matters are obtained after separation, and then the solid phase crystalline matters are washed by ethanol, so that a colorless polyhedral annular organotin oxysulfide cluster crystalline product is obtained, the structural formula of which is shown in a formula (IV) and the crystal parameters of which are shown in a table 1. The yield of the crystalline product prepared in this example was tested to be 60%. As shown in FIG. 13, the crystalline product of the organotin oxysulfide group prepared in this example has a ring structure as can be seen from FIG. 13. The crystalline product prepared in this example has an X-ray powder diffraction pattern as shown in fig. 14, an infrared spectrum as shown in fig. 15, and an X-ray Energy Dispersive Spectroscopy (EDS) as shown in fig. 16.
Table 1 table of crystal parameters of cyclic organotin oxysulfide cluster compounds prepared in each example
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Example 9 application of polynuclear Cyclic organotin oxysulfide Cluster as catalyst in catalytic degradation of dye
The properties of the photocatalytic degradation dye of the cluster compound crystals are illustrated by taking the 12-core cyclic organotin-oxysulfide cluster crystalline product (hereinafter referred to as a cluster compound sample) prepared in example 7.
80mg of cluster compound sample is added into 100mL of methyl blue dye solution with the concentration of 1mmol/L, the mixture is stirred for 6h under dark conditions in the dark to reach adsorption-desorption balance, then a xenon lamp is used as a light source for illumination, 1mL of reaction liquid sample is extracted every 20min, and the concentration of the methyl blue dye in the sample is verified through ultraviolet absorption spectrum.
As can be seen from the test results of fig. 17, 18 and 19, the dye solution (test sample) added with the cluster sample was degraded by 83% in 2 hours; while the dye solution without added cluster crystals (blank sample) was hardly degraded (concentration reduced by only 2%).
It should be noted that, although the foregoing embodiments have been described herein, the scope of the present application is not limited thereby. Therefore, based on the innovative concepts of the present application, alterations and modifications to the embodiments described herein, or equivalent structures or equivalent flow transformations made by the present description and drawings, apply the above technical solution, directly or indirectly, to other relevant technical fields, all of which are included in the scope of the application.

Claims (11)

1. A polynuclear annular organotin oxysulfide cluster compound is characterized in that the cluster compound is formed by connecting a basic building unit A and a basic building unit B through an Sn-S bond, and has a chemical formula (A) n -(B) i Is a ring structure;
wherein i=0, 1 or 2;
when i=0, n is a natural number of 2 or more;
when i=1 or 2, n is a natural number of 1 or more;
the basic construction unit A has the structural formula:
the basic building unit B has the structural formula:
wherein R is selected from C1-C8 alkyl, phenyl, benzyl, p-methylphenyl, or p-ethylphenyl; r' is selected from H or C1-C20 alkyl; r' is selected from H or C1-C20 alkyl.
2. A method of preparing the polynuclear cyclic organotin oxysulfide cluster according to claim 1, comprising the steps of;
s1: adding organic metal tin, a sulfur source and organic amine into organic polyol, and uniformly mixing to obtain a mixed solution, wherein the molar ratio of the organic metal tin to the sulfur source to the organic amine to the organic polyol is 1: (2-10): (10-100): (50-150);
s2: heating the mixed solution to react, and cooling to room temperature to obtain a reaction product, wherein the reaction temperature of the heating reaction is 80-180 ℃ and the reaction time is 76-480 hours;
s3: and (3) separating and purifying the reaction product to obtain the cluster compound.
3. The method according to claim 2, wherein in step S1, the organometallic tin is one of methyl tin, ethyl tin, propyl tin, butyl tin, amyl tin, hexyl tin, octyl tin, phenyl tin, benzyl tin, p-methylphenyl tin, p-ethylphenyl tin.
4. The method according to claim 2, wherein in step S1, the sulfur source is one or a mixture of two of elemental sulfur powder, inorganic sulfide, organic sulfide.
5. The method according to claim 2, wherein in step S1, the organic amine is ethylenediamine, N, N '-dimethylethylenediamine, tetramethylethylenediamine, piperidine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, methylpiperidine, methylpiperazine, dimethylpiperazine, dimethylpiperidine, pentamethyldiethylenetriamine, N, N, N' -triethylethylenediamine, tetraethylethylenediamine, 1-methylpiperazine, 2-methylpiperazine, 1, 4-dimethylpiperazine, 1, 4-diethylpiperazine, 1, 2-dimethylpiperazine, N, one or a mixture of two of N, N ', N' -tetraethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N, N ', N' -tetrabutyldiethylenetriamine, hexaethyltriethylenetetramine, heptamethyltetraethylenepentamine, 1, 4-diethylpiperazine, 3-methyl-1-phenylpiperazine, 1-butylpiperazine, 1-phenethylpiperazine, 3-propylpiperidine, N, N-Dimethylformamide (DMF), N-methylformamide (NMF), N, N-Dimethylacetamide (DMA) or N, N-Diethylformamide (DEF).
6. The method according to claim 2, wherein in step S1, the organic polyol is one or a mixture of two of vicinal diols containing 1 to 40 carbon atoms.
7. The method according to claim 2, wherein the reaction temperature is 100 ℃ to 140 ℃ and the reaction time is 120 to 340 hours.
8. The method according to claim 2, wherein in step S2, an auxiliary agent is further added to the heating reaction, wherein the auxiliary agent is selected from one or more of tin dichloride, zinc chloride, zinc acetate, cadmium chloride, cadmium acetate, ferrocene, cerium nitrate hydrate, 2, 6-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, and 3, 5-dihydroxybenzoic acid.
9. The method according to claim 2, wherein in step S3, the separation and purification comprises:
separating from the reaction product to obtain a solid crystalline substance, and cleaning and purifying the solid crystalline substance by adopting an alcohol solvent to obtain the cluster compound.
10. The method according to claim 9, wherein the alcoholic solvent is one or a mixture of two of a monohydric alcohol or a dihydric alcohol having 1 to 40 carbon atoms.
11. The use of the polynuclear cyclic organotin oxysulfide cluster according to claim 1 as a catalyst for the catalytic degradation of dyes.
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