Half-sandwich rhodium building unit-based six-nuclear triangular prism compound as well as preparation method and application thereof

Abstract

The invention provides a six-core triangular prism compound based on a half-sandwich rhodium building unit as well as a preparation method and application of the six-core triangular prism compound, and belongs to the technical field of chemical synthesis. The six-core triangular prism compound based on the half-sandwich rhodium construction unit provided by the invention contains six rhodium, characterization is performed through single crystal X-ray diffraction, and a single crystal structure shows that the compound based on the half-sandwich rhodium construction unit provided by the invention shows a six-core triangular prism configuration; the distance between the long sides of the metal rhodium is # imgabs 0 #, the distance between the short sides of the metal rhodium is # imgabs 1 #, and the distance between the centers of the metal rhodium is # imgabs 2 #. Nuclear magnetic analysis and crystal structure analysis on the six-core triangular prism compound prove that the compound is of a six-core triangular prism structure in both a liquid phase and a solid phase; and potential application prospects can be realized in the fields of molecular recognition, separation and photo-thermal.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit, and a preparation method and application thereof. Background Art

[0002] Supramolecular coordination compounds are ordered discrete two-dimensional and three-dimensional molecular entities constructed by coordination-driven self-assembly strategies of suitable metal centers and ligands containing multiple binding sites, and have become a promising new research field in supramolecular chemistry. The advantages of this coordination compound are not only its colorful topological structure, but also its unique advantages in the fields of smart materials and nanodevices. Therefore, this field has attracted the attention of many outstanding scientific researchers and has gradually become a highly interesting research topic. They have shown good results in biological simulation, photothermal conversion and other aspects.

[0003] Moreover, half-sandwich iridium, rhodium, and ruthenium compounds containing late transition metals as building blocks of organometallic compounds show unique advantages in the synthesis of supramolecular coordination compounds, such as: the solubility of the compound can be changed; it is conducive to directional bonding and can easily coordinate with ligands. On the other hand, since the metal center of the half-sandwich structure can accommodate a variety of bridging ligands, it provides a variety of functionalized organic ligands to coordinate with it, thereby forming an ideal and functional metal-organic framework compound. However, the most classic supramolecular coordination type hexagonal compound with Cp*M (Cp*=pentamethylcyclopentadiene, M=Rh, Ir) fragment has rarely been reported.

[0004] The assembled Cp*M (M=Rh, Ir) binuclear building blocks and electron-donating ligands with larger π conjugated planes are self-assembled to easily form complex interlocking supramolecular compounds. Only by rationally controlling the conjugated plane of the pyridine ligands can the formation of interlocking topology be avoided. For example, the tridentate pyridine ligand 4,4',4"-(5,5',5"-(2,4,6-trimethoxybenzene-1,3,5-triyl)tri(furan-5,2-diyl))tripyridine containing multiple methoxy groups was self-assembled with the same building block E1 to form a stable twelve-nuclear interlocking cage structure.

[0005] Therefore, it is of great significance to rationally control the size of building blocks and pyridine connectors to synthesize new hexanuclear triangular prism compounds with triple interlocking structures. Summary of the invention

[0006] The purpose of the present invention is to provide a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit, and a preparation method and application thereof. The compound provided by the present invention exhibits a hexanuclear triangular prism structure in both the liquid phase and the solid phase, which enables it to have potential application prospects in the fields of molecular recognition, separation or photothermal fields.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit, having a structure shown in Formula I:

[0009]

[0010] The present invention provides a method for preparing a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit according to the above technical solution, comprising the following steps:

[0011] (1) mixing silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in a first solvent and performing a precipitation reaction to obtain an intermediate solution;

[0012] (2) adding 2,5-dihydroxy-1,4-benzoquinone to the intermediate solution obtained in step (1) to perform a first coordination self-assembly to obtain a semi-sandwich rhodium building unit E1;

[0013] (3) subjecting the half-sandwich rhodium building unit E1 obtained in step (2) and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine to a second coordination self-assembly in a second solvent to obtain a hexanuclear triangular prism compound based on the half-sandwich rhodium building unit.

[0014] Preferably, in step (1), the molar ratio of silver trifluoromethanesulfonate to dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is (4-5):1.

[0015] Preferably, the precipitation reaction time in step (1) is 4 to 5 hours.

[0016] Preferably, the time for the first coordination self-assembly in step (2) is 9 to 10 hours.

[0017] Preferably, after the first coordination self-assembly in step (2) is completed, the product of the first coordination self-assembly is concentrated, solid precipitated, filtered and washed in sequence to obtain a semi-sandwich rhodium building unit E1.

[0018] Preferably, in step (3), the molar ratio of the semi-sandwich rhodium building block E1 to tris[4-(2-pyridin-4-ylvinyl)phenyl]amine is 3:(1.5-2.5).

[0019] Preferably, the time for the second coordination self-assembly in step (3) is 9 to 10 hours.

[0020] Preferably, after the second coordination self-assembly in step (3) is completed, the product of the second coordination self-assembly is concentrated, solid precipitated, filtered and washed in sequence to obtain a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit.

[0021] The present invention provides applications of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit described in the above technical scheme or the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit prepared by the preparation method described in the above technical scheme in the fields of molecular recognition, separation and photothermal fields.

[0022] The hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit provided by the present invention contains six rhodiums. The single crystal X-ray diffraction is used for characterization. The single crystal structure shows that the compound based on the semi-sandwich rhodium building unit provided by the present invention exhibits a hexanuclear triangular prism configuration. The distance between the long sides of the metal rhodium is The distance between the short sides is The distance between the centers is By performing nuclear magnetic resonance analysis and crystal structure analysis on the six-nuclear triangular prism compound, it is proved that the compound exhibits a six-nuclear triangular prism structure in both the liquid phase and the solid phase, which can make it have potential application prospects in the field of molecular recognition, separation or photothermal field. The results of the embodiment show that the yield of the six-nuclear triangular prism compound based on the half-sandwich rhodium building unit provided by the present invention in the preparation process reaches 86%, and the six-nuclear triangular prism compound based on the half-sandwich rhodium building unit has an obvious photothermal conversion effect, and the photothermal conversion effect comes from two aspects: 1. The half-sandwich building unit has an obvious fluorescence quenching effect; 2. The close stacking effect in the solid state inhibits the radiative transition and promotes the non-radiative transition. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A synthetic route for a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit provided by the present invention;

[0024] Figure 2 The six-nuclear triangular prism compound based on the half-sandwich rhodium building unit prepared in Example 1 1 H NMR spectrum;

[0025] Figure 3 The six-nuclear triangular prism compound based on the half-sandwich rhodium building unit prepared in Example 1 1 H- 1 H COSYNMR spectrum;

[0026] Figure 4The six-nuclear triangular prism compound based on the half-sandwich rhodium building unit prepared in Example 1 1 H- 1 H DOSYNMR spectrum;

[0027] Figure 5 The crystal structure of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit prepared in Example 1;

[0028] Figure 6 The temperature change of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit prepared in Example 1 under 730nm laser irradiation. DETAILED DESCRIPTION

[0029] The present invention provides a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit, having a structure shown in Formula I:

[0030]

[0031] In the present invention, the OTf- is preferably CF3SO3 - .

[0032] The hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit provided by the present invention contains six rhodiums. The single crystal X-ray diffraction is used for characterization. The single crystal structure shows that the compound based on the semi-sandwich rhodium building unit provided by the present invention exhibits a hexanuclear triangular prism configuration. The distance between the long sides of the metal rhodium is The distance between the short sides is The distance between the centers is Through nuclear magnetic resonance analysis and crystal structure analysis of the hexanuclear triangular prism compound, it is proved that the compound exhibits a hexanuclear triangular prism structure in both liquid and solid phases, which can make it have potential application prospects in the fields of molecular recognition, separation or photothermal fields.

[0033] The present invention provides a method for preparing a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit according to the above technical solution, comprising the following steps:

[0034] (1) mixing silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in a first solvent and performing a precipitation reaction to obtain an intermediate solution;

[0035] (2) adding 2,5-dihydroxy-1,4-benzoquinone to the intermediate solution obtained in step (1) to perform a first coordination self-assembly to obtain a semi-sandwich rhodium building unit E1;

[0036] (3) subjecting the half-sandwich rhodium building unit E1 obtained in step (2) and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine to a second coordination self-assembly in a second solvent to obtain a hexanuclear triangular prism compound based on the half-sandwich rhodium building unit.

[0037] In the present invention, unless otherwise specified, the raw materials used in the present invention are all commercially available products well known to those skilled in the art.

[0038] The invention mixes silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in a first solvent, performs precipitation reaction, and obtains an intermediate solution.

[0039] In the present invention, the silver trifluoromethanesulfonate is preferably white silver trifluoromethanesulfonate; the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is preferably red dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer; and the first solvent is preferably methanol. The present invention has no special limitation on the specific amount of the methanol, which can be determined according to the technical common sense of those skilled in the art as long as the raw materials can be completely dissolved. The present invention uses the above raw materials, which have high purity, few impurities, and can be dissolved in an organic solution.

[0040] In the present invention, the molar ratio of the silver trifluoromethanesulfonate and the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is preferably (4-5):1, more preferably 4:1. The present invention can ensure full reaction and avoid waste of raw materials by controlling the usage relationship of the silver trifluoromethanesulfonate and the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer.

[0041] In the present invention, the time of the precipitation reaction is preferably 4 to 5 hours, more preferably 4.5 hours. In the present invention, the temperature of the precipitation reaction is preferably room temperature; the precipitation reaction is preferably carried out under light-proof conditions; stirring is performed during the precipitation reaction. The present invention has no special limitation on the stirring rate, which can be determined according to the technical common sense of those skilled in the art to avoid splashing of the solution. The present invention can ensure the normal and sufficient progress of the reaction by controlling the parameters of the precipitation reaction, thereby improving the yield of the product and avoiding waste of raw materials; by continuous stirring during the reaction, the raw materials can be fully contacted, thereby further improving the reaction efficiency.

[0042] After the precipitation reaction is completed, the present invention preferably removes the precipitate of the precipitation reaction; the precipitate is preferably removed by filtering and separation. In the present invention, the precipitate is a white precipitate.

[0043] In the present invention, the structural formula of the intermediate in the intermediate solution is preferably as shown in Formula II:

[0044]

[0045] After obtaining the intermediate solution, the present invention adds 2,5-dihydroxy-1,4-benzoquinone to the intermediate solution to perform the first coordination self-assembly to obtain the semi-sandwich rhodium building unit E1.

[0046] In the present invention, the structural formula of the 2,5-dihydroxy-1,4-benzoquinone is preferably as shown in Formula III:

[0047]

[0048] In the present invention, the molar ratio of the 2,5-dihydroxy-1,4-benzoquinone to the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is preferably 1:(1-2), more preferably 1: 1. The present invention can ensure complete reaction, avoid waste of raw materials and reduce costs by controlling the amount of 2,5-dihydroxy-1,4-benzoquinone added.

[0049] In the present invention, the time of the first coordination self-assembly is preferably 9 to 10 hours, more preferably 9.5 hours; the temperature of the first coordination self-assembly is preferably room temperature; the first coordination self-assembly is preferably carried out under stirring conditions. The present invention has no special limitation on the stirring rate, which can be determined according to the technical common sense of those skilled in the art to avoid splashing of the solution. The present invention can ensure the normal and sufficient progress of the reaction by controlling the parameters of the precipitation reaction, thereby improving the yield of the product and avoiding waste of raw materials; by continuous stirring during the reaction, the raw materials can be fully contacted, thereby further improving the reaction efficiency.

[0050] After the first coordination self-assembly is completed, the present invention preferably concentrates the product of the first coordination self-assembly in sequence, precipitates a solid, filters and washes it to obtain a semi-sandwich rhodium building unit E1.

[0051] In the present invention, the concentration method is preferably evaporation concentration; the concentration is preferably concentrated to 65% of the original volume. The present invention can remove a large amount of solvent through concentration.

[0052] In the present invention, the method of precipitating solid precipitation is preferably to add diethyl ether. The present invention has no special limitation on the specific amount of diethyl ether, which can be determined according to the technical common sense of those skilled in the art until no solid precipitation is precipitated.

[0053] The present invention has no particular limitation on the specific operation of the filtration, and any filtration operation well known to those skilled in the art can be used to separate solids from liquids.

[0054] In the present invention, the detergent used in the washing is preferably ether. The present invention has no particular limitation on the number of washings, as long as the impurities are completely removed.

[0055] In the present invention, the structural formula of the semi-sandwich rhodium building unit E1 is preferably as shown in Formula IV:

[0056]

[0057] After obtaining the half-sandwich rhodium building unit E1, the present invention conducts a second coordination self-assembly of the half-sandwich rhodium building unit E1 and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine in a second solvent to obtain a hexanuclear triangular prism compound based on the half-sandwich rhodium building unit.

[0058] In the present invention, the tri[4-(2-pyridin-4-ylvinyl)phenyl]amine is preferably as shown in Formula V:

[0059]

[0060] In the present invention, the molar ratio of the semi-sandwich rhodium building unit E1 and tris[4-(2-pyridin-4-ylvinyl)phenyl]amine is preferably 3:(1.5-2.5), more preferably 3:2. In the present invention, the second solvent is preferably methanol. The present invention has no special limitation on the specific amount of the methanol, which can be determined according to the technical common sense of those skilled in the art as long as the raw materials can be completely dissolved. The present invention can ensure complete reaction by controlling the amount of each component.

[0061] In the present invention, the time of the second coordination self-assembly is preferably 9 to 10 hours, more preferably 9.5 hours; the temperature of the second coordination self-assembly is preferably room temperature; the second coordination self-assembly is preferably carried out under light-proof conditions; the second coordination self-assembly is preferably carried out under stirring conditions. The present invention has no special limitation on the stirring rate, which can be determined according to the technical common sense of those skilled in the art to avoid splashing of the solution. The present invention can ensure the normal and sufficient progress of the reaction by controlling the parameters of the precipitation reaction, thereby improving the yield of the product and avoiding waste of raw materials; by continuously stirring during the reaction, the raw materials can be fully contacted, thereby further improving the reaction efficiency.

[0062] After the second coordination self-assembly is completed, the present invention preferably concentrates the product of the second coordination self-assembly, precipitates solid, filters and washes it in sequence to obtain a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit.

[0063] In the present invention, the concentration method is preferably evaporation concentration; the concentration is preferably concentrated to 65% of the original volume. The present invention can remove a large amount of solvent through concentration.

[0064] In the present invention, the method of precipitating solid precipitation is preferably to add diethyl ether. The present invention has no special limitation on the specific amount of diethyl ether, which can be determined according to the technical common sense of those skilled in the art until no solid precipitation is precipitated.

[0065] The present invention has no particular limitation on the specific operation of the filtration, and any filtration operation well known to those skilled in the art can be used to separate solids from liquids.

[0066] In the present invention, the detergent used in the washing is preferably ether. The present invention has no particular limitation on the number of washings, as long as the impurities are completely removed.

[0067] In the present invention, the synthesis route of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit is as follows: Figure 1 shown.

[0068] The preparation method provided by the present invention firstly uses silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer to prepare an intermediate, then uses the intermediate and 2,5-dihydroxy-1,4-benzoquinone to synthesize a semi-sandwich rhodium building unit E1, and finally uses the semi-sandwich rhodium building unit E1 and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine to synthesize a hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit.

[0069] The preparation method provided by the invention is simple, and the synthesis conditions are easy to control. By controlling the amount of each component, it can be ensured that there is little waste of raw materials, the raw material cost is low and the yield of the product is high.

[0070] The present invention also provides the application of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit described in the above technical scheme or the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit prepared by the preparation method described in the above technical scheme in the fields of molecular recognition, separation and photothermal fields.

[0071] The present invention has no particular limitation on the specific manner of the application, and the application may be performed according to the technical common sense of those skilled in the art.

[0072] The six-nuclear triangular prism compound based on the half-sandwich rhodium building unit provided by the present invention has important application prospects in the separation of different halogenated benzenes, the separation of benzene and cyclohexane, and the field of photothermal conversion. Since the electron donation and electron deficiency effects can lead to the formation of π-π stacking, the six-nuclear triangular prism compound based on the half-sandwich rhodium building unit provided by the present invention can capture benzene molecules with electron donation effect, and since cyclohexane has no conjugated effect, it cannot be captured. Therefore, the six-nuclear triangular prism compound based on the half-sandwich rhodium building unit provided by the present invention can achieve the separation of benzene and cyclohexane.

[0073] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0074] Example 1

[0075] A hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit has a structure shown in Formula I:

[0076]

[0077] The OTf - CF3SO3 - ;

[0078] The preparation method of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit consists of the following steps:

[0079] (1) white silver trifluoromethanesulfonate and red dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer are mixed in methanol, subjected to precipitation reaction under light-shielding conditions, and then filtered and separated to obtain a yellow intermediate solution; the molar ratio of the silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is 4:1; the precipitation reaction time is 4.5 hours, the precipitation reaction temperature is room temperature, and stirring is performed during the precipitation reaction;

[0080] (2) adding 2,5-dihydroxy-1,4-benzoquinone to the intermediate solution obtained in step (1) to perform a first coordination self-assembly, then concentrating to 65% of the original volume, adding ether until no solid precipitates, filtering and washing with ether to obtain a semi-sandwich rhodium building unit E1; the molar ratio of the 2,5-dihydroxy-1,4-benzoquinone to the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is 1:1; the first coordination self-assembly time is 9.5 h, the first coordination self-assembly temperature is room temperature, and the first coordination self-assembly is performed under stirring conditions;

[0081] (3) The half-sandwich rhodium building unit E1 obtained in step (2) and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine are subjected to a second coordination self-assembly in methanol, and then concentrated to 65% of the original volume, and then ether is added until no solid precipitates. After filtering, a yellow compound is obtained, and after washing with ether, a hexanuclear triangular prism compound based on the half-sandwich rhodium building unit is obtained; the molar ratio of the half-sandwich rhodium building unit E1 and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine is 3:2; the second coordination self-assembly time is 9.5h, the second coordination self-assembly temperature is room temperature, the second coordination self-assembly is carried out under light-proof conditions, and the second coordination self-assembly is carried out under magnetic stirring conditions.

[0082] After calculation, the yield of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit prepared in Example 1 is 86%. It can be seen that the preparation method provided by the present invention can make as many raw materials as possible react during the preparation process, thereby reducing the waste of raw materials.

[0083] The liquid structural stability of the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit obtained in Example 1 was characterized in detail, and the nuclear magnetic resonance spectrum was obtained using a Bruke-DPX400 superconducting nuclear magnetic resonance instrument produced by Bruke, Sweden. 1 H NMR spectrum Figure 2 As shown, 1 H- 1 H COSY NMR spectrum Figure 3 As shown, 1 H- 1 H DOSY NMR spectrum is shown in Figure 4 shown.

[0084] pass Figure 2 The 1HNMR spectrum shows that there is a single peak at 1.69 ppm, which can be attributed to the proton peak of pentamethylcyclopentadienyl. There are two strong 1:1 double peaks at 8.12 and 7.57 ppm.

[0085] Figure 3The 1H-1H COSYNMR spectrum shows obvious coupling, which can be proved to be adjacent hydrogen peaks. The carbon on the pyridine group is directly connected to the nitrogen with higher electronegativity. The inductive effect produces a deshielding effect, so the proton peak on the pyridine carbon appears at a lower field than the proton peaks on other carbons. Therefore, it can be attributed to the pyridine proton peak of ligand L1. The two coupled double peaks appearing at 7.47 and 6.99ppm are the phenyl proton peaks of ligand L1. The olefin proton peaks of L1 appear at 7.43 and 6.94ppm. In addition, the single peak appearing at 4.87ppm is the proton peak of H2O; the proton peak of CD3OD appears at 3.31ppm.

[0086] Through Figure 4 By analyzing the 1H-1H DOSY NMR spectrum, it can be clearly observed that the diffusion coefficients of all signals are consistent, which reflects that the compound is still a complete assembly in the solution, proving that the hexanuclear triangular prism compound is relatively stable in the solution.

[0087] The crystal structure of the hexanuclear triangular prism compound based on the half-sandwich rhodium building unit obtained in the example was determined using a Bigaku AFC10 X-ray single crystal diffractometer produced by Rigaku Corporation of Japan. The crystal structure of the hexanuclear triangular prism compound based on the half-sandwich rhodium building unit is as follows: Figure 5 As shown. Figure 5 It can be seen that the single crystal structure exhibits a triangular prism configuration, and the distance between the long sides of the metal rhodium in the compound is The distance between the short sides is The distance between the centers is

[0088] The hexanuclear triangular prism compound (5 mg) based on the semi-sandwich rhodium building unit obtained in Example 1 was placed in a high temperature resistant sample tank, and the sample was irradiated with 730 nm near-infrared light. At the same time, the temperature change of the sample was monitored with a near-infrared imager. The results are as follows: Figure 6 As shown. Figure 6 It can be seen that as time goes by, the temperature change (26.3-88.7°C) can be clearly observed, and the results show that the hexanuclear triangular prism compound based on the half-sandwich rhodium building unit has an obvious photothermal conversion effect. This photothermal conversion effect comes from two aspects: 1. The half-sandwich building unit has an obvious fluorescence quenching effect; 2. The close stacking effect in the solid state inhibits the radiative transition and promotes the non-radiative transition.

[0089] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit having a structure shown in Formula I:

2. The method for preparing the hexanuclear triangular prism compound based on the semi-sandwich rhodium building unit according to claim 1, comprising the following steps: (1) mixing silver trifluoromethanesulfonate and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in a first solvent and performing a precipitation reaction to obtain an intermediate solution; (2) adding 2,5-dihydroxy-1,4-benzoquinone to the intermediate solution obtained in step (1) to perform a first coordination self-assembly to obtain a semi-sandwich rhodium building unit E1; (3) subjecting the half-sandwich rhodium building unit E1 obtained in step (2) and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine to a second coordination self-assembly in a second solvent to obtain a hexanuclear triangular prism compound based on the half-sandwich rhodium building unit.

3. The preparation method according to claim 2, characterized in that: In the step (1), the molar ratio of silver trifluoromethanesulfonate to dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is (4-5):

1.

4. The preparation method according to claim 2, characterized in that: The precipitation reaction time in step (1) is 4 to 5 hours.

5. The preparation method according to claim 2, characterized in that: The time of the first coordination self-assembly in step (2) is 9 to 10 hours.

6. The preparation method according to claim 2, characterized in that: After the first coordination self-assembly in step (2) is completed, the product of the first coordination self-assembly is concentrated, solid precipitated, filtered and washed in sequence to obtain a semi-sandwich rhodium building unit E1.

7. The preparation method according to claim 2, characterized in that: In the step (3), the molar ratio of the semi-sandwich rhodium building unit E1 and tri[4-(2-pyridin-4-ylvinyl)phenyl]amine is 3:(1.5-2.5).

8. The preparation method according to claim 2, characterized in that: The time for the second coordination self-assembly in step (3) is 9 to 10 hours.

9. The preparation method according to claim 2, characterized in that: After the second coordination self-assembly in step (3) is completed, the product of the second coordination self-assembly is concentrated, solid precipitated, filtered and washed in sequence to obtain a hexanuclear triangular prism compound based on a semi-sandwich rhodium building unit.

10. Application of the hexanuclear triangular prism compound based on a half-sandwich rhodium building unit according to claim 1 or the hexanuclear triangular prism compound based on a half-sandwich rhodium building unit prepared by the preparation method according to any one of claims 2 to 9 in the fields of molecular recognition, separation and photothermal fields.

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