A butyl tin-cyclo iridium salicylaldehyde schiff base complex with AIE characteristics, and a preparation method and application thereof

Abstract

The application discloses a butyl tin-cyclo iridium salicylaldehyde Schiff base complex with an aggregation-induced emission (AIE) property, a preparation method of the complex and anti-cancer application of the complex. The structural formula of the complex is shown as formula (I), and R is one of hydrogen, chlorine, bromine, methyl, methoxy and trifluoromethoxy. The growth inhibition rates of the target compound on human alveolar basal epithelial carcinoma cells (A549) and cisplatin-resistant cancer cells (A549 / DDP), cervical cancer cells (Hela) and human lung normal epithelial cells (BEAS-2B) are tested, and it is found through comparison that the target complex shows potential anti-proliferation activity and is superior to cisplatin. In addition, the target compound shows unique AIE emission characteristics. The target compound can target the mitochondria of A549 cells and cause the decline of the mitochondrial membrane potential, thereby showing anti-cancer activity.

Description

Technical fields:

[0001] This invention relates to organometallic compounds, specifically to a butyltin-cycloiridium salicylaldehyde Schiff base complex with AIE properties, its preparation method, and its applications, belonging to the field of chemical pharmaceuticals. Background technology:

[0002] In the 21st century, cancer remains one of the most prevalent and deadly human diseases. Chemotherapy is a common clinical treatment for cancer. However, most platinum-based drugs used clinically suffer from drawbacks such as drug resistance and significant toxic side effects. These shortcomings have spurred the exploration of other transition metal anticancer drugs, including Ru(II), Rh(III), Ir(III), and Sn(IV) complexes (Chem. Soc. Rev. 2015, 44, 8818-8835). The third transition metal iridium has shown potential antiproliferative activity against cancer cells (Acc. Chem. Res. 2014, 47, 1174-1185). Based on structural characteristics, iridium anticancer complexes can be divided into two types: half-sandwich structure and cyclic iridium structure (Inorg. Chem. 2023, 62, 3395-3408). Among them, cycloiridium complexes are widely used in bioimaging, biosensing, and anticancer fields due to their excellent photophysical properties (Inorg. Chem. 2013, 52, 974-982). Butyltin compounds also exhibit significant antitumor activity (Appl. Organomet. Chem. 2018, 32, 4475), but their severe toxicity greatly limits their application. Furthermore, cyclometal complexes and butyltin compounds exhibit weak fluorescence or aggregation-induced quenching (ACQ) due to concentration, which is highly detrimental to research on subcellular tissue targeting. It wasn't until Tang Benzhong's team discovered the aggregation-induced emission (AIE) effect that effectively avoided fluorescence quenching caused by molecular aggregation. Metal compounds with AIE properties have been widely used in photocatalysis, light-emitting diodes, and biomedicine (ACS Cent. Sci. 2020, 6, 1689-1712). However, multi-active-center heteronuclear metal complexes with AIE properties are rare in anticancer drug development. Summary of the Invention:

[0003] Therefore, this invention introduces a tributyltin molecule with good anticancer potential to enhance the overall anticancer activity of the complex. Furthermore, due to the presence of the imine bond in the Schiff base, the nitrogen atom in its hybrid orbital possesses a lone pair of electrons, giving the Schiff base excellent coordination ability. It can coordinate with metallic iridium to obtain an iridium-tin multimetallic center complex with AIE characteristics, allowing the target complex to exhibit both good anticancer activity and excellent photophysical properties. Its excellent AIE luminescence properties can be used to detect the target site (mitochondria) of the target complex in cancer cells, making it a promising candidate for novel mitochondrial-targeted metal anticancer drugs. A cyclic iridium salicylaldehyde Schiff base complex has the structure shown in formula (II):

[0004]

[0005] R is selected from one of chlorine, bromine, methyl, methoxy, and trifluoromethoxy.

[0006] A butyltin-cycloiridium salicylaldehyde Schiff base complex, the structure of which is shown in formula (I):

[0007]

[0008] R is selected from one of hydrogen, chlorine, bromine, methyl, methoxy, and trifluoromethoxy.

[0009] Furthermore, the chemical structural formula of the butyltin-cycloiridium salicylaldehyde Schiff base complex of the present invention is as follows:

[0010]

[0011] This invention provides a method for preparing the above-mentioned complexes: A salicylaldehyde Schiff base benzoic acid compound reacts with a dimer of basic iridium (Ir1) to obtain the complexes (Ir2-Ir6) shown in formula (II), wherein the salicylaldehyde Schiff base benzoic acid is (E)-4-((5-chloro-2-hydroxybenzaldehyde)amino)benzoic acid, (E)-4-((5-bromo-2-hydroxybenzaldehyde)amino)benzoic acid, (E)-4-((2-hydroxy-5-methylbenzaldehyde)amino)benzoic acid, (E)-4-((2-hydroxy-5-methoxybenzaldehyde)amino)benzoic acid, or (E)-4-((2-hydroxy-5-(trifluoromethoxy)benzaldehyde)amino)benzoic acid); the complex shown in formula (II) reacts with hexabutyltin oxide (Bu6Sn2O) molecules to obtain the target complex shown in formula (I), and the specific reaction route is as follows:

[0012]

[0013] Furthermore, when the compound is of formula (1), it is prepared by the following method:

[0014] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.045 g (E)-4-((2-hydroxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixture of 20 mL dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, a yellow solid powder product [(ppy)2Ir(L1)] was obtained.

[0015] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (R=H) and 17.19 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the orange-yellow solid target product (1).

[0016] Furthermore, when the compound is of formula (2), it is prepared by the following method:

[0017] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.051 g (E)-4-((5-chloro-2-hydroxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixed solution of dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, the target product (Ir2) was obtained as a yellow solid powder.

[0018] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir2, R=Cl) and 16.43 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the orange-yellow solid target product (2).

[0019] Furthermore, when the compound is of formula (3), it is prepared by the following method:

[0020] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.060 g (E)-4-((5-bromo-2-hydroxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixture of 20 mL dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, the target product (Ir3) was obtained as an orange-yellow solid powder.

[0021] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir3, R=Br) and 15.54 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the orange-yellow solid target product (3).

[0022] Furthermore, when the compound is of formula (4), it is prepared by the following method:

[0023] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.048 g (E)-4-((2-hydroxy-5-methylbenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixture of 20 mL dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, the target product (Ir4) was obtained as an orange solid powder.

[0024] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir4, R=Me) and 16.87 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the orange solid target product (4).

[0025] Furthermore, when the compound is of formula (5), it is prepared by the following method:

[0026] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.051 g (E)-4-((2-hydroxy-5-methoxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixture of 20 mL dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, the target product (Ir5) was obtained as an orange-red solid powder.

[0027] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir5, R = OCH3) and 16.52 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the orange-red solid target product (5).

[0028] Furthermore, when the compound is of formula (6), it is prepared by the following method:

[0029] (1) 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.061 g (E)-4-((2-hydroxy-5-(trifluoromethoxy)benzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A mixture of 20 mL dichloromethane and methanol (1:1, v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure. The mixture was dissolved in dichloromethane and purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, the target product (Ir6) was obtained as a red solid powder.

[0030] (2) 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir6, R = OCF3) and 15.44 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent, and the mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to obtain the red solid target product (6).

[0031] This invention provides an application of butyltin-cycloiridium salicylaldehyde Schiff base complexes prepared by the above method in the field of anticancer drug preparation. These complexes exhibit potential anticancer activity, providing a fundamental structural platform for the design and development of novel transition metal anticancer drugs. Simultaneously, the target complexes exhibit aggregation-induced emission (AIE) properties, which facilitates in-situ tracking and detection of drug targeting sites within cancer cells.

[0032] The beneficial effects of this invention are as follows:

[0033] (1) This invention proposes the design of a butyltin-cycloiridium salicylaldehyde Schiff base multimetallic core anticancer complex. Compared with single cycloiridium complexes, the introduction of tributyltin molecules effectively improves the overall anticancer activity and exhibits a synergistic effect;

[0034] (2) The target complex of the present invention has aggregation-induced emission (AIE) properties, which facilitates the exploration of its target location in cancer cells and the study of its anti-cancer mechanism. Attached image description:

[0035] Figure 1 The above is the 1H NMR spectrum of the complex Ir2 of this invention.

[0036] Figure 2 The above is the 1H NMR spectrum of the complex Ir3 of this invention.

[0037] Figure 3 The above is the 1H NMR spectrum of the complex Ir4 of this invention.

[0038] Figure 4 The above is the 1H NMR spectrum of the complex Ir5 of this invention.

[0039] Figure 5 The above is the 1H NMR spectrum of the complex Ir6 of this invention.

[0040] Figure 6 This is the 1H NMR spectrum of complex 1 of the present invention.

[0041] Figure 7 The above is the 1H NMR spectrum of complex 2 of the present invention.

[0042] Figure 8 The above is the 1H NMR spectrum of complex 3 of the present invention.

[0043] Figure 9 The above is the 1H NMR spectrum of complex 4 of this invention.

[0044] Figure 10 The above is the 1H NMR spectrum of complex 5 of the present invention.

[0045] Figure 11 The above is the 1H NMR spectrum of complex 6 of this invention.

[0046] Figure 12 This is the mass spectrometry of the complex Ir2 of this invention.

[0047] Figure 13 This is the mass spectrometry of the complex Ir3 of this invention.

[0048] Figure 14 This is the mass spectrometry of the complex Ir4 of this invention.

[0049] Figure 15 This is the mass spectrometry of the complex Ir5 of this invention.

[0050] Figure 16 This is the mass spectrometry of the complex Ir6 of this invention.

[0051] Figure 17 This is the mass spectrometry of coordination compound 1 of the present invention.

[0052] Figure 18 This is the mass spectrometry of coordination compound 2 of the present invention.

[0053] Figure 19 This is the mass spectrometry of coordination compound 3 of the present invention.

[0054] Figure 20 This is the mass spectrometry of complex 4 of the present invention.

[0055] Figure 21 This is the mass spectrometry of coordination compound 5 of the present invention.

[0056] Figure 22 This is the mass spectrometry of coordination compound 6 of the present invention.

[0057] Figure 23 This is a cell tissue targeting test diagram of complex 6 of the present invention.

[0058] Figure 24 This is a diagram showing the changes in mitochondrial membrane potential induced by complex 6 of the present invention.

[0059] Figure 25 This is a graph showing the AIE property test results of complex 6 of the present invention. Detailed implementation method:

[0060] The present invention is further illustrated by embodiments of some representative complexes described below, but these descriptions do not limit the present invention.

[0061] The starting compounds used in the synthesis of the target complexes are commercial products or can be prepared by known synthetic methods. All methods for preparing organic target complexes are available in the literature and are fundamental and obvious to synthetic chemists. Therefore, the following descriptions of the synthetic methods can be considered detailed and specific.

[0062] Example 1

[0063] 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.051 g (E)-4-((5-chloro-2-hydroxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A 1:1 mixture of dichloromethane and methanol (v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The solution was purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, 0.128 g of the target product (Ir2) was obtained as a yellow solid powder; the yield was 88.3%. The characterization spectrum is shown below. Figure 1 and Figure 12 As shown: 1 H NMR(500MHz,DMSO)δ8.90(d,J=5.6Hz,1H),8.65(d,J=5.8Hz,1H),8.23(s,1H),8.15(d,J=8.1Hz,1H),7 .95–7.87(m,3H),7.70(d,J=7.8Hz,1H),7.43–7.37(m,2H),7.37–7.33(m,1H),7.28(d,J=8.4Hz,2H),7. 23(d,J=7.7Hz,1H),7.13(dd,J=9.2,2.9Hz,1H),6.78(t,J=7.5Hz,1H),6.62(t,J=7.4Hz,1H),6.42(tt, J=14.7,7.3Hz,4H),6.08(d,J=8.2Hz,2H),6.02(d,J=7.6Hz,1H),5.93(d,J=7.6Hz,1H).ESI-MS(m / z):C 36 H 25 O3N3ClIr:Calcd for 775.1214;Found,776.1284,[M+H] + .

[0064] Example 2

[0065] 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.060 g (E)-4-((5-bromo-2-hydroxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A 1:1 mixture of dichloromethane and methanol (v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The solution was purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, 0.130 g of the target product (Ir3) was obtained as an orange-yellow solid powder; the yield was 85.0%. The characterization spectrum is shown below. Figure 2 and Figure 13 As shown: 1 H NMR (500MHz, DMSO) δ8.89(d,J=5.7Hz,1H),8.63(d,J=5.9Hz,1H),8.22(s,1H),8.14(d,J=8.1Hz,1H),7.98–7 .85(m,4H),7.69(d,J=7.8Hz,1H),7.52(d,J=2.7Hz,1H),7.39(td,J=6.0,2.5Hz,1H),7.36–7.33(m,1H),7.2 7(d,J=8.3Hz,2H),7.24–7.19(m,2H),6.78(t,J=7.4Hz,1H),6.61(t,J=7.4Hz,1H),6.45(t,J=7.2Hz,1H),6. 39(dd,J=8.3,5.4Hz,2H),6.08(d,J=8.1Hz,2H),6.02(d,J=7.5Hz,1H),5.93(d,J=7.5Hz,1H).ESI-MS(m / z):C 36 H 25 O3N3BrIr:Calcd for 819.0709;Found,820.0780,[M+H] + .

[0066] Example 3

[0067] 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.048 g (E)-4-((2-hydroxy-5-methylbenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A 1:1 mixture of dichloromethane and methanol (v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The solution was purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, 0.113 g of the target product (Ir4) was obtained as an orange solid powder; the yield was 80.1%. The characterization spectrum is shown below. Figure 3 and Figure 14 As shown: 1 H NMR(500MHz,DMSO)δ8.95–8.88(m,1H),8.67(d,J=5.6Hz,1H),8.18–8.11(m,2H), 7.96–7.82(m,4H),7.69(d,J=7.8Hz,1H),7.39–7.21(m,6H),6.93–6.86(m,2H),6. 77(t,J=7.4Hz,1H),6.60(t,J=7.3Hz,1H),6.46–6.36(m,3H),6.09(d,J=8.2Hz,1H ),6.02(d,J=7.4Hz,1H),5.94(d,J=7.5Hz,1H),2.50–2.50(m,3H).ESI-MS(m / z):C 37 H 28 O3N3Ir:Calcd for 755.1760;Found,756.1832,[M+H] + .

[0068] Example 4

[0069] 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.051 g (E)-4-((2-hydroxy-5-methoxybenzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A 1:1 mixture of dichloromethane and methanol (v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The solution was purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, 0.121 g of the target product (Ir5) was obtained as an orange-red solid powder; the yield was 78.6%. The characterization spectrum is shown below. Figure 4 and Figure 15 As shown: 1H NMR (500MHz, DMSO) δ8.92–8.87(m,1H),8.65(d,J=5.7Hz,1H),8.16–8.09(m,2H),7.95–7.86(m,3H ),7.69(d,J=7.7Hz,1H),7.39–7.30(m,2H),7.30–7.19(m,4H),7.06(d,J=1.8Hz,1H),7.00(dd,J= 8.7,2.3Hz,1H),6.77(t,J=7.5Hz,1H),6.60(t,J=7.4Hz,1H),6.44(t,J=7.3Hz,1H),6.37(dd,J=1 3.9,8.0Hz,2H),6.05(dd,J=27.8,7.8Hz,3H),5.93(d,J=7.4Hz,1H),2.11(s,3H).ESI-MS(m / z):C 37 H 28 O4N3Ir:Calcd for771.1709;Found,772.1781,[M+H] + .

[0070] Example 5

[0071] 0.100 g (Ir1), 0.062 g anhydrous sodium acetate, and 0.061 g (E)-4-((2-hydroxy-5-(trifluoromethoxy)benzaldehyde)amino)benzoic acid were placed in a 100 mL Schlenk flask. A 1:1 mixture of dichloromethane and methanol (v / v) was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The solution was purified by silica gel column chromatography using dichloromethane / methanol (20:1, v / v) as the eluent. After removing the solvent and drying, 0.100 g of the target product (Ir6) was obtained as a red solid powder; the yield was 84.4%. The characterization spectrum is shown below. Figure 5 and Figure 16 As shown: 1H NMR (500MHz, DMSO) δ8.92(d,J=5.6Hz,1H),8.65(d,J=5.9Hz,1H),8.34(s,1H),8.16(d,J=8.2Hz,1H),7.97 –7.89(m,3H),7.71(d,J=7.7Hz,1H),7.44–7.39(m,2H),7.39–7.32(m,2H),7.31(d,J=8.5Hz,2H),7.22(d, J=7.7Hz,1H),7.16(dd,J=9.4,3.1Hz,1H),6.79(t,J=7.5Hz,1H),6.62(t,J=7.4Hz,1H),6.51–6.43(m,2H) ,6.40(t,J=7.4Hz,1H),6.23(d,J=8.1Hz,2H),6.01(d,J=7.6Hz,1H),5.92(d,J=7.5Hz,1H).ESI-MS(m / z):C 37 H 25 O4N3F3Ir:Calcd for 825.1426;Found,826.1497,[M+H] + .

[0072] Example 6

[0073] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (R=H) and 17.19 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 62.1 mg of the orange-yellow solid target product (1); the yield was 89.3%. The characterization spectrum is shown below. Figure 6 and Figure 17 As shown: 1HNMR(500MHz, CDCl3)δ8.89(d,J=5.2Hz,2H),8.85–8.82(m,2H),8.07(s,2H),7.87(d,J=8.1Hz,2H),7.72–7.63(m,4H),7.57(d,J= 7.6Hz,2H),7.51(d,J=8.2Hz,2H),7.41(d,J=8.5Hz,4H),7.23(ddd,J=8.6,6.9,1.8Hz,2H),7.14–7.08(m,4H),7.06–7.02(m,2H), 6.98(dd,J=6.0,2.9Hz,2H),6.86–6.81(m,2H),6.73–6.66(m,4H),6.49(dt,J=5.0,4.1Hz,4H),6.38(t,J=7.2Hz,2H),6.25(d,J=7 .4Hz,2H),6.14(dd,J=8.4,5.6Hz,6H),1.62(s,13H),1.37(d,J=3.8Hz,12H),1.26(s,13H),0.92(t,J=7.3Hz,18H).ESI-MS(m / z):C 48 H 52 O3N3IrSn:Calcd for 1031.2660;Found,1032.2732,[M+H] + .

[0074] Example 7

[0075] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir2, R=Cl) and 16.43 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 63.5 mg of the target product (2) in an orange-yellow solid; the yield was 92.6%. The characterization spectrum is shown below. Figure 7 and Figure 18 As shown: 1H NMR (500MHz, MeOD) δ8.94(d,J=5.6Hz,1H),8.79(d,J=5.9Hz,1H),8.20(s,1H),8.02(d,J=8.0Hz,1H),7.87–7.80(m,2H),7.73(dd,J=1 4.2,5.7Hz,3H),7.64(d,J=7.7Hz,1H),7.36(d,J=8.2Hz,2H),7.27(dd,J=7.8,4.5Hz,2H),7.22–7.18(m,1H),7.15–7.10(m,2H),6.81 (t,J=7.6Hz,1H),6.63(t,J=7.2Hz,2H),6.56(dd,J=9.0,5.5Hz,1H),6.49(t,J=7.3Hz,1H),6.45–6.39(m,1H),6.16(dd,J=7.5,3.7Hz ,2H),6.05(d,J=7.7Hz,1H),1.64(dt,J=7.2,4.6Hz,6H),1.39–1.35(m,6H),1.18–1.12(m,6H),0.93(t,J=7.4Hz,9H).ESI-MS(m / z):C 48 H 51 O3N3ClIrSn:Calcd for 1065.2270;Found,1066.2330,[M+H] + .

[0076] Example 8

[0077] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir3, R = Br) and 15.54 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 60.8 mg of the orange-yellow solid target product (3); the yield was 89.9%. The characterization spectrum is shown below. Figure 8 and Figure 19 As shown: 1H NMR (500MHz, MeOD) δ8.93(d,J=5.2Hz,1H),8.78(d,J=5.5Hz,1H),8.18(s,1H),8.02(d,J=8.1Hz,1H),7.83(ddd,J =15.4,8.2,1.3Hz,2H),7.76–7.71(m,2H),7.39–7.36(m,2H),7.29–7.17(m,4H),7.12(t,J=7.3Hz,1H),6.81(dd,J =10.8,4.1Hz,1H),6.66–6.61(m,2H),6.56–6.48(m,2H),6.44–6.39(m,1H),6.16(d,J=7.7Hz,2H),6.05(d,J=7.6 Hz,1H),1.69–1.58(m,6H),1.38(dt,J=14.8,7.3Hz,6H),1.21–1.09(m,6H),0.93(t,J=7.3Hz,9H).ESI-MS(m / z):C 48 H 51 O3N3BrIrSn:Calcd for 1109.1765; Found,1110.1833,[M+H] + .

[0078] Example 9

[0079] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir4, R=Me) and 16.87 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 64.7 mg of the orange solid target product (4); the yield was 93.6%. The characterization spectrum is shown below. Figure 9 and Figure 20 As shown: 1H NMR(500MHz,MeOD)δ8.93(d,J=5.7Hz,1H),8.82(d,J=6.3Hz,1H),8.15(s,1H),8.00(d,J=8.0Hz,1H),7.83–7.78(m,2H),7.75–7.69(m,2H) ,7.63(d,J=7.5Hz,1H),7.36(d,J=8.5Hz,2H),7.27–7.22(m,1H),7.18–7.13(m,1H),7.11(d,J=7.8Hz,1H),7.05–7.02(m,2H),6.81–6.77(m ,1H),6.62(dd,J=10.9,4.2Hz,1H),6.52(d,J=8.5Hz,1H),6.50–6.45(m,1H),6.41(td,J=7.4,1.2Hz,1H),6.15(d,J=9.5Hz,2H),6.05(d,J =7.6Hz,1H),2.17(s,3H),1.63(ddd,J=12.8,10.8,6.5Hz,5H),1.41–1.28(m,5H),1.27–1.06(m,5H),0.93(t,J=7.3Hz,7H).ESI-MS(m / z):C 49 H 54 O3N3IrSn:Calcd for 1045.2816; Found,1046.2889,[M+H] + .

[0080] Example 10

[0081] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir5, R = OCH3) and 16.52 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 64.8 mg of the orange-red solid target product (5); the yield was 94.3%. The characterization spectrum is shown below. Figure 10 and Figure 21 As shown: 1H NMR(500MHz,MeOD)δ8.95–8.91(m,1H),8.83(dd,J=5.8,0.7Hz,1H),8.18(s ,1H),8.01(d,J=8.1Hz,1H),7.81(td,J=9.0,1.5Hz,2H),7.75–7.68(m,2H) ,7.66–7.61(m,1H),7.36(d,J=8.6Hz,2H),7.25(ddd,J=7.2,5.8,1.3Hz,1H ),7.16(ddd,J=7.2,5.8,1.3Hz,1H),7.13–7.10(m,1H),6.90(dd,J=9.2,3.3 Hz,1H),6.83–6.78(m,2H),6.63–6.61(m,1H),6.55(d,J=9.3Hz,1H),6.48( td,J=7.5,1.2Hz,1H),6.42(td,J=7.4,1.3Hz,1H),6.17(dd,J=7.5,5.5Hz,2 H),6.07(dd,J=7.6,0.8Hz,1H),3.69(s,3H),1.70–1.55(m,6H),1.37(dq,J =14.7,7.4Hz,6H),1.22–1.09(m,6H),0.93(t,J=7.4Hz,9H).ESI-MS(m / z):C 49 H 54 O4N3IrSn:Calcd for 1061.2766; Found,1062.2834,[M+H] + .

[0082] Example 11

[0083] 0.050 g of cycloiridium salicylaldehyde Schiff base complex (Ir6, R = OCF3) and 15.44 μL of hexabutyltin oxide (Bu6Sn2O) were placed in a Dean-Stark apparatus, with 90 mL of a mixed solution of benzene and ethanol (2:1, v / v) as the solvent. The mixture was heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a mixed solution of dichloromethane and petroleum ether (1:2, v / v) to give 62.7 mg of the red solid target product (6); the yield was 92.9%. The characterization spectrum is shown below. Figure 11 and Figure 22 As shown: 1H NMR(500MHz,DMSO)δ8.89(d,J=5.8Hz,1H),8.66(d,J=5.6Hz,1H),8.22(s,1H),8.14(d,J=8.3Hz,1H),7.92–7.87(m,2H), 7.85(d,J=8.2Hz,1H),7.70(d,J=7.9Hz,1H),7.39(t,J=6.5Hz,1H),7.33–7.29(m,1H),7.25(d,J=8.1Hz,2H),7.18(t,J=6 .3Hz,2H),6.78(t,J=7.4Hz,1H),6.61(t,J=7.4Hz,1H),6.43–6.30(m,4H),6.16(d,J=8.1Hz,2H),6.02(d,J=7.5Hz,1H), 5.92(d,J=7.3Hz,1H),1.58–1.54(m,6H),1.28(d,J=7.3Hz,6H),1.09–1.04(m,6H),0.84(d,J=7.3Hz,9H).ESI-MS(m / z):C 49 H 51 O4N3F3IrSn:Calcd for1115.2483;Found,1116.2555,[M+H] + .

[0084] Example 12

[0085] The experimental steps for inhibiting the proliferation of cancer cells and normal cells by butyltin-cycloiridium salicylaldehyde Schiff base complexes with anticancer activity are as follows:

[0086] (1) Preparation of drug solution: Dissolve the test complex in dimethyl sulfoxide (DMSO) to prepare a stock solution of a certain concentration, and then dilute it sequentially with cell culture medium to prepare a working solution with a certain concentration gradient.

[0087] (2) Evaluation of cell growth inhibition (MTT method):

[0088] 1) Seed the cell suspension into 96-well culture plates;

[0089] 2) Pre-culture cells in drug-free medium under the following environmental conditions: 5% CO2, 310K for 24 hours.

[0090] Then add the test solution and continue culturing for 24 hours;

[0091] 3) Add 15 μL of 5 mg / mL MTT solution to each well of the culture plate, and then incubate for 4 h to form purple crystalline substance (formazan);

[0092] 4) Wash away the culture medium in the wells, add 100 μL of DMSO to dissolve the precipitate (formazan), shake on a shaker in the dark for 15 min to fully dissolve the formazan, and then measure the optical density value of each well using an ELISA reader (wavelength set: 570 nm).

[0093] 5) Each experiment was repeated three times, IC 50 = Average ± SEM.

[0094] Table 1 shows the inhibition rates of the target compound (I) and cisplatin on the growth of human alveolar basal epithelial carcinoma cells (A549), human lung adenocarcinoma cells resistant to cisplatin (A549 / DDP), cervical cancer cells (HeLa), and normal human lung epithelial cells (BEAS-2B).

[0095] Table 1

[0096]

[0097] As demonstrated in Example 12, under the same conditions, the activity of the target complexes was superior to that of cisplatin, particularly against A549 cells. Furthermore, tests on normal cells (BEAS-2B) showed that some of the target complexes exhibited selectivity. Additionally, compared to the poorer anticancer efficacy (IC50) of cycloiridium salicylaldehyde Schiff base complexes (Ir2-Ir6), the target complexes showed superior activity. 50 The introduction of butyltin molecules (>100 μM) enhanced the overall anticancer activity, and the potential anticancer activity of the target complex further confirms its potential as a novel anticancer drug. Furthermore, compared to cisplatin, the complex also showed excellent activity against cisplatin-resistant human lung adenocarcinoma cells (A549 / DDP), making it a potential alternative to cisplatin.

[0098] Example 13

[0099] The AIE characteristics of the target complex were tested by observing changes in fluorescence emission when the proportion of water (a poor solvent) in the acetonitrile solution was continuously increased. Fluorescence emission was measured using an F-4600 fluorescence spectrophotometer. A series of mixed solutions (2.0 × 10⁻⁶) containing acetonitrile and water of complex 6 at the same concentration were prepared by adding water to the acetonitrile solution of complex 6 at a specific ratio. -5 (mol / L), and then the fluorescence emission spectrum of the mixed solution was measured. For example... Figure 25 As shown, the fluorescence intensity of the complex increases significantly with increasing water content, confirming that complex 6 has good AIE properties.

[0100] Example 14

[0101] In the organelle targeting assay, we used laser confocal microscopy to detect the targeting of the target complex in A549 cells. Lyso Tracker Deep Red (LTDR), Mito Tracker Deep Red (MTDR), and 4',6-diamidinyl-2-phenylindole dihydrochloride (DAPI) were used as fluorescent probes for lysosomes and mitochondria, respectively. After incubating A549 cells with the target complex (10 μmol / L) at 37°C for 1 h, organelle probes (500 nmol / L) were added for staining for 30 min. The cell plates were washed three times with PBS buffer (pH: ~7.2) before confocal microscopy detection. The LTDR was excited at 405 nm and collected at 490-570 nm; the MTDR was excited at 405 nm and emitted at 500-580 nm; the DAPI was excited at 405 nm and collected at 410-484 nm; the target complex 6 was excited at 405 nm and collected at 580-650 nm. Tests were conducted as follows... Figure 23 As shown, the colocalization coefficient (PCC) of complex 6 in mitochondria was 0.86, while the PCCs in lysosomes and nuclei were 0.11 and 0.03, respectively, confirming that the target complex mainly targets the mitochondria of A549 cells.

[0102] Example 15

[0103] Changes in mitochondrial membrane potential in A549 cells co-incubated with the drug for a period of time were examined using flow cytometry. 5,5',6,6'-tetrachloro-1,1',3,3'-tetraethylbenzimidazole carbonyl cyanine iodide (JC-1) was used as the probe. Generally, when the mitochondrial membrane potential is high, JC-1 exists in an aggregated state and exhibits red fluorescence. Conversely, JC-1 emits green fluorescence when present in monomeric form, indicating a lower mitochondrial membrane potential. Figure 24 As shown, with the increase of complex 6 concentration, the green fluorescence intensity significantly increases, while the red fluorescence weakens. When the concentration of complex 6 increases from 0.5 × IC50, the intensity of green fluorescence decreases. 50 Increased to 2.0×IC 50 At that time, the proportion of cells with depolarized mitochondrial membranes increased by 45.23%. The increased green / red fluorescence intensity ratio further confirms that mitochondrial dysfunction is the main cause of cancer cell death.

Claims

1. A Schiff base complex of iridium salicylaldehyde, characterized in that, Its structure is shown in equation (II): ； In formula (II), R is selected from one of chlorine, bromine, methyl, methoxy, and trifluoromethoxy; in formula (II), when R is chlorine, the specific structural formula is shown in formula Ir2; when R is bromine, the specific structural formula is shown in formula Ir3; when R is methyl, the specific structural formula is shown in formula Ir4; when R is methoxy, the specific structural formula is shown in formula Ir5; when R is trifluoromethoxy, the specific structural formula is shown in formula Ir6. 。 2. A method for preparing a cycloiridium salicylaldehyde Schiff base complex according to claim 1, characterized in that, Includes the following steps: The basic iridium dimer Ir1 reacts with a salicylaldehyde-benzoic acid Schiff base, wherein the salicylaldehyde-benzoic acid Schiff base is ( E )-4-((5-chloro-2-hydroxybenzaldehyde)amino)benzoic acid, ( E )-4-((5-bromo-2-hydroxybenzaldehyde)amino)benzoic acid, ( E )-4-((2-hydroxy-5-methylbenzaldehyde)amino)benzoic acid, ( E )-4-((2-hydroxy-5-methoxybenzaldehyde)amino)benzoic acid, ( E )-4-((2-hydroxy-5-(trifluoromethoxy)benzaldehyde)amino)benzoic acid, the reaction route is as follows: 。 3. The method for preparing a cycloiridium salicylaldehyde Schiff base complex according to claim 2, characterized in that, It is prepared by the following method: (1) When the complex is of formula Ir2, it is prepared by the following method: Add 0.100 g of basic iridium dimer Ir1, 0.062 g of anhydrous sodium acetate, and 0.051 g of ( E 4-((5-chloro-2-hydroxybenzaldehyde)amino)benzoic acid was placed in a 100 mL Schlenk flask, and a 1:1 (v / v) mixture of dichloromethane and methanol was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The mixture was purified by silica gel column chromatography using a 20:1 (v / v) dichloromethane / methanol solution. After removing the solvent and drying, the target product Ir2 was obtained as an orange-yellow solid powder. (2) When the complex is of formula Ir3, it is prepared by the following method: Mix 0.100 g of basic iridium dimer Ir1, 0.062 g of anhydrous sodium acetate, and 0.060 g of ( E 4-((5-bromo-2-hydroxybenzaldehyde)amino)benzoic acid was placed in a 100 mL Schlenk flask, and a 1:1 (v / v) mixture of dichloromethane and methanol was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The mixture was purified by silica gel column chromatography using a 20:1 (v / v) dichloromethane / methanol solution. After removing the solvent and drying, the target product Ir3 was obtained as an orange-yellow solid powder. (3) When the complex is of formula Ir4, it is prepared by the following method: Add 0.100 g of basic iridium dimer Ir1, 0.062 g of anhydrous sodium acetate, and 0.048 g of ( E 4-((2-hydroxy-5-methylbenzaldehyde)amino)benzoic acid was placed in a 100 mL Schlenk flask, and a 1:1 (v / v) mixture of dichloromethane and methanol was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The mixture was purified by silica gel column chromatography using a 20:1 (v / v) dichloromethane / methanol solution. After removing the solvent and drying, the target product Ir4 was obtained as an orange solid powder. (4) When the complex is of formula Ir5, it is prepared by the following method: Add 0.100 g of basic iridium dimer Ir1, 0.062 g of anhydrous sodium acetate, and 0.051 g of ( E 4-((2-hydroxy-5-methoxybenzaldehyde)amino)benzoic acid was placed in a 100 mL Schlenk flask, and a 1:1 (v / v) mixture of dichloromethane and methanol was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The mixture was purified by silica gel column chromatography using a 20:1 (v / v) dichloromethane / methanol solution. After removing the solvent and drying, the target product Ir5 was obtained as an orange-red solid powder. (5) When the complex is of formula Ir6, it is prepared by the following method: Add 0.100 g of basic iridium dimer Ir1, 0.062 g of anhydrous sodium acetate, and 0.061 g of ( E 4-((2-hydroxy-5-(trifluoromethoxy)benzaldehyde)amino)benzoic acid was placed in a 100 mL Schlenk flask, and a 1:1 (v / v) mixture of dichloromethane and methanol was used as the reaction solvent. The mixture was stirred at room temperature under a nitrogen atmosphere for 12 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was dissolved in dichloromethane. The mixture was purified by silica gel column chromatography using a 20:1 (v / v) dichloromethane / methanol solution. After removing the solvent and drying, the target product Ir6 was obtained as a red solid powder.

4. A butyltin-cycloiridium salicylaldehyde Schiff base complex, characterized in that, Its structure is shown in equation (I): ； In formula (I), R is selected from one of hydrogen, chlorine, bromine, methyl, methoxy, and trifluoromethoxy; in formula (I), when R is hydrogen, the specific structural formula is shown in formula (1); when R is chlorine, the specific structural formula is shown in formula (2); when R is bromine, the specific structural formula is shown in formula (3); when R is methyl, the specific structural formula is shown in formula (4); when R is methoxy, the specific structural formula is shown in formula (5); when R is trifluoromethoxy, the specific structural formula is shown in formula (6). 。 5. A method for preparing a butyltin-cycloiridium salicylaldehyde Schiff base complex as described in claim 4, characterized in that, Includes the following steps: iridium salicylaldehyde Schiff base complexes The target complex, shown in formula (I), is obtained by reacting with hexabutyltin oxide molecules. The reaction route is as follows: 。 6. The method for preparing a butyltin-cycloiridium salicylaldehyde Schiff base complex according to claim 5, characterized in that, It is prepared by the following method: (1) When the complex is of formula (1), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex with R=H and 17.19 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the orange-yellow solid target product (1). (2) When the complex is of formula (2), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex with R=Cl and 16.43 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the orange-yellow solid target product (2). (3) When the complex is of formula (3), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex with R=Br and 15.54 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the orange-yellow solid target product (3). (4) When the complex is of formula (4), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex with R=Me and 16.87 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the orange solid target product (4). (5) When the complex is of formula (5), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex (R=OCH3) and 16.52 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the orange-red solid target product (5). (6) When the complex is of formula (6), it is prepared by the following method: 0.050 g of a cycloiridium salicylaldehyde Schiff base complex with R=OCF3 and 15.44 g of... μ L-hexabutyltin oxide was placed in a Dean-Stark apparatus, with 90 mL of a 2:1 volume ratio of benzene and ethanol as the solvent, and heated under reflux at 110 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the resulting solid was recrystallized in a 1:2 volume ratio of dichloromethane and petroleum ether to obtain the red solid target product (6).

7. The application of the butyltin-cycloiridium salicylaldehyde Schiff base complex prepared by the preparation method of claim 6 in the field of preparing anticancer drugs.

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