Comparative study of cerium-manganese ratios in the design of Ce-Mn-binuclear LDH-based Cu complex: a potent nanocatalyst for the green synthesis of spiro[acridine-9,3’-indole]triones | Scientific Reports

Scientific Reports volume 14, Article number: 26578 (2024) Cite this article

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The Ce-Mn binuclear LDH was prepared at four different molar ratios of Ce to Mn (1:1, 1:2, 1:3, and 1:4), modified with both 3-chloropropyltrimethoxysilane (CPTMS) and N-amino-phthalimide (NAP), complexed with Cu(II), and characterized by the FT-IR, ICP, XPS, XRD, BET, UV/Vis, EDX, SEM, SEM-mapping, TEM, and TGA-DTA techniques. The ICP, XPS, BET, and UV-vis techniques showed that the 1:4 molar ratio of Ce to Mn is the best, therefore it was used as a heterogeneous nanocatalyst for the green synthesis of fourteen spiro[acridine-indole]triones from the three-component condensation reaction of isatin, aniline, and 1,3-diketone in mild reaction conditions. The advantages of this method include the absence of harmful organic solvents, easy separation of the catalyst and products, and rapid achievement of excellent yields. Furthermore, the activity of the catalyst was maintained even after four consecutive runs without a significant loss of activity.

Double-layered hydroxides (LDHs) are a group of layered solids whose semi-hydrophilic structure consists of divalent and trivalent metal cations, interlayer anions, and water1,2. Among the desirable properties of LDHs are high thermal stability, bio-compatibility, low manufacturing cost, ease of preparation, and low toxicity3,4,5. LDHs have a wide role in the field of catalysts due to their ability to control the level and adjustability6,7,8.

LDHs under the same interlayer anions have better crystallinity and stability, and the charge density of LDHs layers and interlayer anions increases and affects the electrostatic attraction and interlayer anion exchange capacity. However, charge density has a greater effect on crystallinity and leads to changes in LDHs performance9,10. As a result, the larger surface area allows for more active sites11, which are effective for removing various contaminants including heavy metals, organic dyes, and anions12, as well as catalyzing various reactions, including oxidation, hydrogenation, and acid-based catalysis13. LDHs often contain bimetallic active sites that increase the efficiency of electron transfer and the rate of free radical production and are a promising substrate for catalytic reactions due to their unique properties, affordability, and ability to prevent metal leaching14,15,16,17,18.

Lanthanides and actinides are the F elements that many researchers use these elements in the structure of LDHs today19,20. Cerium is the second and rarest earth element from the lanthanide series with the oxidation and reduction capability of various Ce3+/Ce4+ electronic states21,22.

Manganese is the fifth most abundant metal in the earth’s crust and the second transition metal after iron, and to its physicochemical similarity to iron, it exists in the environment in the form of multiple valence states, which are the most common oxidation states of Mn2+/Mn3+ in nature23,24.

The integration of manganese and cerium due to the large ionic radius of cerium and oxidation states indicates a good interaction of these two metals in the LDH structure.

Spiro-indoles are one of the most important classes of heterocyclic compounds that due to their structural properties, have extensive activity in pharmaceutical and biological fields25.

Among them, acridines play an important role in the design of drug compounds such as anti-malaria26, anti-bacterial27, anti-inflammatory28, and anti-tumor29 drugs. An important strategy for the synthesis of these compounds is the synthesis through multicomponent reactions (MCRs) which has attracted a lot of attention in the last few decades. Some advantages of MCRs over classical synthesis include atom economy, simple procedures, savings in solvent, time, and energy, simple equipment, lower costs, and to synthesize libraries of compounds bearing several biological responses30,31.

Therefore, the synthesis of acridines by the MCRs method was reported with p-TSA32,33, CoFe2O4/OCMC/Cu (BDC)34, UiO-66-NH235, MW36,37, DES38, and Cu3TiO439.

In this report, we were able to prepare four binuclear LDHs at different cerium to manganese ratios (1:1, 1:2, 1:3, and 1:4), and by comparing these ratios through XPS, ICP, BET, and UV-vis analyses, and the desired LDH (1:4 ratio) was selected. Then, the selected binuclear-Ce-Mn-LDH surface was modified with both CPTMS and NAP and complexed with Cu(II) (Scheme 1).

Synthesis of Ce-Mn-LDH@CPTMS@NAP@Cu.

Finally, the selected LDH was characterized by FT-IR, ICP, XPS, XRD, EDX, BET, UV/Vis, SEM, SEM-mapping, TEM, and TGA-DTA techniques and used as a potent nanocatalyst for the green synthesis of spiro[acridine-9,3’-indole]triones 1(a-n) from the reaction of isatin, aniline, and various diketones in ethanol at 60 °C in short reaction time and high yield (Scheme 2).

Synthesis of 1(a-n).

All chemicals [Ce(NO3)3.6H2O, Mn(NO3)2.4H2O, Cu(OAc)2.2H2O, NAP, Na2CO3, NaOH, toluene, ethanol, and, methanol, etc.] were purchased from the Aldrich and Merck chemical companies and used as received.

A BUCHI 510 was used to determine melting points in open capillary tubes. Fourier Transform Infrared (FT-IR) spectra were recorded on a Perkin Elmer GX spectrophotometer using KBr. 1H and13C NMR spectra were recorded on a BRUKER AVANCE 300 MHz instrument in DMSO-d6. Crystalline structures of products were collected on a Bruker D8 Advance powder diffracto-meter instrument (XRD) with Cu Kα as the incident radiation (λ = 1/56054 A°) (40 kV, 100 mA). The catalyst particles’ morphology was determined via the SEM images on a Philips XL-30 operated at 30 kV accelerating voltage. Qualitative detection of the Mn and Ce elements in the Ce-Mn-LDH was performed by using EDX in an ESEM (SIGM, Germany) instrument. The structure morphologies of the catalyst particles were determined via the TEM images using an EM10C instrument with an accelerating voltage of 100 kV. TGA-DTA analysis was performed with a heating rate of 30 °C/min over a temperature range of 25–1200 °C using the Perkin Elmer Pyris Diamond apparatus. To measure and determine the chemical composition and types of bonding on the surface, as well as the oxidation states of elements, X-ray Photoelectron Spectroscopy (XPS) analysis was obtained with FlexPS (SPECS, Germany). The ICP measure-ments for the metal content evaluation were performed using a Perkin Elmer 5300 DV ICP/OES. TLC (silica gel SIL G/UV 254 plates) was used to monitor the reaction progress. Ultrasonic device 2200 ETH SONICA was used for ultrasonication. The BET analysis was performed for the adsorption and desorption of gas molecules on a solid surface using a BELSORP MINI II. The ultraviolet-visible (UV/Vis) of the samples was recorded by applying a JASCO V-670 spectrophotometer in the wavelength range of 200–700 nm.

The Ce-Mn-binuclear LDH-base copper complex was synthesized in the following four stages:

Solution-A was prepared by dissolving Ce(NO3)3.6H2O (2.6 g, 7 mmol, ) and Mn(NO3)2.4H2O (7.02 g, 28 mmol) (mole ratio: 1:4) in water (50 mL). Solution-B was prepared by dissolving Na2CO3 (10.6 g, 0.1 mol) and NaOH (4 g, 0.1 mol) (mole ratio: 1:1) in water (50 mL). Solution-B was added dropwise to solution-A with vigorous stirring until the pH of the new solution reached 10 with further stirring and heating at 60 °C for 24 h. Then, the prepared dark brown Ce-Mn-LDH was washed several times with water and oven-dried.

A (1.0 g) was dispersed in toluene (50 mL) with ultrasonication for 15 min and CPTMS (11 mmol, 2.0 mL) was added dropwise and the mixture refluxed at 110 °C for 12 h. B was then collected and washed with toluene and ethanol and vacuum-dried.

B (1.0 g) was dispersed in ethanol by ultrasonication for 10 min and NAP (0.5 g, 3 mmol) (50 mL) was added dropwise to the reaction mixture and refluxed for 48 h. C was then collected washed with ethanol and vacuum dried.

C (1.0 g) was dispersed in methanol (50 mL) by ultrasonication for 10 min to get a uniform suspension. The solution of Cu(OAc)2.2H2O (5% w/v) in methanol was then added dropwise to the reaction mixture and refluxed for 48 h. D was then collected washed with ethanol and vacuum dried.

A mixture of isatin (147 mg, 1 mmol), aniline (931 mg, 1 mmol), 1,3-diketone (280 mg, 2 mmol), and D (20 mg) was stirred in ethanol at 60 °C for an appropriate time. After completion of the reaction (TLC: n-hexane/acetone 10:4), the mixture was cooled to room temperature, the resulting reaction mixture diluted by ethanol, and the catalyst separated by centrifugation. After removing the solvent, the product was washed with warm water (3 × 20 mL) and cold ethanol (3 × 5 mL), dried under reduced pressure, and characterized with the comparison of their IR, NMR, and melting points with authentic samples54.

Low surface area and leaching of metal ions from the surface of LDH composites reduce the efficiency of the catalyst process. As a result, in this work, to improve the surface area and increase the catalytic performance, different molar ratios of Ce to Mn (1:1, 1:2, 1:3, and 1:4) were synthesized and characterized with ICP-OES, XPS, BET, and UV-Vis.

D was synthesized in four molar ratios of 1:1 (sample one), 1:2 (sample two), 1:3 (sample 3), and 1:4 (sample four) of Ce to Mn and were used separately as catalysts in the model reaction (1 mmol of isatin, 1 mmol of aniline and 2 mmol of dimedone, synthesis of 1a). Then, the content of copper was determined in D using ICP analysis, before (fresh) and after (used) its use.

The results obtained from ICP show that the leaching of copper from the surface of the used D (sample four) is lower than the other three samples. This lower leaching and better retention of copper ions inside the catalyst shows better stability and activity compared to the other three samples, which is consistent with UV-Vis spectra and BET analysis, as well (Table 1).

Figure 1. shows the UV spectra of (1) the copper acetate solution (blue), and (2) the remained copper acetate filtrate from the product of the reaction between copper acetate solution and four different molar samples of D (green).

Then, to determine the amount of the loaded copper on it, the amount of copper in the copper acetate solution was measured before adding to the ligand and after that, using the UV/Vis spectrum. The UV absorption spectrum of copper acetate in D (sample four) showed that all copper acetate was relatively consumed indicating a strong interaction between copper ions and the ligand (Ce-Mn-LDH@CPTMS@NAP) to form a more stable copper complex compared to the other three samples.

Comparison of the UV-Vis spectra of fresh copper acetate (blue) with the remained copper acetate filtrate (green) in four different ratios of D.

The textural properties of the LDH composite with four different molar ratios of Ce to Mn were investigated by nitrogen absorption-desorption analysis, and the obtained results (the surface area values, pore volumes, and pore diameters) were listed as below (Table 2).

According to Table 2, with increasing the mass ratio of Mn to Ce, the specific surface area (20.787 m2/g) and the pore volume (0.1316 cm3/g) of D (sample four) decreases, and the pore diameter (25.325 nm) increases. This observation is consistent with the findings of Huang et al., who reported that the specific surface area is inversely related to the pore size40.

As a result, with increasing the pore diameter, the specific surface area decreases, and the larger pores enhance adsorption capacity, allowing molecules or ions to be captured effectively. Therefore, the larger pores at D (sample four) confirm the presence of a porous and macroporous structure, which is significant for its potential applications such as adsorbent and catalyst (Fig. 2).

The BET and BJH analysis of D with 1:1, 1:2, 1:3 and 1:4 ratios of Ce/Mn.

The XPS analysis was performed to investigate the capacity of elements on the D surface with different molar ratios of Ce to Mn (1:1, 1:2, 1:3, and 1:4). The XPS spectra show the presence of carbon, oxygen, nitrogen, silicon, cerium, and manganese elements in D (Figs. 3, 4, 5 and 6).

The XPS Analysisfor the 1:1 ratio (a) Cu2p, (b) Ce3d, (c) Mn2p, (d) O1s, (e) C1s, and (f) Si2p.

The XPS Analysisfor the 1:2 ratio (a) Cu2p, (b) Ce3d, (c) Mn2p, (d) O1s, (e) C1s, and (f) Si2p.

The XPS Analysis for the 1:3 ratio (a) Cu2p, (b) Ce3d, (c) Mn2p, (d) O1s, (e) C1s, and (f) Si2p.

The XPS Analysis for the 1:4 ratio (a) Cu2p, (b) Ce3d, (c) Mn2p, (d) O1s, (e) C1s, and (f) Si2p.

Also, the corresponding Table 3 shows shifts of XPS peaks and binding energies of all elements in four prepared LDHs which are consistent with previous reports24,41,42,43,44,45.

The XPS Analysis of 1:1, 1:2, 1:3, and 1:4 molar ratios for Cu2p, Ce3d, Mn2p, O1s, C1s, Si2p, and N1s elements were investigated and compared which reveal the oxidation states of Cu2p through three distinct peaks across four samples.

The peaks with binding energies of 935.81, 935.87, 935.77, and 935.99 eV for Cu2p3/2, and 945.28, 955.17, 954.95, and 955.51 eV for Cu2p1/2 are clear indications for the presence of Cu and Cu+ ion, respectively. In addition, the peak found within the range of 941.65, 947.24, 947.58, and 947.94 eV is attributed to the Cu2+ ion located on the LDH composite structure’s surface.

Table 1 represents data suggesting that an increase in the Mn to Ce mass ratio is associated with an increase in both the peak intensity and the Cu2p bond energy. This trend indicates a strengthening of the Cu-N bond and, consequently, increasing the stability of the copper complex. These observations are also confirmed by the results obtained from ICP and UV/Vis analyses.

The Ce3d spectrum is characterized by high-resolution peaks in the range of 875–918 eV, representing the Ce3d5/2 and Ce3d3/2 states. Specifically, the Ce3d3/2 state is represented by peaks at (902.26, 906.51), (901.65, 906.62), (903.69, 918.02), and (904.01, 918.17) eV. Meanwhile, the Ce3d5/2 state is denoted by peaks at (887.83, 884.13), (875.54, 886.41), (875.92, 886.31), and (876.05, 886.38) eV. These peaks confirm the presence of Ce3+ oxidation state in the structure of Ce-Mn-LDH in all four investigated ratios.

In the broad Mn2p spectrum, two distinct peaks are observed. The Mn2p3/2 peaks are located at (642.94, 643.02, 643.66, 643.58,) eV, and the Mn2p1/2 peaks are found at (652.36, 654.40, 654.70, 655.72) eV. These peaks are indicative of the presence of Mn2+ and Mn3+ ions within the material.

The O1s spectrum shows a set of peaks in the range of (531.81, 533.17), (532.92, 532.27), (530.79, 532.49), and (532.30, 533.52) eV. These peaks are related to metal-oxygen bonds (M-O), (C = O), and water molecules adsorbed on the surface, respectively.

The C1s spectrum covers a wide range with peaks (290.00, 290.64, 290.40, and 290.80) eV corresponding to the carboxylate group (O-C = O). In addition, the peaks representing C = C and carbonate ions (CO32−) are in the range of (284.46, 285.74), (281.63, 286.16), (282.35, 285.81), and (284.58, 286).

The Si2p spectrum reveals peaks at (88.69, 96.58, 99.94), (95.65, 99.19, 103.77), (95.16, 99.89, 104.15), and (96.04, 101.3, 104.3) eV, which are indicative of (Si), (Si-C), and (Si-O) bonds. Additionally, peaks at (110.01, 107.04, 107.54, and 108.95) eV are attributed to (SiO2).

The analysis of binding energy results shows that increasing the molar ratio of manganese to cerium leads to an increase in peak intensity and binding energies.

As a result, with the increase of binding energy, the electric charge density increases to enhance the electrostatic interactions or chemical bonding between the layers to create a strong network of Ce-Mn-LDH composite with high properties and surface changes. This modification leads to the formation of a stable copper complex that improves the catalytic properties.

Therefore, the obtained results from the BET, UV-Vis, XPS, and ICP analysis showed that D (sample four) is the best material to be used as a potent catalyst for the synthesis of 1(a-n).

The structure and morphology of D were determined by Fourier-Transform Infrared spectroscopy (FT-IR), X-ray Diffraction analysis (XRD), Energy Dispersive X-ray analysis (EDX), EDX-Mapping, Scanning Electron Microscopy (SEM), Transmission Electron Micro-scopy (TEM), Thermo-Gravimetric-Differential Thermal Analysis (TGA-DTA), Ultraviolet-visible (UV-Vis) spectroscopy, Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), X-ray Photoelectron Spectroscopy (XPS), and Brunauer–Emmett–Teller (BET).

Figure 7 shows the FT-IR spectra of A, B, C, and D.

In curve A, the bands at 534–862 cm−1 are due to the LDH lattice vibrations (Mn-O, Ce-O, Ce-O-Mn)46,47,48. The broad peak around 3445 cm−1 is related to the stretching of -OH groups attached to metal ions. The bending vibration of interlayer water is found at 1636 cm−1 and absorption bands at 1740 and 1383 cm−1 indicate the stretching vibration of C = O and C-O. The band in 1449 cm−1 is due to the asymmetric band of in the CO2−.

Curve B shows the absorption peaks at 1037 and 1135 cm−1 which are attributed to the Si-O-M and Si-O-Si bonds confirming the modification of the surface of the LDH.

In curve C, a band at 3435 cm−1 is related to the NH bond, and the peaks at 2842 and 2958 cm−1 belong to the aliphatic CH group. Also, the weak bands at 1145, and 1309 cm−1 are attributed to the C-O and C-N vibration bands, respectively. In addition, the two peaks at 1418, and 1640 cm−1 belong to the C-N and N-H bonds.

In curve D, the peak at about 497 cm−1 is related to the Cu stretching modes.

Comparison of the FT-IR spectra of A, B, C, and D.

The XRD structural information of A and D is shown in Fig. 8. The sharp and symmetrical peaks indicate the structural specifications of hydrotalcite. There are diffraction peaks at 2θ = 15.85°, 24.1°, 26.45°, 31.3°, 44.95°, 51.55°, 60°, and 62.9°, corresponding to the (003), (006), (111), (220), (009), and (110) crystal planes of Ce-Mn LDH. The (003) peak shows the degree of crystallinity of structure and the success of Ce-Mn LDH. The diffraction peaks at 2θ = 23.65°, and 26.15° can be related to a metal oxide containing Ce and Mn. The XRD pattern of D is broad with low intensity due to the large ionic radius of Ce in layers47,48,49,50. the amount of Cu increased the intensity of the peaks between 2= 35° to 61° increased. The appearance of peaks corresponding to copper metal at 2θ = 60° indicates the successful formation of D51.

The XRD pattern of A and D.

The crystal structure of D before and after its application in the model reaction was studied by XRD analysis. Figure 9 shows that the crystal structure of D remained unchanged after the reaction confirming its stability and capability.

The XRD pattern of the catalyst D before and after the model reaction.

To evaluate the catalyst content, the EDX analysis was used to confirm the presence of elements, namely C, O, N, Mn, Ce, Si, and Cu (Fig. 10).

The EDX analysis of D.

Figure 11 shows the qualitative elemental mapping, indicating the nice distribution of the expected chemical elements in D, namely Ce, Mn, C, O, N, Si, Cu, and all elements.

The elemental mapping images of D.

The surface and size of the particle catalyst were confirmed by the SEM images (Fig. 12). According to these SEM images, the spherical shape and the average particle size are estimated to be in the nanometer range (30–70 nm).

The SEM images of D.

The crystalline structure and morphology of D were studied by the TEM images (Fig. 13). According to the basis of the TEM images, the core-shell structure and nature of the layered structure of the LDH phases suggest a strong interaction between the LDH sheets.

The TEM images of D.

The thermal behavior of D was determined by the TGA-DTA curves in the temperature range of 25 to 1000 °C. At about 68.29 °C, organic solvents were lost. The weight loss at about 369.89 °C is probably related to the removal of water CPTMS and NAP. The weight decrease at about 399.45 °C is related to the loss of carbonate ions (with the CO2 evolution) and the dehydroxylation of the LDH to show that the layered structure of D is stable up to 400 °C. The weight loss at about 450 °C is probably related to the decomposition of LDH. As the temperature increases, mass loss increases up to 1000 °C (Fig. 14).

The TGA-DTA curve of D.

To optimize the synthesis of 1(a-n), the one-pot three-component condensation reaction of isatin, aniline, and dimedone was carried out in various temperatures, catalyst amount, and solvents in the presence of D. The best optimal condition (a model reaction) was found to be the 1:1:2 moles of isatin, aniline, and dimedone with 20 mg of D at 60 °C in ethanol (Table 4).

According to Table 4, in optimizing the reaction conditions for the preparation of 1(a-n) by D, the highest yield was obtained using 20 mg of catalyst at 60 °C in ethanol. But with the increase of temperature or amount of catalyst, the yield decreased and the reaction time increased. Increasing the amount of catalyst and temperature probably increases the rate of the reverse reaction, so the yield decreases and the reaction takes more time.

Based on the optimized results of the model reaction, spiro[acridine-9,3’-indole]triones 1(a-n) were synthesized in similar conditions with high yields and short reaction times (Table 5). Since all prepared compounds were known, so they were characterized with the comparison of their spectroscopic data and melting points with authentic samples.

According to Table 5, electron-withdrawing groups on aniline relatively increase the yield (entries 2–4), while the electron-releasing groups decrease it (entries 5, 6, 9, 10, 13, and 14).

Yield: 96%, m.p. 251–254 °C; IR: ʋ = 3329, 2960, 1724, 1694, 1647, 1599, 1475, 1377, 1348, 1229, 1129, 1199 and 905 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 0.95 (d, J = 7.0 Hz, 12 H, CH3), 1.79–2.12 (m, 4 H, CH2), 2.27–2.51 (m, 4 H), 6.67 (d, J = 7.6 Hz, 1 H, H-Ar), 6.72–6.85 (m, 2 H, H-Ar), 6.90 (s, 1H, H-Ar), 6.93 (s, 1H, H-Ar), 7.04 (s, 1H, H-Ar), 7.09 (d, J = 7.6 Hz, 1 H, H-Ar), 7.40 (s, 1H, H-Ar ), 8.85 (s, 1H, H-Ar ), 10.98 (s, 1H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 203.9, 194.6, 182.3, 168.6, 144.7, 133.5, 131.7, 129.7, 128, 126.9, 121.9, 121.6, 120.3, 113, 111.7, 109.8, 108.5, 101.4, 100.6, 59.0, 54.2, 50.6, 46.8, 33.6, 32.8, 31.5, 29.1, 27.3 and 26.4 ppm.

Yield: 98%, m.p. 270–272 °C; IR: ʋ = 3430, 3057, 2962.97, 1733, 1711, 1667, 1617, 1470, 1346, 1315, 1223, 1168, 1031, 902, 747 and 675 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 0.96 (s, 12 H, CH3), 1.86–2.25 (m, 4 H, CH2), 2.42–2.70 (m, 4 H, CH2), 6.75 (dd, 3 H, J = 4.2 Hz, H-Ar), 7.05 (d, J = 7.5 Hz, 1 H, H-Ar), 10.28 (s, 1H, N-H). 13C NMR (75 MHz, DMSO-d6) δC = 195.5, 178.7, 163.9, 144.3, 134.5, 128.2, 122.6, 121.1, 113.4, 108.9, 51, 32.1, 28.4 and 27.0 ppm.

Yield: 95%, m.p. 254–258 °C; IR: ʋ = 3331, 2960.07, 1724, 1693, 1647, 16, 1473, 1374, 1348, 1229, 1200, 1129, 905, 754 and 558 cm−1. 1H NMR (300 MHz, DMSO-d6) δH = 0.93–1.04 (m, 12 H, CH3), 2.03 (s, 2 H, CH2), 2.35 (s, 2 H, CH2), 5.29 (d, J = 5.0 Hz, 1 H, N-H), 6.43–8.20 (m, 6 H, H-Ar), 8.80 (s, 1H, H-Ar) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 196.09, 193.68, 160.11, 138.70, 129.55, 128.36, 124.77, 115.98, 97.72, 50.60, 42.48, 40.97, 40.64, 40.31, 39.97, 39.64, 39.30, 38.97, 32.68, 28.34 ppm.

Yield: 94%, m.p. 222–228 °C; IR: ʋ = 3330, 3238, 3157, 3099, 2897, 1724, 1694, 1647, 1572, 1599, 1488, 1378, 1348, 1278, 1129, 1020, 905, 753, 608 and 558 cm−11H NMR (300 MHz, DMSO-d6) δH = 0.99 (d, J = 4.1 Hz, 12 H, CH3), 2.03 (d, J = 4.3 Hz, 4 H, CH2), 2.33 (d, J = 4.5 Hz, 4 H, CH2), 5.31 (s, 1H, N-H), 7.04–7.17 (m, 4 H, H-Ar), 7.50 (d, J = 6.8, 3.1 Hz, 3 H, H-Ar), 8.80 (s, 1H, H-Ar) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 196.13, 159.96, 139.16, 132.46, 125.03, 116.37, 97.84, 50.59, 42.48, 40.63, 40.30, 39.97, 39.64, 39.31, 32.67, 28.34 ppm.

Yield: 88%, m.p. 258–260 °C; IR: ʋ = 3330, 3109, 2961, 2890, 1724, 1694, 1600, 1647, 1474, 1378, 1349, 1229, 1200, 1129, 905, 756 and 558 cm−1. 1H NMR (300 MHz, DMSO-d6) δH = 0.95 (s, 12 H, CH3), 1.87–2.11 (m, 4 H, CH2), 2.29–2.50 (m, 4 H, CH2), 3.32 (s, 3 H, CH3), 6.42–6.88 (m, 3 H, H-Ar), 6.87–7.28 (m, 3 H, H-Ar), 7.38 (s, 1H, H-Ar), 8.85 (s, 1H, H-Ar), 10.95 (s, 1H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 203.82, 194.60, 182.24, 168.62, 144.74, 133.52, 131.64, 127.94, 121.93, 120.27, 112.96, 111.68, 109.78, 108.49, 101.35, 79.59, 59.11, 54.20, 50.65, 47.28, 46.87, 40.94, 40.63, 40.30, 39.97, 39.63, 39.30, 33.62, 32.76, 31.52, 29.08, 27.25, 26.46 ppm.

Yield: 87%, m.p. 260–262 °C; IR: ʋ = 3329, 3101, 2962, 2884, 1724, 1694, 1647, 1599, 1488, 1378, 1349, 1129, 1199, 1114, 905, 756, 608 and 558 cm−1. 1H NMR (300 MHz, DMSO-d6) δH = 0.95 (s, 12 H, CH3), 1.91–2.09 (m, 3 H, CH2), 2.21 (s, 2 H, CH2), 2.43 (d, J = 24.6 Hz, 2 H, CH2), 3.85 (s, 3 H, OCH3), 6.68 (td, J = 16.1, 10.9 Hz, 3 H, H-Ar), 6.98 (ddd, J = 21.0, 17.2, 7.6 Hz, 5 H, H-Ar), 8.84 (s, 1H, H-Ar), 10.92 (s,1 H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 203.82, 194.62, 182.25, 144.75, 134.64, 133.54, 127.96, 126.35, 125.41, 121.94, 119.92, 115.18, 113.67, 111.90, 109.80, 102.89, 101.36, 54.21, 50.66, 47.29, 42.72, 40.96, 40.64, 40.31, 39.97, 39.64, 39.30, 38.98, 33.63, 32.76, 31.53, 28.38, 27.26, 26.47 ppm.

Yield: 89%, m.p. >350 °C; IR: ʋ = 3460, 3118, 3076, 2795, 1721, 1611, 1563, 1502, 1469, 1245, 1032, 937, 812 and 668 cm−1. 1H NMR (300 MHz, DMSO-d6) δH = 3.47 (d, J = 8.8 Hz, 3 H, OCH3), 5.04 (s, 2 H, N-H), 6.68 (d, J = 7.8 Hz, 1 H, H-Ar), 6.88 (t, J = 7.6 Hz, 1 H, H-Ar), 7.14 (t, J = 7.8 Hz, 2 H, H-Ar), 10.53 (s, 1H, N-H), 11.16 (s, 2 H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 176.12, 167.93, 150.65, 143.60, 138.92, 129.28, 128.51, 124.71, 121.92, 114.48, 109.93, 53.96, 51.20, 40.52, 40.19, 39.85, 39.52, 39.19 ppm.

Yield: 86%, m.p. 233–238 °C; IR: ʋ = 3304, 3366, 3263, 3099, 2958, 2928, 2845, 1765, 1716, 1685, 1619, 1482, 1428, 1409, 1365, 1337, 1252, 1184, 1120, 1028, 796, 790, 691 and 509 cm−1. 1H NMR (300 MHz, DMSO-d6) δH = 5.03 (s, 2 H, N-H), 6.66 (t, J = 7.2 Hz, 1 H, H-Ar), 6.87 (t, J = 8.0 Hz, 2 H, H-Ar), 7.11 (q, J = 7.6 Hz, 2 H, H-Ar), 10.53 (s, 1H, N-H), 11.16 (s, 2 H, N-H) ppm.

13C NMR (75 MHz, DMSO-d6) δC = 176.10, 167.91, 150.64, 143.61, 129.24, 128.51, 124.71, 121.89, 112.67, 109.91, 53.93, 51.18, 40.92, 40.58, 40.24, 39.91, 39.58, 39.24, 38.91 ppm.

Yield: 87%, m.p. >350 °C; IR: ʋ = 3186, 3081, 2956, 1733, 1706, 1612, 1558, 1469, 1389, 1352, 1253, 814 and 668 cm−11H NMR (300 MHz, DMSO-d6) δH = 5.03 (s, 2 H, N-H), 6.67 (d, J = 7.7 Hz, 1 H, H-Ar), 6.87 (t, J = 7.5 Hz, 1 H, H-Ar), 7.11 (d, J = 7.5 Hz, 2 H, H-Ar), 10.52 (s, 1H, N-H), 11.15 (s, 2 H, N-H) ppm 13C NMR (75 MHz, DMSO-d6) δC = 176.11, 167.89, 150.65, 143.61, 138.87, 129.25, 128.52, 125.14, 124.71, 123.26, 121.90, 112.68, 109.91, 53.94, 51.19, 40.91, 40.58, 40.24, 39.90, 39.57, 39.23, 38.91 ppm.

Yield: 95%, m.p. 266–270 °C; IR: ʋ = 3366, 3263, 3096, 2845, 1770, 1712, 1619, 1482, 1470, 1409, 1348, 1229, 1184, 1120, 1028, 980, 769, 676 and 550 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 5.07 (s, 2 H, N-H), 6.71 (d, J = 7.6 Hz, 1 H, H-Ar), 6.92 (t, 1 H, H-Ar), 7.12–7.22 (m, 2 H, H-Ar), 10.60 (s, 1H, N-H), 11.16 (s, 1H, N-H), 11.23 (s, 1H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 176.2, 168.1, 150.8, 143.6, 129.3, 128.6, 124.8, 110 and 54 ppm.

Yield: 91%, m.p. 200–203 °C; IR: ʋ = 3156, 3095, 3037, 2905, 2846, 1732, 1671, 1621, 1576, 1476, 1429, 1315, 1178, 1025, 976, 932, 757, 685 and 630 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 0.95 (d, J = 7.0 Hz, 12 H, CH3), 1.79–2.12 (m, 4 H, CH2), 2.19–2.54 (m, 4 H, CH2), 6.67 (d, J = 7.6 Hz, 1 H, H-Ar ), 6.72–6.85 (m, 2 H, H-Ar ), 6.90 (s, 1H, H-Ar ), 6.93 (s, 1H, H-Ar ), 7.04 (s, 1H, H-Ar), 7.09 (d, J = 7.6 Hz, 1 H, H-Ar), 7.40 (s, 1H, H-Ar), 8.85 (s, 1H, H-Ar ), 10.98 (s, 1H, N-H) ppm 13C NMR (75 MHz, DMSO-d6) δC = 176, 165.3, 160, 152.7, 143.5, 138.8, 133.4, 131.2, 130.4, 125.2, 124.9, 124.4, 123.6, 123.2, 122.2, 116.9, 116.7, 116.1, 112.7, 110.3, 101.3, 78.8 and 40.5 ppm.

Yield: 88%, m.p. 281–285 °C; IR: ʋ = 3353, 3239, 3070, 2928, 1720, 1682, 1643, 1547, 1486, 1346, 1214 and 778 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 6.87 (d, J = 3.7 Hz, 2 H, H-Ar), 7.21–7.30 (m, 2 H, H-Ar), 7.36 (dd, 2 H, H-Ar), 7.45–7.51 (m, 2 H, H-Ar), 7.55 (td, J = 3.7 Hz, 3 H, H-Ar), 7.81 (ddd, J = 3.7 Hz, 2 H, H-Ar), 8.47 (dd, J = 16.1, 2 H, H-Ar), 10.91 (s, 1H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 181.1, 162.2, 150.5, 146.3, 139.9, 137.9, 135.1, 134.4, 131.5, 130.8, 129.9, 128.4, 127.5, 127.2, 123.7, 123, 121.8, 118.5, 116.9, 84.4 and 51.5 ppm.

Yield: 86%, m.p. 245–248 °C; IR: ʋ = 330, 3101, 2960, 2900, 1724, 1693, 1646, 1599, 1515, 1487, 1378, 1348, 1239, 1129, 1199, 1032, 905, 756, 608 and 558 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 0.92–1.08 (m, 12 H, CH3), 1.83–2.12 (m, 4 H, CH2), 2.17–2.42 (m, 4 H, CH2), 6.52–6.89 (m, 4 H, H-Ar), 6.90–7.26 (m, 3 H, H-Ar), 7.41 (d, J = 7.8 Hz, 1 H, H-Ar ), 8.85 (s, 1H, H-Ar), 10.99 (s, 1H, N-H) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 203.9, 194.7, 182.3, 168.7, 144.7, 133.5, 128, 126.8, 122, 121.6, 120.3, 109.8, 101.4, 59.1, 54.2, 50.6, 47.3, 46.9, 33.7, 32.8, 31.5, 29.1, 27.3 and 26.4 ppm.

Yield: 83%, m.p. 279–284 °C; IR: ʋ = 3417, 3318, 3224, 2930, 2856, 1725, 1687, 1617, 1565, 1486, 1384, 1346, 1193, 1067, 894, 762, 680 and 559 cm−1; 1H NMR (300 MHz, DMSO-d6) δH = 5.57 (s, 1H, N-H), 6.60–6.87 (m, 3 H, H-Ar), 6.96–7.39 (m, 6 H, H-Ar), 7.49–8.14 (m, 5 H, H-Ar) ppm. 13C NMR (75 MHz, DMSO-d6) δC = 199.5, 163.8, 152.4, 138.8, 134.4, 133.2, 132, 127.4, 125.6, 125.1, 124.4, 124, 123.7, 123.2, 121.6, 116.8, 116.1, 115.3, 112.6, 109.4 and 91.4 ppm.

Table 6 shows the comparison of the previous methods (entries 1–10) used for the synthesis of 1(a-n) with our proposed method (entry 11). As can be seen, in our proposed method, the reaction will take place in a shorter reaction time (20 min) and higher yield (98%).

Scheme 3 shows the possible mechanism for the synthesis of 1(a-n) by D. The nucleophilic addition of the amino group of aniline to the activated carbonyl group by D will form intermediate I, which by deletion of water from I, intermediate II will be formed. The nucleophilic addition of intermediate II to the activated carbonyl group of isatin will form intermediate III which is its tautomerization and internal cyclization will form the intermediates IV, and V, respectively. De-cyclization of V will form VI and its nucleophilic attack to the activated dimedone will form the intermediate VII. Consecutive removal of two water molecules and tautomerization will form the intermediates VIII, IX, and X (product).

Proposed mechanism for the synthesis of 1(a-n).

The catalytic recyclability and stability of D was investigated using a model reaction. After synthesis of 1a, ethanol was added to the reaction mixture to separate the catalyst (Ce-Mn-LDH@CPTMS@NAP@Cu) by centrifugation. Then, it was washed several times with ethanol/ water, and oven dried at 80 °C, which showed no significant decrease in the catalyst activity even after four consecutive runs (Fig. 15).

Recyclability test of D.

The FT-IR spectra of D before and after the consecutive runs of recovery showed a very nice similarity (Fig. 16).

The FT-IR spectra of the fresh and the used D.

In this study, different ratios of cerium to manganese were investigated to provide suitable support for modifying the surface of the Ce-Mn-LDH composite. Results from the ICP, XPS, BET, and UV-vis, techniques showed that the Ce-Mn-LDH composite with the 1:4 ratio of cerium to manganese is the best fit to have a specific surface area with high porosity to form a stable complex. Also, to evaluate the catalytic performance of D, it was used in the synthesis of spiroacridinetriones with high yields, short reaction times, and good recyclability.

Data AvailabilityAll data generated or analyzed during this study are included in the Supporting Information.

Shen, Z. et al. MgAl-LDH/LDO-catalyzed hydrothermal deoxygenation of microalgae for low-oxygen biofuel production. ACS ES&T Engin. 1, 989–999 (2021).

Article Google Scholar

Wang, L. et al. Exploiting Co defects in CoFe-Layered double hydroxide (CoFeLDH) derivatives for highly efficient photothermal cancer therapy. ACS Appl. Mater. Interf. 12, 54916–54926 (2020).

Article Google Scholar

Guo, Y. et al. Layered double hydroxides as thermal stabilizers for poly(vinyl chloride): A review. Appl. Clay Sci. 211, 106–198 (2021).

Article Google Scholar

Taviot-Guého, C. et al. Tailoring hybrid layered double hydroxides for the development of innovative applications. Adv. Funct. Mater. 28, 1703868 (2018).

Article Google Scholar

Ma, J. et al. Removal of radionuclides from aqueous solution by manganese dioxide-based nanomaterials and mechanism research: A review. ACS ES&T Engin. 1, 685–705 (2021).

Article Google Scholar

Yan, Q. et al. Recent advances in layered double hydroxides (LDHs) derived catalysts for selective catalytic reduction of NOx with NH3. J. Hazard. Mater. 400, 123260 (2020).

Article PubMed Google Scholar

Tang, S. et al. Recent advances in the application of layered double hydroxides in analytical chemistry: A review. Anal. Chim. Acta. 103, 32–48 (2020).

Article Google Scholar

Gao, Z. et al. Synthesis of Ce-doped NiAl LDH/RGO composite as an efficient photocatalyst for photocatalytic degradation of ciprofloxacin. J. Environ. Chem. Eng. 9, 105405 (2021).

Article Google Scholar

Xie, S. et al. Zeolite/ZnAl-layer double hydroxides with different Zn/Al ratios and intercalated anions as the substrate of constructed wetlands: Synthesis, characterization, and purification effect of Hexavalent chromium. Environ. Sci. Pollut Res. Int. 30, 19814–19827 (2023).

Article PubMed Google Scholar

Kameliya, J. et al. Layered double hydroxide materials: A review on their preparation, characterization, and applications. Inorganics. 11, 121 (2023).

Article Google Scholar

Shao, M., Wei, M., Evans, D. G. & Duan, X. Layered double hydroxide materials in photocatalysis. Struct. Bond. 166, 105–136 (2015).

Article Google Scholar

Wang, Y. et al. Insights into the role of metal cation substitution on the anionic dye removal performance of CoAl-LDH. Colloids Surf. A. 636, 128139 (2022).

Article Google Scholar

Zhang, F., Xiang, X., Li, F. & Duan, X. Layered double hydroxides as catalytic materials: Recent development. Catal. Surv. Asia. 12, 253–265 (2008).

Article Google Scholar

Wu, L. et al. Deciphering highly resistant characteristics to different pHs of oxygen vacancy-rich Fe2Co1-LDH/PS system for bisphenol A degradation. Chem. Eng. J. 385, 123620 (2020).

Article Google Scholar

Lu, X., Wang, K., Wu, D. & Xiao, P. Rapid degradation and detoxification of metronidazole using calcium sulfite activated by CoCu two-dimensional layered bimetallic hydroxides: Performance, mechanism, and degradation pathway. Chemosphere. 341, 140150 (2023).

Article PubMed Google Scholar

Gong, C. et al. Heterogeneous activation of peroxymonosulfate by Fe-Co layered doubled hydroxide for efficient catalytic degradation of Rhoadmine B. Chem. Eng. J. 321, 222–232 (2017).

Article Google Scholar

Yang, S. et al. Rapid removal of tetrabromobisphenol A by α-Fe2O3-x@Graphene@Montmorillonite catalyst with oxygen vacancies through peroxymonosulfate activation: Role of halogen and α-hydroxyalkyl radicals. Appl. Catal. B-Environ. 260, 118129 (2020).

Article Google Scholar

Ma, Y. et al. Sulfate radical induced degradation of Methyl Violet azo dye with CuFe layered doubled hydroxide as heterogeneous photoactivator of persulfate. J. Environ. Manag. 227, 406–414 (2018).

Article Google Scholar

Ibrahimzadea, L. et al. Theoretical and experimental characterization of Pr/Ce co-doped hydroxyapatites. J. Mol. Struct. 1240, 130557 (2021).

Article Google Scholar

Cao, X., Kong, L., Gu, Z. & Xu, X. Ce and P123 modified layered double hydroxide (LDH) composite for the synthesis of polypropylene glycol monomethyl ether. RSC Adv. 12, 23183–23192 (2022).

Article ADS PubMed PubMed Central Google Scholar

Chen, B. H. & Inbaraj, B. S. Various physicochemical and surface properties controlling the bioactivity of cerium oxide nanoparticles. Crit. Rev. Biotechnol. 38, 1003–1024 (2018).

Article PubMed Google Scholar

Ghosh, S. K. Diversity in the family of manganese oxides at the nanoscale: From fundamentals to applications. ACS Omega. 5, 25493–25504 (2020).

Article PubMed PubMed Central Google Scholar

Haynes, W. M. (ed). CRC Handbook of Chemistry and Physics, CRC Press/Taylor and Francis, Boca Raton, FL, 95th Edition, Internet Version 2015, accessed December (2014).

Kaur, A., Chahal, P. & Hogan, T. .L. Selective fabrication of SiC/Si diodes by excimer laser under ambient conditions. Ieee Electr. Device L. 37, 142–145 (2015).

Article ADS Google Scholar

Nikoofar, K. & Khani, S. New crown ether-based nano ionic liquid ([DB-18-C-6K+][OH–] nIL): A versatile nanocatalyst for the synthesis of spiro[indoline-3,2′-quinoline] derivatives via the cascade four-component reaction of arylanilines, dialkyl acetylene dicarboxylates, isatins, and Diketone. Catal. Lett. 148, 1651–1658 (2018).

Article Google Scholar

Dhengale, S. D. et al. An efficient and convenient heterogeneous Cu/MCM-41 catalyst for the synthesis of 7,10, 11,12-tetrahydrobenzo[c]acridin-8(9H)-one derivatives. Res. Chem. Intermed. 49, 1581–1600 (2023).

Article Google Scholar

Sahiba, N. et al. A facile biodegradable chitosan-SO3H catalyzed acridine‐1,8‐dione synthesis with molecular docking, molecular dynamics simulation and density functional theory against human topoisomerase II beta and staphylococcus aureus tyrosyl‐tRNA synthetase. J. Mol. Struct. 1268, 133676 (2022).

Article Google Scholar

Vilkova, M. et al. Discovery of novel acridine-chalcone hybrids with potent DNA binding and antiproliferative activity against MDA-MB-231 and MCF-7 cells. Med. Chem. Res. 31, 1323–1338 (2022).

Article Google Scholar

Borkova, L. et al. Synthesis and biological evaluation of triterpenoid thiazoles derived from betulonic acid, dihydrobetulonic acid, and ursonic acid. Eur. J. Med. Chem. 185, 111806 (2020).

Article PubMed Google Scholar

Das, P. et al. Integrating bifunction-ality and chemical stability in covalent organic frameworks via one-pot multicomponent reactions for solar-driven H2O2 production. J. Am. Chem. Soc. 145, 2975–2984 (2023).

Article PubMed Google Scholar

Neto, B. A. D., Beck, P. S., Sorto, J. E. P. & Eberlin, M. N. In melting points, we trust: A review on the misguiding characterization of multicomponent reactions adducts and intermediates. Molecules 27, 7552 (2022).

Article PubMed PubMed Central Google Scholar

Gobinath, P. et al. Grindstone chemistry: Design, one-pot synthesis, and promising anticancer activity of spiro[acridine-9,2-indoline]-1,3,8-trione derivatives against the MCF-7 cancer cell line. Molecules 25, 5862 (2020).

Article PubMed PubMed Central Google Scholar

Gündüza, M. G., Tahirb, M. N., Armakovic, S., Koçakd, C. O. & Armakovic, S. J. Design, synthesis, and computational analysis of novel acridine-(sulfadiazine/sulfathiazole) hybrids as antibacterial agents. J. Mol. Struct. 118, 639–649 (2019).

Google Scholar

Ghasemzadeh, M. A. & Ghaffarian, F. Preparation of core/shell/shell CoFe2O4/ OCMC/Cu (BDC) nanostructure as a magnetically heterogeneous catalyst for the synthesis of substituted xanthenes, quinazolines and acridines under ultrasonic irradiation. Appl. Organomet. Chem. 34, e5580 (2020).

Article Google Scholar

Karami, Z. & Khodaei, M. M. Preparation, characterization, and application of supported phosphate acid on the UiO-66-NH2 as an efficient and bifunctional catalyst for the synthesis of acridines. Res. Chem. Intermed. 49, 1545–1561 (2023).

Article Google Scholar

Aday, B., Ulus, R., Tanç, M., Kaya, M. & Supuran, C. T. Synthesis of novel 5-Amino-1,3,4-thiadiazole-2-sulfonamide containing acridine sulfonamide/carboxamide compounds and investigation of their inhibition effects on human carbonic anhydrase I, II, IV and VII. Bioorg. Chem. 77, 101–105 (2018).

Article PubMed Google Scholar

Kumar, A. et al. Microwave assisted synthesis of N-substituted acridine-1,8-dione derivatives: Evaluation of antimicrobial activity. J. Heterocycl. Chem. 59, 1180–1190 (2022).

Article Google Scholar

Rather, I. A., Alotaibi, S. H., Alotaibi, M. T., Altaf, M. & Ali, R. Deep Eutectic Solvent (DES)-mediated one-pot multicomponent green approach for naphthalimide-centered acridine-1,8-dione derivatives and their photophysical properties. ACS Omega. 7, 35825–35833 (2022).

Article PubMed PubMed Central Google Scholar

Arunachalapandi, M. & Roopan, S. M. Visible light-activated Cu3TiO4 photocatalyst for the one-pot multicomponent synthesis of imidazo-pyrimido acridines. Inorg. Chem. Commun. 148, 110310 (2023).

Article Google Scholar

Huang, F. L. et al. Dynamic wettability and contact angles of poly (vinylidene fluoride) nanofiber membranes grafted with acrylic acid. Express Polym. Lett. 4, 551–558 (2010).

Article Google Scholar

Darvishi, S., Ensafi, A. A. & Mousaabadi, K. Z. Design and fabrication of electrochemical sensor based on NiO/Ni@C-Fe3O4/CeO2 for the determination of niclosamide. Sci. Rep. 14, 7576 (2024).

Article ADS PubMed PubMed Central Google Scholar

Amano, M. E., Betancourt, I., Arellano-Jimenez, M. J., Sánchez-Llamazares, J. L. & Sánchez-Valdés, C. F. Magnetocaloric response of submicron (LaAg) MnO3 manganite obtained by Pechini method. J. Sol-Gel Sci. Techn. 78, 159–165 (2016).

Article Google Scholar

Nayak, S. & Parida, K. Superlative photoelectrochemical properties of 3D MgCr-LDH nanoparticles influencing towards photoinduced water splitting reactions. Sci. Rep. 12, 9264 (2022).

Article ADS PubMed PubMed Central Google Scholar

Xu, X., Yu, X., Guo, K., Dong, L. & Miao, X. Alkaline media regulated NiFe-LDH-based nickel–Iron phosphides toward robust overall water splitting. Catal 13, 198 (2023).

Google Scholar

Blyth, R. I. R. et al. XPS studies of graphite electrode materials for lithium-ion batteries. Appl. Surf. Sci. 167, 99–106 (2000).

Article ADS Google Scholar

Article Google Scholar

Tao, X., Han, Y., Sun, C., Huang, L. & Xu, D. Plasma modification of NiAlCe–LDH as improved photocatalyst for organic dye wastewater degradation. Appl. Clay Sci. 172, 75–79 (2019).

Article Google Scholar

Wanga, Y., Liu, X., Zhang, N., Qiu, G. & Ma, R. Cobalt-doped Ni-Mn layered double hydroxide nanoplates as high-performance electrocatalyst for oxygen evolution reaction. Appl. Clay Sci. 165, 277–283 (2018).

Article Google Scholar

Zhang, T. et al. Dry reforming of ethane over FeNi/Al–Ce–O catalysts: Composition-induced strong metal–support interactions. Engineering. 18, 173–185 (2022).

Article Google Scholar

Wagassa, A. N., Tufa, L. T., Lee, J. & Zereffa, E. A. Shifa. T.A. Controllable Doping of Mn into Ni0.075-xMnxAl0.025(OH)2(CO3)0.0125·yH2O for efficient adsorption of fluoride ions. Glob Chall. 7, 2300018 (2023).

Article PubMed PubMed Central Google Scholar

Guo, W., Zhao, Y. F., Yan, X., Fan, B. & Li, R. Silylated layered double hydroxide nanosheets prepared by a large-scale synthesis method as hosts for intercalation of metal complexes. Appl. Catal. A Gen. 522, 101–108 (2016).

Article Google Scholar

Mousavi, S. R., Nodeh, H. R. & Foroumadi, A. Magnetically recoverable graphene-based nano -particles for the one-pot synthesis of acridine derivatives under solvent-free conditions. Polycycl. Aromat. Compd. 41, 746–760 (2021).

Article Google Scholar

Bhosle, M. R., Shaikh, M. A., Lalit, D. N., Bondle, K. G. M. & Sangshetti, J. N. ChCl:2ZnCl2 catalyzed efficient synthesis of new sulfonyl decahydroacridine-1,8-diones via one-pot multicomponent reactions to discover potent antimicrobial agents. Polycycl. Aromat. Compd. 40, 1175–1186 (2020).

Article Google Scholar

Jadhav, A. M., Balwe, S. G., Lim, K. T. & Jeong, Y. T. A novel three-component method for the synthesis of spiro[chromeno[4’,3’:4,5]pyrimido[1,2-b]indazole-7,3’-indoline]-2’,6(9H)-dione. Tetrahedron 73, 2806–2813 (2017).

Article Google Scholar

Wang, B. W., Li, L., Liu, H. D. & Chen, D. S. Efficient one-pot synthesis of spiro[indoline-3, 11’pyrazolo[3,4-a]acridine]-2,10‘(1’H)-dione derivatives catalyzed by L-Proline. Polycycl. Aromat. Compd. 42, 3291–3301 (2020).

Article Google Scholar

Chate, A. V., Kamdi, S. P., Bhagat, A. N., Sangshetti, J. N. & Gill, C. H. β-Cyclodextrin catalyzed one-pot four component auspicious protocol for synthesis of spiro[acridine-9,3′-indole]-2′,4,4′(1′H,5′H,10H)trione as a potential antimicrobial agent. Synth. Commun. 481, 701–1714 (2018).

Gill, C. H., Chate, A. V., Shinde, G. Y., Sarkate, A. P. & Tiwari, V. S. One-pot, four-component synthesis and SAR STUDIES of spiro[pyrimido[5,4-b]quinoline-10,50-pyrrolo[2,3-d]pyrimidine] derivatives catalyzed by b-cyclodextrin in water as potential anticancer agents. Res. Chem. Intermed. 44, 4029–4043 (2018).

Article Google Scholar

Mohammadi, H. & Shaterian, H. R. Sulfonated magnetic nanocatalyst and application for synthesis of novel spiro[acridine–9,5′–thiazole]-1,4′–dione derivatives. Res. Chem. Intermed. 46, 1109–1125 (2020).

Article Google Scholar

Reddy, M. M. & Sivaramakrishna, A. A facile L-Proline catalyzed one-pot synthesis of xanthene and acridine based quinolones via Knoevenagel condensation reaction. ChemistrySelect 5, 4816–4821 (2020).

Article Google Scholar

Abdoli, M., Nami, N. & Hossaini, Z. One-pot synthesis of spiro-acridine/indoline and indoline derivatives using (MWCNTs)-COOH/La2O3 hybrid as an effective catalyst. J. Heterocycl. Chem. 58, 523–533 (2021).

Article Google Scholar

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The authors are grateful to the Bu-Ali Sina University for the support of this work.

The financial support rendered by the University of Bu-Ali Sina is gratefully acknowledged.

Department of Organic Chemistry, Faculty of Chemistry and Petroleum Sciences, Bu-Ali Sina University, Hamedan, Iran

Samira Javadi & Davood Habibi

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Samira Javadi did the lab experiment.Davood Habibi led the project as a supervisor.

Correspondence to Davood Habibi.

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Javadi, S., Habibi, D. Comparative study of cerium-manganese ratios in the design of Ce-Mn-binuclear LDH-based Cu complex: a potent nanocatalyst for the green synthesis of spiro[acridine-9,3’-indole]triones. Sci Rep 14, 26578 (2024). https://doi.org/10.1038/s41598-024-75724-3

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