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. 2026 Jul 2;16(34):32669–32683. doi: 10.1039/d6ra00116e

New organic–inorganic rod-like hybrids constructed from Keggin-type polyoxomolybdate and a Cu(ii) dithiocarbamate complex: crystal structure, dye adsorption and antibacterial activity

Masoumeh Javanmard a, Saeed Farhadi a,✉, Michal Dusek b, Monika Kucerakova b, Keivan Javanmard a, Mansoureh Maleki c
PMCID: PMC13325550  PMID: 42395709

Abstract

Novel rod-like organic–inorganic crystalline hybrid materials, namely {Cu[S2CN(CH2Ph)2]2}[H3PMo12O40], (abbreviated as Cu(diBzDTC)2-H3POMo), were synthesized by reacting copper(ii) chloride, in situ prepared N,N-dibenzyldithiocarbamic acid (HdiBzDTC) and H3PMo12O40 polyoxomolybdate (H3POMo) in methanol. The resulting hybrid material was characterized using various techniques, including single-crystal X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), UV-vis spectroscopy, scanning electron microscopy (SEM) with an energy-dispersive X-ray (EDX) analyzer, transmission electron microscopy (TEM), thermogravimetry and differential thermal (TG/DTA) analyses, elemental analysis, and zeta potential measurements. SEM and TEM images validated the presence of a highly porous rod-like structure in the hybrid sample. Single-crystal X-ray diffraction analysis disclosed that the crystal structure of the hybrid is composed of a single H3POMo building block alongside a Cu(diBzDTC)2 unit. These units were connected through electrostatic and van der Waals interactions to form a three-dimensional supramolecular framework. H3POMo clusters fill in the cages and holes constructed by the Cu(diBzDTC)2 molecules. The presence of H3POMo building blocks in the hybrid structure made it highly efficient and selective in adsorbing cationic organic pollutants, with a removal efficiency of 96% for methylene blue within 40 min, even when mixed with other substances. The hybrid can be easily separated and reused without any alteration in its structure. Additionally, the hybrid displayed significant antibacterial activity against Gram-negative and Gram-positive bacteria, including A. aureus, S. epidermidis, B. cereus, E. coli, and K. pneumoniae., with inhibition zone diameters of 13–21 mm, as determined by the disk diffusion method. To the best of our knowledge, the Cu(diBzDTC)2-H3POMo represents the first example of a hybrid based on POMs and dithiocarbamate complexes.

New rod-like organic–inorganic hybrids of {Cu[S2CN(CH2Ph)2]2}[H3PMo12O40] were synthesized and used for antimicrobial applications and organic dye-contaminated water treatment.graphic file with name d6ra00116e-ga.jpg

1. Introduction

The use of sulfur-containing ligands in coordination compounds has been a topic of interest.1 Among these ligands, dithiocarbamates (R2NCS2−) are noteworthy for their classical anionic properties.2 As a result, dithiocarbamate-based coordination complexes have been extensively studied due to their ability to coordinate with various metal ions in different binding modes.3 These metal complexes exhibit unique structural characteristics and have various applications, including being used as high-pressure lubricants in industry, fungicides, pesticides, and vulcanization accelerators.4 In addition, dithiocarbamates have also been utilized in medicine as an anti-alcoholic drug,5 anticancer agent,6 and co-adjuvant in AIDS treatment.7 This is attributed to their strong metal binding capacity, making them potential inhibitors of enzymes.8,9 Furthermore, dithiocarbamate complexes are promising single-source materials for bulk metal sulfides10–12 and have been shown to possess antibacterial and antifungal properties.13–16 For example, recently antibacterial activity of dibenzildithiocarbamate derivates and their transition metal complexes have been reported.17 The mechanisms of action for these activities involve the reaction between dithiocarbamates and the HS-groups of important enzymes, transferring the alkyl group from the dithioester to the HS-function of the enzyme.18 All dithiocarbamates include a disulfur moiety, allowing for monodentate or bidentate binding of metal ions. The nitrogen atom can also be modified to alter the physico-chemical properties of the resulting metal complex, particularly its solubility and lipophilicity. The M-S2CNR2 core, with M representing a metal and R representing an alkyl group, has the potential to be highly useful in synthetic processes due to its stable bidentate ligand structure. Incorporating diverse organic substituents into this system allows for precise adjustments of the biological properties of the resulting complex. While numerous dithiocarbamate-metal complexes have been synthesized, research is scarce on their combination with functional materials.19,20

Polyoxometalates (POMs) are anionic soluble clusters of early transition-metal oxide that have garnered significant attention due to their versatile structures and physical and chemical properties.21 They have been studied extensively in various fields including catalysis, biology, magnetism, optics, sensing, medicine, antibacterial activity, and materials science.22–25 POMs are also important building blocks in the design and synthesis of inorganic–organic hybrid materials, as they possess numerous oxygen atoms for coordination and unique electronic and molecular properties.26–32 In recent years, there has been a growing interest in functionalizing POMs with organic ligands or metal–organic moieties, leading to the discovery of novel compounds with diverse structures and properties by altering the building blocks, connection modes, and surface charge density of POM units.33–40 One successful strategy for creating POM-based hybrid materials is through the incorporation of transition-metal complexes.41–43 The large number of potential coordination sites on POMs makes them ideal for integration with transition-metal complexes, resulting in the formation of new architectures with modified properties.44,45 The interaction between POMs and transition-metal complexes can occur through covalent or non-covalent supramolecular interactions, leading to the formation of supramolecular structures.46–48 As such, some inorganic–organic hybrid materials based on POMs and metal-Schiff base complexes have been reported in literature.49–51 However, the design and synthesis of POM-based hybrid materials remains a challenging task. Recently, our research group have synthesized inorganic–organic hybrid materiasl based on POMs and a metal-semicarbazone complexes.52

In this study, we report on a new rod-like organic–inorganic hybrid material, namely bis(N,N-dibenzyldithiocarbamato)copper(ii)12-molybdophosphate with formula of {Cu[S2CN(CH2Ph)2]2}[H3PMo12O40] (abbreviated as Cu(diBzDTC)2-H3POMo). The hybrid material was synthesized by reacting copper(ii) chloride, in situ prepared N,N-dibenzyldithiocarbamic acid (HdiBzDTC), and H3PMo12O40 (H3POMo) in methanol. The as-prepared rod-like organic–inorganic hybrid material was thoroughly characterized, and its efficacy in adsorbing various organic pollutants in aqueous solutions was examined. The study also investigated the impact of different variables, such as the quantity of adsorbent, concentration of dye, and pH levels, on the adsorption process's efficiency. In addition, the hybrid's potential as an antibacterial agent against Gram-negative and Gram-positive bacteria was evaluated using the disk diffusion method.

2. Experimental

2.1. Materials

Dibenzyl amine ((C6H5CH2)2NH, 98%), copper(ii)chloride dihydrate (CuCl2·2H2O, 99%), carbon disulphide (CS2, 99%), phosphomolybdic acid (H3PMo12O40, H3POMo, 98%), ethanol (C2H5OH, 99%), methanol (CH3OH, 99%), dichloromethane (CH2Cl2, 99%), methylene blue (MB, C16H18ClN3S, 98%), methyl orange (MO, C14H14N3NaO3S, 98%), rhodamine B (RhB, C28H31ClN2O3, 98%), Nutrient Agar and Dextrose Agar were purchased from Merck Chemical Co and utilized as received.

2.2. Synthesis of Cu[S2CN(CH2Ph)2]2 complex, Cu(diBzDTC)2

In an ice bath at 4 °C, mixing 20 mmol of carbon disulfide and 20 mmol of dibenzylamine in 20 mL of ethanol resulted in a yellow solution of N,N-dibenzyldithiocarbamic acid (HdiBzDTC). Next, 10 mmol of CuCl2·2H2O was dissolved in water and added to the in situ prepared N,N-dibenzyldithiocarbamic acid solution. This caused a brown precipitate of Cu(diBzDTC)2 to form. The precipitate was then washed with methanol and dried, resulting in the final product of C30H28N2S4Cu. Yield: 80%. Anal. calc. for C30H28N2S4Cu1: C, 59.23; H, 4.64; N, 4.60; S, 21.08%. Found: C, 60.30; H, 6.64; N, 4.50; S, 21.15%. NMR data of dibenzyldithiocarbamate ligand (400 MHz, DMSO-d6): δH (ppm) 5.25(4H, s, benzylic CH2–), 7.25 (10H, m, 2C6H5–). Mass spectrum data of the dibenzyldithiocarbamate ligand: m/z = 295 (M+, ion molecular peak), 273 (C15H15NS2)+, 197 (C14H15N)+, 121 (C8H11N)+, 105 (C7H9N)+, 91 (C6H5CH2–)+ and 77 (C6H5)+. Mass spectrum data of the bis(dibenzyldithiocarbamate) copper(ii) complex: m/z = 610–612 (M+ = ion molecular peaks), 273 (C15H15NS2)+, 197 (C14H15N)+, 121 (C8H11N)+, 105 (C7H9N)+, 91 (C6H5CH2−)+ and 77 (C6H5)+

2.3. Synthesis of Cu(diBzDTC)2-H3POMo hybrid material

A solution of Cu(diBzDTC)2 (0.025 M, 20 mL) in methanol was sonicated using a high-density ultrasonic probe with a power output of 200 W and a frequency of 20 kHz. Next, 10 mL of a methanolic solution of H3POMo (0.05 M) was added to the mixture, which was sonicated for 30 minutes. The resulting brown precipitate was collected, filtered, washed with methanol, and dried. The yield was 0.28 g. To prepare single crystals, 150 mg of H3POMo was dissolved in 10 mL of methanol and added to a solution of 100 mg of Cu(diBzDTC)2 in 20 mL of methanol. The mixture was stirred for 30 minutes at room temperature. After a week, dark brown crystalline materials suitable for X-ray crystallography were obtained. The crystals were collected, washed with methanol, and dried in air. The yield was 0.15 g. Anal. calc. for C30H28Cu1Mo12N2O40.4P1S4: C, 14.82; H, 1.16; N, 1.15; S, 5.28%. Found: C, 15.10; H, 1.25; N, 1.21; S, 5.32%.

2.4. Characterization methods

FT-IR spectra were obtained using a Schimadzu 160 Fourier transform infrared (FT-IR) spectrophotometer in transmission mode over a 4000 to 400 cm−1 range with KBr pellets. Powder X-ray diffraction (PXRD) patterns were acquired on a PANalytical/Xpert pro MPD X-ray diffractometer using Ni-filtered Cu Kα radiation (λ = 1.54059 Å). The MIRA3 TESCAN scanning electron microscope (SEM) with an energy-dispersive X-ray (EDX) analyzer was used to observe the shape and morphology of the samples. A Bandeline GM 2200 multiwave ultrasonic generator, operating at 20 kHz with a maximum power output of 200 W, was employed to synthesize of the hybrid material. Transmission electron microscopy (TEM) images were taken on an EM10C electron microscope operating at a voltage of 100 kV. Optical absobance spectra of dyes were obtained from a Cary 100 Varian UV-vis spectrophotometer in a 200–800 nm wavelength range. Thermogravimetry and differential thermal (TG/DTA) analyses were performed on a Mettler Toledo TGA 851e instrument in flowing N2 in a 25–800 °C temperature region with a 10 °C min−1 heating rate. The surface charge of the materials was investigated by zeta potential measurements on a HORIBA Scientific Zetasizer (Japan).

2.5. X-ray crystallographic study

The crystal structure of the hybrid compound was determined using single-crystal X-ray diffraction, performed on a Gemini four-circle diffractometer (Oxford Diffraction). The instrument utilized a sealed copper X-ray tube and an Atlas S1 CCD detector. Data processing was carried out using the software package CrysAlis,53 which applied corrections based on the crystal shape and spherical harmonic functions (ABSPACK). Structure solution was achieved using Superflip,54 and refined with software Jana 2020.55 Disordered atoms were identified through examination of the difference electron density map. Harmonic refinement was applied only to heavy elements, as it minimally impacted agreement factors but caused instability when applied to light elements. Such a situation is typical for data of suboptimal quality, which does not allow refinement of structural details like displacement ellipsoids of light atoms. Using constraints to keep proper displacement ellipsoids would create a formally correct structure model with similar agreement factors; using isotropic refinement seems a fair approach that does not hide the refinement problems. Hydrogen atoms were located in the difference Fourier maps and positioned at calculated positions for carbon atoms. The positions of hydrogen atoms attached to oxygen atoms were refined with restrained geometry, adhering to standard practices. Crystallographic data, including details of data collection and structure refinement, are compiled in Table 1. The temperature reported (120 K) in Table 1 corresponds to the temperature at which the crystallographic measurements were performed.

Table 1. Crystallographic data and structure refinement parameters for the Cu(diBzDTC)2-H3POMo hybrid.

Chemical formula C30H28Cu1Mo12N2O40.4P1S4
Formula weight 2437.000
Crystal description Dark brown
Temperature (K) 120
Crystal system Triclinic
Space group P̄1
a (Å) 10.7251(7)
b (Å) 12.5557(5)
c (Å) 13.3876(4)
α (0) 91.236(3)
β (0) 105.159(4)
γ (0) 97.140(4)
Volume (Å3) 1723.81
Z 1
Density (ρcalc., g cm−3) 2.348
µ (mm−1) 19.711
T min, Tmax 0.071,0.550
Theta (max) 66.990
R (reflections) 0.0745(4002)
wR2 (reflections) 0.0972(6036)
S 2.8
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2.6. Adsorption tests

The adsorption capacity of the Cu(diBzDTC)2-H3POMo hybrid adsorbent for dyes was evaluated through a series of experiments conducted at 25 °C in 100 mL beakers. In a typical experiment, 40 mg of the hybrid material was added to 50 mL of a dye solution with an initial concentration of 25 mg L−1. The mixture was stirred in the dark and samples (3 mL) were collected at predetermined time intervals. The adsorbent was then separated from the solution via centrifugation, and the concentrations of MB, RhB, and MO dyes in the supernatant were determined using UV-vis spectrophotometry at wavelengths of 664 nm, 556 nm, and 465 nm, respectively. Subsequently, the influence of various parameters on adsorption performance was assessed under comparable conditions, including varying the amount of hybrid adsorbent (20–50 mg), initial dye concentrations (5–35 mg L−1), and initial pH values (2–10). To investigate the material's ability to selectively adsorb dyes, 40 mg of Cu(diBzDTC)2-H3POMo was added to 50 mL of a mixed dye solution containing both MB and MO (each at 25 mg L−1), and the mixture was stirred. The adsorption process was monitored periodically using UV-vis spectroscopy. The removal efficiency (R, %) of the hybrid adsorbent was then calculated using eqn (1).

R (%) = (C0 − Ct) × 100/C0 1

C0 and Ceq represent the initial and equilibrium dye concentrations (mg L−1) respectively. The adsorption capability of the Cu(diBzDTC)2-H3POMo sample towards RhB and MO dyes was also evaluated under conditions similar to those described above.

2.7. Antibacterial tests

The antibacterial efficacy of Cu(diBzDTC)2-H3POMo hybrid was evaluated against several bacterial strains, including Gram-negative Escherichia coli (PTCC 1330) and Klebsiella pneumoniae (PTCC 1290), and Gram-positive Bacillus cereus (PTCC 1015), Staphylococcus aureus (1431), and Staphylococcus epidermidis (PTCC 1114). Using the modified Kirby–Bauer disk diffusion method, bacteria were cultured in Nutrient agar medium for 24 h at 37 °C and diluted to 4 × 106 cfu mL−1 in saline.56–58 The diluted suspension was spread onto Mueller–Hinton agar plates, and discs saturated with 30 or 50 µl of Cu(diBzDTC)2-H3POMo were placed atop. Amikacin served as a positive control. After incubation at 37 °C for 24 h, the diameter of inhibition zones around each disc was measured and expressed in millimeters. Mean values for each organism were determined.

3. Results and discussion

3.1. Crystal structure description of the hybrid

Single-crystal X-ray diffraction analysis of the hybrid compound revealed the presence of H3POMo cluster and Cu(diBzDTC)2 complex within the unit cell. The asymmetric unit contains one Cu(diBzDTC)2 complex and a disordered H3POMo cluster. Detailed crystallographic data is provided in Table 1 and a visual representation is shown in Fig. 1. Analysis of the CIF file (SI) identified disorder in the polyanion's oxygen atoms, a common issue with POMs due to their large size and numerous heavy atoms. The quality of the crystals was suboptimal, leading to imperfect intensity data and high atomic displacement parameter (ADP) max/min ratios for some atoms, which did not improve the R factors. Therefore, disordered atoms in Fig. 1 were isotropically refined. As shown in Fig. 2, the asymmetric unit contains one Cu(diBzDTC)2 complex and a disordered H3POMo. The H3POMo polyanion features a central PO4 tetrahedron surrounded by 12 MoO6 octahedra, arranged in four Mo3O13 groups. The central PO4 tetrahedron shares its oxygen atoms with four {Mo3O13} groups, each composed of three edge-sharing {MoO6} octahedra. These {Mo3O13} subunits are linked via corner-sharing. As provided in Table 2, P–O distances range from 1.520–1.584 Å, with O–P–O angles varying from 107.3–112°. Based on coordination modes, Mo–O distances fall into three categories: Mo–Ot (terminal oxygen) of 1.45–1.88 Å, Mo–Ob–Mo (bridging oxygen) of 1.65–2.09 Å, and Mo–Oc–Mo (central oxygen) of 2.43–2.50 Å. These values are consistent with reported data for the POM.59,60 The Cu atom is coordinated by four sulfur atoms from two dithiocarbamate ligands, forming a square planar CuS4 environment. The C–S bond length of copper complex ranges between 1.72–1.73 Å; these values are less than the typical C–S bond (1.80 Å), hence showing a partial double bond character typical to dithiocarbamate complexes.61 The trans S1–Cu1–S1 and S2–Cu1–S2 angles are 180.0°, which are consistent with reported dithiocarbamate complexes with square planar environment. As shown in Table 1S, Cu–S distances range from 2.190 to 2.191 Å. These values are shorter than those reported for the starting Cu(diBzDTC)2 (2.292 to 2.323 Å).62,63 As shown in Fig. 3 and 1S, H3POMo cluster and Cu(diBzDTC)2 units form a supramolecular structure with alternating arrangement. This structure is stabilized by a network of weak van der Waals interactions between groups of the complex and the polyoxometalate (Fig. 3, Tables 1S and 2S).

Fig. 1. ORTEP diagram with 50% thermal ellipsoids of the Cu(diBzDTC)2-H3POMo hybrid compound as determined by X-ray crystallography.

Fig. 1

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Fig. 2. Unit cell packing of the Cu(diBzDTC)2-H3POMo hybrid compound as determined by X-ray crystallography.

Fig. 2

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Table 2. Average of inhibition zones of Cu(diBzDTC)2-H3POMo hybrid against various Gram-positive and Gram-negative bacterial strains.

Bacteria Type Average inhibition zone diameter (mm)
diBzDTC ligand H3POMo Cu(diBzDTC)2 complex Amikacina Cu(diBzDTC)2-H3POMo
A. aureus Gram-positive 14 ± 0.2 8 ± 0.2 18 ± 0.3 17 ± 0.5 21 ± 0.5
S. epidermidis Gram-positive 13 ± 0.3 8 ± 0.2 16 ± 0.4 15 ± 0.4 19 ± 0.3
B. cereus Gram-positive 11 ± 0.3 5 ± 0.3 14 ± 0.5 14 ± 0.5 17 ± 0.6
E. coli Gram-negative 8 ± 0.2 5 ± 0.2 9 ± 0.4 10 ± 0.3 13 ± 0.5
K. pneumonia Gram-negative 9 ± 0.2 6 ± 0.3 11 ± 0.3 13 ± 0.7 15 ± 0.4
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a

Amikacin used as a standard antibiotic under similar conditions.

Fig. 3. Views of supramolecular structure of Cu(diBzDTC)2-H3POMo hybrid along b-axes (above picture) and some weak van der Waals interactions (down picture). The H3POMo clusters fill in the cages and holes constructed by the Cu(diBzDTC)2 complex.

Fig. 3

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3.2. FT-IR analysis

Fig. 4 presents the FT-IR spectra of the Cu(diBzDTC)2 complex, H3POMo, and their hybrid material, in single crystal and rod-like powder forms. The FT-IR spectrum of Cu(diBzDTC)2 complex is presented in Fig. 4(a). The weak bands at 3050 and 2915 cm−1 are assigned to the C–H stretching vibration in the benzene ring and the C–H vibration of the methylene (CH2) group, respectively. The absorption band of 1505 cm−1 is attributed to the skeletal stretching vibration of the C Created by potrace 1.16, written by Peter Selinger 2001-2019 C bond in the benzene ring.64 The band at 750 cm−1 is specified to the out-of-plane C–H bending vibration in ring benzene and is characteristic of monosubstitution on the benzene ring.64 The absorption band at 1235 cm−1 corresponds to the skeletal stretching vibration of the C–N bond. The absorption bands at 1010 and 980 cm−1 are assigned to the stretching vibrations of the C Created by potrace 1.16, written by Peter Selinger 2001-2019 S/C–S bonds.65–67 In the H3POMo – spectrum in Fig. 4(b), strong characteristic bands within the 780–1100 cm−1 range are observed. In this spectrum, characteristic bands at 1060, 960, 887 and 775 cm−1 are attributed to ν(P–O), ν(Mo Created by potrace 1.16, written by Peter Selinger 2001-2019 Ot), ν(Mo–Ob–Mo) and ν(Mo–Oc–Mo), respectively.68–70 In the spectra of hybrid material, characteristic bands at 1054, 956, 864 and 773 cm−1 for rod-like powder sample (Fig. 4(c)), and 1055, 955, 862 and 773 cm−1 for single crystal sample(Fig. 4(c)) are attributed to ν(P–O), ν(Mo Created by potrace 1.16, written by Peter Selinger 2001-2019 Ot), ν(Mo–Ob–Mo) and ν(Mo–Oc–Mo), respectively. Specifically, the C–N band shifts to a higher frequency at 1527 cm−1, while the ν(C–S) band shifts to lower frequencies at 960 and 875 cm−1. These spectral shifts highlight the strong interaction between the Cu(diBzDTC)2 complex and the H3POMo polyanion in the hybrid material. Additionally, because of the overlapping of the strong absorption bands of H3POMo (750–1100 cm−1) with bands related to the dithiocarbamate functional group, some noticeable features of Cu(diBzDTC)2 complex were not identified in the hybrid material. A characteristic absorption band near 2300 cm−1 appears in several of the FTIR spectra (e.g., Fig. 4(c)), which can be attributed to atmospheric carbon dioxide that interacts with the samples during measurement. Additionally, the broad band centered at approximately 3500 cm−1 corresponds to O–H stretching vibrations associated with water molecules incorporated within the hybrid framework structure.

Fig. 4. FT-IR spectra of (a) Cu(diBzDTC)2 complex, (b) H3POMo polyoxometalate, (c) Cu(diBzDTC)2-H3POMo single crystal sample, and (d) Cu(diBzDTC)2-H3POMo powder sample.

Fig. 4

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3.3. PXRD analysis

The crystalline phase purity of the Cu(diBzDTC)2-H3POMo hybrid material was confirmed through PXRD analysis. As shown in Fig. 5(a)–(c), the experimental PXRD patterns are in good agreement with the simulated pattern, indicating high phase purity and crystallinity of the single-crystal and powder samples. While the patterns exhibit a strong resemblance, slight discrepancies in peak intensities between the experimental and simulated PXRD patterns suggest the potential preferred orientation of particles within the powdered sample. Applying the Scherrer formula (D = 0.9λ/(β cos θ)) to the PXRD data, the average diameter size of the hybrid was estimated to be 45 nm. This calculation utilizes the wavelength of Cu Kα radiation (λ), the full width at half maximum of the diffraction peak (β), and the Bragg angle (θ).

Fig. 5. Powder XRD patterns of Cu(diBzDTC)2-H3POMo hybrid: (a) simulated pattern from the single-crystal data, (b) single-crystal sample and (c) the powdered sample.

Fig. 5

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3.4. Morphological studies

To understand the structure and morphology of the Cu(diBzDTC)2-H3POMo hybrid compound, SEM and TEM analyses were employed. SEM images in Fig. 6(a)–(e) in various magnification show rod-shaped particles with diameters ranging from 50–90 nm and lengths of 1–3 µm. TEM analysis in Fig. 6(f) further revealed that these hybrid nanorods have a smooth surface, porous composition, and average dimensions of 70 nm in diameter and 4–10 µm in length. The formation of rol-like particles can be related to the presence of H3POMo anions as template and benzylic groups in the Cu(diBzDTC)2 complex.

Fig. 6. (a)–(e) SEM images and (f) TEM image of the Cu(diBzDTC)2-H3POMo hybrid material.

Fig. 6

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3.5. EDX analysis

To confirm the chemical purity and stoichiometry of the hybrid, EDX analysis was performed. The EDX spectrum in Fig. 7(a) indicated the presence of Cu, S, N, C, P, Mo and O at their respective keV values. Moreover, EDX mapping analysis in Fig. 7(b) revealed a homogeneous distribution of these elements throughout the sample, further supporting the purity and homogeneity of the nano-rod hybrid compound. According to the EDX quantification results in the inset of Fig. 7(a), the atomic ratios of the C : N : O : P : S : Cu : Mo were found to be 33.45 : 2.15 : 42.67 : 1.02 : 4.22 : 1.00 : 12.57. The atomic ratios of Cu : N : S and P : Mo were approximately 1 : 2 : 4 and 1 : 12, respectively, as expected for the Cu dithiocarbamate complex and H3PMo12O40. The measured oxygen-to-other element atomic ratio exceeded the value expected from stoichiometry, implying that water molecules have become incorporated into the hybrid framework. This inference is corroborated by FT-IR spectroscopy, which reveals the characteristic OH vibrations of adsorbed H2O.

Fig. 7. (a) EDX spectrum and (b) SEM image and the corresponding elemental mappings of the Cu(diBzDTC)2-H3POMo hybrid material.

Fig. 7

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3.6. Thermal analysis

The thermal stability of the Cu(diBzDTC)2-H3POMo hybrid material was evaluated using thermogravimetric analysis (TG-DTA) under a nitrogen atmosphere, with a heating rate of 10 °C per min (Fig. 8(a)). The results showed that the material remained stable up to 180 °C. Between 180 and 250 °C, a 34% weight loss occurred, likely due to the removal of diBzDTC ligands, which is in close agreement with the calculated value of 34.5%. Further decomposition of the entire structure was observed between 200 and 550 °C, resulting in a significant weight loss of 17%. The weight loss of all steps to be about 51% which is consistent with the theoretical value (53.5%) calculated for the formation of CuS-1/2P2O5–12MoO3 from the complex. The DTA curve of the Cu(diBzDTC)2–H3POMo complex, shown in Fig. 8(a), displays three distinct peaks that correspond well with the TG results. The sharp endothermic peak observed around 250 °C is attributed to the decomposition of Cu(diBzDTC)2 part leading to the formation of CuS. Two additional, smaller endothermic peaks appearing at approximately 450 °C and 540 °C are associated with the breakdown of the H3POMo cluster, which produces a mixture of ½ P2O5 and 12 MoO3.

Fig. 8. (a) TG-DTA analysis and (b) BET specific surface area analysis of the Cu(diBzDTC)2-H3POMo hybrid material.

Fig. 8

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3.7. BET specific surface area analysis

The Cu(diBzDTC)2–H3POMo hybrid sample underwent analysis to determine its surface area, pore volume, and corresponding pore size distribution. As illustrated in Fig. 8(b), the nitrogen adsorption–desorption isotherms exhibit a typical type IV pattern with an H1-type hysteresis loop at higher relative pressures, indicating the presence of mesoporous structures. The measured BET specific surface area for sample is 75.45 m2 g−1, while its total pore volume is 0.1 cm3 g−1. The average pore diameter, calculated from the adsorption and desorption branches of the N2 isotherms using the Barrett–Joyner–Halenda (BJH) method, is approximately 15.5 nm.

3.8. Adsorption capability of the Cu(diBzDTC)2-H3POMo hybrid material

After successful synthesis, the Cu(diBzDTC)2-H3POMo hybrid material was evaluated for its ability to remove organic toxic dyes from contaminated water. Three dyes (MB, RhB, and MO) with varying charges and sizes were selected for the experiments. Adsorption was monitored via characteristic absorption bands at 664 nm for MB, 556 nm for RhB, and 465 nm for MO. A gradual decrease in absorption intensity indicated reduced dye concentrations in the solution. UV-visible spectra in Fig. 9(a) and (b) showed efficient removal of cationic MB and RhB within 40 min, with 96% and 68% removal rates, respectively. However, the Cu(diBzDTC)2-H3POMo hybrid exhibited very low adsorption capacity for the anionic MO dye, with only a slight decrease in absorption after 40 min as shown in Fig. 9(c). This suggests selective adsorption of cationic dyes due to their strong electrostatic interaction with negatively charged H3POMo molecules within the hybrid. In a mixed MB + MO dye solution the hybrid selectively adsorbed MB, which is evident from the disappearance of its absorption peak and the persistence of the MO peak in Fig. 9(d). This confirmed the hybrid's ability to distinguish between cationic and anionic dyes in wastewater. The hydrophilic properties of H3POMo allow for dye molecule penetration through the hybrid framework. Negatively charged H3POMo anions within the structure interact strongly with positively charged MB and RhB molecules, facilitating high adsorption efficiency. However, RhB's steric bulk hinders its access to active sites, limiting its removal efficiency. Conversely, MO's smaller size enables penetration, but its negative charge inhibits its adsorption due to repulsive forces with the negatively charged H3POMo anions in the hybrid. These results demonstrate that the hybrid material selectively adsorbs cationic dyes, such as MB and RhB, while exhibiting no affinity for anionic dyes like MO. This selective behavior confirms that the PMo12O403− (POMo) polyanions are the active species the hybrid material. Then, these polyanions encapsulated within the cages and cavities formed by the Cu(diBzDTC)2 complex (as shown in Fig. 3) serve as the primary active sites.

Fig. 9. The adsorption capability of Cu(diBzDTC)2-H3POMo hybrid toward different organic dyes: (a) MB, (b) RhB, (c) MO and (d) mixed dyes (MB + MO). Conditions: [dye] = 25 mg L−1 in 50 mL; adsorbent dose = 40 mg; adsorption time = 40 min; temperature = 25 °C.

Fig. 9

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3.8.1. Effect of the adsorbent dose

The study examined the removal of MB dye through adsorption process by utilizing different quantities of the hybrid adsorbent. As illustrated in Fig. 10(a), the MB dye adsorption efficiency considerably improved with the increasing adsorbent amounts, rising from 43% for 20 mg, to 81% for 30 mg, then to 96% for 40 mg, and finally reaching 99% for 50 mg This improvement is linked to the increased surface area and the greater availability of active sites on the hybrid adsorbent. However, only a slight increase in dye adsorption was noted with 50 mg of the adsorbent. Consequently, 40 mg was identified as the optimal quantity for subsequent experiments.

Fig. 10. Effects of (a) adsorbent dose, (b) initial dye concentration, and (c) initial pH on the adsorption efficiency of Cu(diBzDTC)2-H3POMo hybrid toward MB dye solutions. (d) Zeta potential analysis in a neutral aqueous solution (pH = 6.5–7) of the Cu(diBzDTC)2-H3POMo hybrid material. Conditions: [MB]0 = 25 mg L−1, 50 mL (for a and c); adsorbent dose = 40 mg (for b and c); pH = 6 (for a and b); and temperature = 25 °C.

Fig. 10

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3.8.2. Effect of the initial dye concentration

The initial dye concentration is a key factor that influences the adsorption characteristics of an adsorbent in wastewater treatment processes. As illustrated in Fig. 10(b), the impact of the initial concentration of MB on the adsorption process is notable. At lower initial concentrations of 5, 15, and 25 mg L−1, the Cu(diBzDTC)2-H3POMo hybrid can achieve an adsorption efficiency of 99 up to 95%. Otherwise, a decrease in the adsorption efficiency from 95 to 62% was observed with increasing initial concentration to 35 mg L−1, which can be explained by the deficiency of active sites needed for high MB concentration.

3.8.3. Effect of the initial pH

pH is crucial in determining the adsorption characteristics of materials because it influences the surface charges of the adsorbent. The adsorption process was analyzed at different pH levels to investigate how pH impacts the adsorption of MB molecules onto the Cu(diBzDTC)2-H3POMo hybrid. As illustrated in Fig. 10(c), there was a marked increase in adsorption percentage with rising pH. At pH 2, only 15% adsorption was observed within 50 min, while at pH 6, this figure jumped to approximately 96% in the same time frame. At pH 8, the adsorption reached 98% in just 30 min, and at pH 10, complete adsorption (100%) was achieved in only 20 min. These findings suggest that basic conditions facilitate the adsorption of MB molecules. High negative charges from the H3POMo in the hybrid allow for effective binding with cationic dyes. Additionally, as the pH increases, more deprotonated H3POMo polyanions become available, leading to enhanced adsorption of the cationic MB molecules. For further confirmation, the surface charge of the synthesized Cu(diBzDTC)2-H3POMo hybrid material was assessed using zeta potential analysis in a neutral aqueous solution (pH = 6.5–7) and results is shown in Fig. 10(d). The obtained zeta potential value of −21.5 mV indicates a strong negative surface charge, which can be attributed to the presence of H3POMo polyanions. These findings suggest that the adsorption efficiency of the cationic MB dye onto the Cu(diBzDTC)2-H3POMo hybrid is likely to be relatively high. Consequently, H3POMo, as the main component of the hybrid, enhances adsorption efficiency and optimizes performance for cationic species.

3.8.4. Comparison of the adsorptive activity of the synthesized hybrid with its components

To evaluate the adsorption performance of the hybrid in relation to its individual components, a series of tests was conducted under identical conditions by using 40 mg of each adsorbent sample. As illustrated in Fig. 11, the adsorption efficiency values for H3POMo, Cu(diBzDTC)2 complex and Cu(diBzDTC)2-H3POMo as adsorbents in the removal of MB were found to be 33, 20, 96%, respectively, within 50 min. These results indicate that the synthesized hybrid exhibits superior efficiency compared to the individual components. The enhanced catalytic activity of the composite can be attributed to the effective dispersion of H3POMo anions within the porous surface of Cu(diBzDTC)2 network, along with the synergistic interactions among the hybrid's constituent components. This synergistic effect, combined with the uniform distribution of H3POMo anions within the hybrid matrix, significantly enhances the adsorption process. The introduction of H3POMo into Cu(diBzDTC)2 framework resulted in the removal of dye molecules efficiently. To verify these synergistic effects, a physical mixture of the components (H3POMo + Cu(diBzDTC)2) was evaluated as an adsorbent. The results revealed a lower efficiency (58%) compared to the Cu(diBzDTC)2-H3POMo nanocomposite (96%), as shown in Fig. 11.

Fig. 11. The adsorption efficiency of the synthesized Cu(diBzDTC)2-H3POMo hybrid (a) with its components toward MB dye solutions. Sample a = the Cu(diBzDTC)2-H3POMo hybrid, sample b = Cu(diBzDTC)2 (20 mg)+ H3POMo (20 mg) physical mixture, sample c = H3POMo polyanion and sample d = Cu(diBzDTC)2 complex. Conditions: [MB]0 = 25 mg L−1, 50 mL; adsorbent dose = 40 mg; pH = 6 (for a and b); and time = 50 min, temperature = 25 °C.

Fig. 11

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3.8.5. Recyclability and stability

The recyclability and stability of adsorbents are crucial for their practical application. To investigate the desorption process, the dye-adsorbed hybrid was dispersed in 150 mL of methanol. Methanol, as an organic solvent, efficiently desorbs the MB organic dye from the solid adsorbent. The dye dissolves readily in methanol, making it an excellent leaching medium. Then, as the mixture was stirred, the dye molecules slowly detached from the adsorbent hybrid, causing the methanol solution to become blue color. Fig. 12(a) illustrates the UV-vis absorption spectrum from the desorption experiment in the methanol solution of adsorbent within 4 h. A distinct UV-vis absorption peak for MB was observed, and its intensity increased gradually, indicating that MB could be completely desorbed after several washes with fresh methanol. Additionally, adsorbent can be easily separated after the adsorption process and reused multiple times. As shown in Fig. 12(b), the adsorption performance declined by approximately 8% after the fourth cycle. The Cu and Mo metals concentrations in the filtrate were less than 0.1% as determined by ICP-AES analysis.

Fig. 12. (a) Time-dependent UV-vis spectrum changes of MB dye during the desorption process from the MB@adsorbent in methanol (the inset illustrates how the color changes of the methanolic MB@adsorbent mixture over time). (b) Recyclability of the Cu(diBzDTC)2-H3POMo hybrid. Conditions: [MB]0 = 25 mg L−1, 30 mL; adsorbent dose = 40 mg; adsorption time = 50 min; temperature = 25 °C.

Fig. 12

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Additionally, the structural stability of the recovered adsorbent was validated through XRD, FT-IR, SEM, and EDX analyses (Fig. 13). As illustrated in Fig. 13(a)–(c) and 2S(a) and (b), the PXRD patterns, FT-IR, and EDX spectrum and quantitative results (the inset of Fig. 13(c)) of the recovered hybrid showed little to no significant changes during four recycling runs when compared to those of the fresh hybrid material in Fig. 4, 5 and 7. The morphology of the recycled hybrid after four adsorption cycles was also examined (Fig. 13(d)). It was evident that the recovered adsorbent retained nearly its original size and morphology in Fig. 6. These findings reaffirm that the adsorbent is durable and effective for treating colored wastewater.

Fig. 13. (a) FT-IR spectrum, (b) PXRD pattern, (c) EDX spectrum and (d) SEM image of the recovered Cu(diBzDTC)2-H3POMo hybrid after the fourth cycle of adsorption process.

Fig. 13

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3.9. Antibacterial activity

The antibacterial efficacy of Cu(diBzDTC)2-H3POMo hybrid sample was evaluated against various Gram-positive and Gram-negative bacterial strains, including A. aureus, S. epidermidis, B. cereus, E. coli, and K. pneumoniae. The concentration of the hybrid was standardized at 0.5 µg mL−1 in DMSO solvent, and its effectiveness was compared to those of the diBzDTC ligand, H3POMo, Cu(diBzDTC)2 complex and amikacin as a standard antibiotic at the same concentration (Table 2). The biological activity of metal dithiocarbamate complexes is well-documented.17 In this study, the agar well-diffusion method was used for both antibacterial and antifungal assessments, with each experiment performed in triplicate. After the incubation period, the radial growth of the colonies was measured, and the average diameter was recorded. The zone of inhibition served as an indicator of biocidal activity, as outlined in Table 2. A zone measuring 20 mm or more signifies significant activity; 10–12 mm indicates good activity; 7–9 mm suggests low activity, while zones below 7 mm are considered insignificant. As shown in Table 2, the Cu(diBzDTC)2-H3POMo hybrid exhibited remarkable antibacterial properties against these pathogens, demonstrating superior efficacy compared to the diBzDTC ligand, H3POMo, Cu(diBzDTC)2 complex and well-known amikacin antibiotic, probably due to its ability to exhibit cooperative effects between Cu(diBzDTC)2 complex and H3POMo cluster for specific targets. Notably, its antibacterial activity against A. aureus was greater than that observed with S. epidermidis, B. cereus, E. coli, and K. pneumoniae. Differences in the structure and chemical composition of the cell walls among S. epidermidis, B. cereus, E. coli, and K. pneumoniae contribute to this variation. Typically, E. coli shows weaker tolerance to chemical stressors, including antibiotics, compared to A. aureus, S. epidermidis, B. cereus, and K. pneumoniae. This indicates that E. coli is particularly susceptible to the hybrid material. The promising antimicrobial properties exhibited by Cu(diBzDTC)2-H3POMo position it as a promising candidate for the next generation of antimicrobials.

4. Conclusions

A novel organic–inorganic hybrid material was successfully synthesized through the reaction between a well-defined H3POMo unit and a copper(ii)-dibenzyldithiocarbamate coordination complex. The resulting Cu(diBzDTC)2-H3POMo hybrid was characterized using various physical techniques, which confirmed its crystal structure. This hybrid material demonstrated the ability to selectively adsorb cationic dyes, such as MB and RhB, from water within 40 minutes, achieving removal efficiencies of 96% and 68%, respectively. The adsorbent efficiently removes cationic dyes such as MB and RhB, but exhibits lower affinity towards the anionic MO dye. This is because of the strong electrostatic interactions between the positively charged dye molecules and the negatively charged POMs in the hybrid. Moreover, the hybrid could be easily recycled and reused without any structural changes. Furthermore, the Cu(diBzDTC)2-H3POMo hybrid exhibited superior antibacterial properties compared to standard antibiotics, particularly against Gram-positive bacteria like A. aureus and S. epidermidis. In summary, considering its easy separation, large availability, and significant antibacterial activity, the Cu(diBzDTC)2-H3POMo hybrid shows great potential as a candidate material for advanced antimicrobial applications and the treatment of organic dye-contaminated water. Our laboratory is currently investigating the assembly of other metal dithiocarbamates and POMs, as well as the potential applications of the resulting hybrids.

Author contributions

Masoumeh Javanmard: data curation, investigation, formal analysis, methodology, writing – original draft. Saeed Farhadi: supervision, conceptualization, writing – review & editing. Michal Dusek: crystallographic experiments, single-crystal analysis, writing – review & editing. Monika Kucerakova: crystallographic experiments, single-crystal analysis, writing – review & editing Keivan Javanmard: formal analysis, writing – review & editing, Mansoureh Maleki: formal analysis, writing – review & editing.

Conflicts of interest

The authors declare that they have no conflicts of interest.

Supplementary Material

RA-016-D6RA00116E-s001
RA-016-D6RA00116E-s002

Acknowledgments

This work was supported by Lorestan University and Iran Nanotechnology Initiative Council. We acknowledge CzechNanoLab Research Infrastructure supported by MEYS CR (LM2023051) for the financial support of the crystallographic part of this work.

Data availability

Data for this article are available upon request from the corresponding author.

CCDC 2421315 contains the supplementary crystallographic data for this paper.71

Supplementary information (SI) is available. See DOI: https://doi.org/10.1039/d6ra00116e.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Data Citations

  1. CCDC 2421315: Experimental Crystal Structure Determination, 2026, 10.5517/ccdc.csd.cc2m8kyf [DOI]

Supplementary Materials

RA-016-D6RA00116E-s001
RA-016-D6RA00116E-s001.pdf (321.3KB, pdf)
RA-016-D6RA00116E-s002
RA-016-D6RA00116E-s002.cif (364.9KB, cif)

Data Availability Statement

Data for this article are available upon request from the corresponding author.

CCDC 2421315 contains the supplementary crystallographic data for this paper.71

Supplementary information (SI) is available. See DOI: https://doi.org/10.1039/d6ra00116e.

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