AIE-active sulfone infused two-dimensional manganese(II) porphyrin based covalent organic framework as an effective photocatalytic tool for oxidative construction of N-S bond
Available accessResearch articleFirst published online February, 2025
AIE-active sulfone infused two-dimensional manganese(II) porphyrin based covalent organic framework as an effective photocatalytic tool for oxidative construction of N-S bond
Sulfone-infused AIE-active 2-D manganese-porphyrin-based microporous COF (Mn-P) has been synthesized through a C-S coupling reaction. This process involved reacting manganese(II) tetra(p-bromophenyl) porphyrin with sulfur powder, using a catalytic amount of benzotriazole and copper iodide, under an inert nitrogen atmosphere at 100°C for 10–11 h. Mn-P has been used as a potential candidate for photocatalytic investigation due to its favorable optical and electrochemical band gap (1.78 eV). The size distribution study shows a narrow and uniform microporous structure with an average pore diameter of 1.80 nm along with ∼20.23 m2/g surface area. In the presence of sunlight as well as in aerobic conditions, the Mn-P proved its efficient photocatalytic role in the oxidative construction of N-S bond and the generation of 1,2,4-thiadiazole in excellent yield (93–97%).
Polymeric materials based on 1D, 2D, and 3D structural motifs play remarkable roles in the field of science and engineering through their semiconducting and light-harvesting properties.1 These materials due to high flexibility in ligand design, develop meso/microporous structures with control pore parameters and show their high applicability in gas absorption and photocatalysis.2 Motivated by the process of natural photosynthesis, significant efforts have been directed toward shaping innovative artificial light-harvesting systems.3 These systems not only intend to develop fundamental aspects of natural photosynthesis such as photoinduced electron transfer, but also create clean and sustainable energy to address the global energy challenges.4 Specifically, to attain an optimal energy collection efficiently, aside from maintaining a relatively high donor-to-acceptor ratio, another crucial factor is a densely packed organization of donors.5 However, these close and condensed configurations often result in the quenching of donor fluorescence, primarily due to the aggregation-caused quenching (ACQ) effect. This phenomenon may lead to diminished energy collection efficiencies. So, in recent years, research interest has been more directed towards suppressing the ACQ effects.6 This leads to a focus on developing innovative artificial light-harvesting systems that favor aggregation-induced emission properties.7
For the first time, Luo et al. in 2001 reported a silole-based system that can show an enhanced aggregation-induced phenomenon.8 In 2003, Chen et al. fabricated light-emitting diodes based on silole.9 Since then, AIE active species explored well in small molecules as well as in polymeric materials. Among these, polymeric materials possess several advantages over small ones as they offer numerous benefits which include ease of functionalization, structural diversity, and excellent thermal stability that give them significant potential in practical applications such as in organic light-emitting diodes,10 light-emitting liquid crystals,11 and circularly polarized luminescence (CPL).12 In polymers, Tang et al. (2003) initially developed AIE-based polymers using the silole-containing linear polyacetylenes.13 Ever since the reporting of the first AIE polymer by Tang et al., the development and utilization of AIE active polymers has consistently broadened.14 Later on, in 2013 Wang et al. synthesized the luminescent metal-organic framework that is AIE-active via incorporating tetraphenylethene (TPE) in UiO-isoreticular Zr MOF, which exhibits effective photocatalytic activities useful in oxidative coupling reactions.15 In the same line, Chang et al. reported an AIE-active covalently linked porphyrin with BMVC chromophore and their nanoparticles.16
In continuation with our group's research interest17,18,19,20 in the design and development of AIE21,22 active materials as well as 1-D and 2-D sulfone functionalized polymers, the present work is centered on the synthesis and characterization of an excellent 2-D manganese-porphyrin based covalent organic polymeric framework (Mn-P). The synthesized 2-D COF, Mn-P has been investigated for their optical (AIE) as well as its photocatalytic activity. An interesting structural feature of this assembly is the involvement of the sulfone23,24 (-SO2-) linker in the development of two-dimensional metalloporphyrin COF. The synthesis of Mn-P has been carried out by the direct reaction of Mn-TB with sulfur powder in the presence of a catalyst as mentioned in Scheme 1. The authenticity of Mn-P has been established by IR, XPS, XRD, and UV-visible spectroscopy. The compound texture, surface morphology, and thermal stability have been investigated by using XRD, SEM-EDX, BET, and TGA analysis.
Synthesis of sulfone-bridged 2D porphyrin assembly, Mn-P.
Materials and methods
Materials and instruments
In the experiment, all required chemicals were used as received from suppliers without any further purification. The compounds 4-Bromobenzaldehyde, Copper Iodide, Benzotriazole, and Sulphur powder have been purchased from Sigma Aldrich. Propionic acid, Manganese Acetate, Potassium Carbonate, Pyrrole, DMF, Ethanol, Chloroform, and other solvents were purchased from LOBA Chemie chemicals. The purification of solvents has been carried out according to commonly known literature procedures. To perform reactions, oven-dried glassware has been used. The progress of the reactions was monitored by TLC (Merck Millipore DC Kieselgel 60 F-254 aluminum sheets). For the recording of 1H-NMR and 13C-NMR spectra, the Brucker Advance NEO-500 MHz instruments were used and tetramethyl silane was taken as an internal standard. IR data was recorded using Perkin Elmer Spectrum IR Version 10.6.1. To record the UV-Vis absorption spectra, a UV-1900 UV-Visible Spectrophotometer by Shimadzu was used. XPS experiments were performed using X-Ray001 400um-FG ON. XRD was performed using A D5000 diffractometer. TGA 4000 was used for TGA analysis. Morphology was studied using the JSM-IT500 model of JEOL. CV studies were performed on MetrohmAutolab PGSTAT204. A morphological study is carried out using the JSM-IT500 model from JEOL.
Preparation of TB
Tetra (4-bromophenyl) porphyrin has been synthesized using the well-known reported method. Initially, 100 ml of propionic acid has been refluxed at 145 °C. Once the propionic acid begins to reflux, 1.14 ml (1 eq) of distilled pyrrole and 3 g (1 eq) of 4-bromobenzaldehyde are added in a baked 2-neck round bottom flask. To clean the condenser containing traces of pyrrole and 4-bromobenzaldehyde, 25 ml of propionic acid is added again. Then, the mixture is allowed to reflux for 30 min. The flask was then left to cool to room temperature and left for 24 h for aerial oxidation. The resulting dark brown slurry is filtered through Whatman filter paper no. 41 and rinsed thoroughly with water, followed by methanol, until a clear solution is obtained. The shiny purple-colored precipitate is dried in an oven at 100 °C overnight.25
Preparation of Mn-TB
Manganese porphyrin has been prepared by the reaction of 0.5 g (1 eq) of TB and 1.31 g (10 eq) of manganese acetate in 5 ml of N,N-dimethyl formamide (DMF) at 150 °C in a baked round bottom flask. The mixture is refluxed for 4 h, after which it is removed from the oil bath and left to cool at room temperature. Subsequently, ice-cold water is introduced into the flask and placed the solution in an ice bath for 20 min to induce precipitation. The resulting green colored mixture is then filtered and washed with small quantities of distilled water to remove excess DMF. The obtained green crystalline product is then dried under the vacuum for 24 h.
Preparation of Mn-P
In the synthesis, in a baked round-bottomed flask, the reaction of Mn-TB has been performed with sulfur powder in the presence of CuI and K2CO3 in DMF. At first, CuI 0.0066 gm (0.2 eq) and 0.008 gm (0.4 eq) Benztriazole are added in 3 ml of DMF in an inert environment (N2) and the 200 mg (1 eq) of Mn-TB is added into the stirred solution. After that, 0.1 gm (4 eq) K2CO3 and 0.0235 gm (4 eq) sulfur powder is added. After 10–11 h of heating along with continuous stirring at 100 ˚C, a greyish-black color precipitate is obtained. The purification of the polymeric compound, Mn-P, first it is first washed with chloroform and then benzene through the soxhlet extraction method to remove the monomeric species along with other impurities to get the purest state of Mn-P.
Result and discussion
The IR spectra of the starting monomeric molecule Mn-TB and polymeric material Mn-P have been comparatively studied to validate the formation of new bonds, specifically C-S, and –SO2- linkages. According to reported literature, the vibrational band associated with the C-Br bond26,27 is typically observed within the range of 1069–1072 cm−1. In the case of the molecular compound Mn-TB, the C-Br-related band is observed at 1071 cm−1 (Figure 1(a)) while bands at 590,1483, 1007, and890/801 cm−1represent C = C, C = N, Mn-N and C-H bonds (twisting and wagging modes), respectively.28 The generation of Mn-P from Mn-TB has been proposed through sulfone bridging and the same can be evident through IR. In the IR spectrum of Mn-P(Figure 1(b)), an intense band at 615 cm−1 is assigned to C-S bond formation i.e., C-S stretching vibration.29 Furthermore, a doublet band is observed at 1008 and 1094 cm−1, indicating the in-situ oxidation of bridged sulfides and the formation of SO2 groups in the assembly.30
Ir spectra of (a) Mn-TB (b) Mn-P.
The elemental presence and functionalities in Mn-P have been analyzed through XPS data. The Mn 2p XPS spectrum (Figure 2(b)) is fitted with two peaks at 641.6 eV and 653.2 eV, corresponding to Mn 2p3/2 and Mn 2p1/2 species, respectively,31 and in addition to this, a satellite peak is also observed at 646.8 eV as per the literature report.32 In the C1s spectrum (Figure 2(a)), three prominent peaks at 284.7 eV, 285.6 eV, and 287.1 eV correspond to C = C (sp2), C-S, and C-N bonds33 while the N 1s spectrum in Figure 2(d) shows two specific binding energies at 394.9 eV and 399.9 eV corresponding to pyridinic (-N = C-) and pyrrolic nitrogen of the porphyrin ring.34 The XPS data of these functionalities favors the structural identity of sulfone-infused 2D manganese(II) tetraphenyl porphyrin assembly (Mn-P). To find out the state of sulfur which is present in the polymeric structure, in Figure 2(c), the S 2p spectrum has been analyzed and it is observed that one specific energy band appears at 168.3 eV relates to -S(O)2- group.35,36 In addition to this, the S 2p spectrum shows peaks at 163.5 eV and 164.6 eV, attributed to the presence of the S-C bond (S 2p3/2 and 2p1/2).37 The XPS peak table (Figure S1b) shows the presence of all expected elements such ascarbon, oxygen, sulfur, nitrogen, and manganese.
XPS spectra of Mn-P; (a) C 1s, (b) Mn 2p, (c) S 2p, and (d) N 1s.
A thermo-gravimetric study has been conducted on polymer (Mn-P) to evaluate its thermal stability. The TGA analysis of Mn-P (Figure 3), shows two distinct stages of decomposition. Initially, from 0 to ∼140°C, desorption of interlayer absorbed water molecules takes place with a weight loss of 3.6%. This was followed by the continuous decomposition of remaining porphyrin residue from 141 to 800 °C with a weight loss of 54.11% and residue of ∼42.3%. Differential thermal analysis (DTA)has also been employed for Mn-P and it has been observed that at 140 °C a strong endothermic process is taking place and the second decomposition step starts from this point onward(Figure S3).38
Thermogravimetry analysis (TGA) of Mn-P.
The surface morphology and elemental composition of Mn-P (Figure 4) has been investigated through SEM-EDX study. The polymer exhibits a modified morphology, showcasing selective fine rods covered with fluffy powdered materials. In Figure S4, the SEM-EDX shows the presence of C, N, O, S, and Mn elements as expected. It supports the XRD patterns of Mn-P related to a crystalline and amorphous mixed-state.
Scanning Electron Microscopic (SEM) images of Mn-P.
Through the comparative XRD data analysis of Mn-TB and Mn-P, it can be proposed that Mn-P (Figure 5) (crystallinity value 69%) is more crystalline than Mn-TB (Figure S2) (49%). The XRD pattern of Mn-P indicates a crystalline nature as evident from sharp signals at 13.28, 15.95, 21.35, 23.83, 25.31, 27.91, 29.85, 30.92, 37.12, 40.63, and 43.39° (2θ), with corresponding d-spacing values of 6.66 Å, 5.54 Å, 4.15 Å, 3.73 Å, 3.35 Å, 3.19 Å, 3.06 Å, 2.89 Å, 2.41 Å, 2.23 Å and 2.08 Å, respectively and this confirms the short-range order with a noticeable crystalline disorder.39 Additionally, the presence of Mn can be confirmed by the appearance of a diffraction peak at 29.9° in both the XRD pattern of Mn-P and Mn-TB.40,41,42,43 The average crystalline nature of Mn-P polymeric material is found to be less than 100 nm as calculated by the Scherrer equation34 (63.46 nm).
XRD pattern of Mn-P.
The nitrogen adsorption-desorption isotherms (BET) of Mn-P at 77.35 K exhibit a Type IV profile with an H4 hysteresis loop as classified by IUPAC.44 The H4 loops are characterized by slowly rising at low P/Po which is followed by a rapid surge at high P/Po.45,46 In Figure 6 it is visible that adsorption of N2 is taking place on the surface of Mn-P very fast at relative pressure ∼0.9 to achieve complete saturation followed by plateau region while the desorption branch exhibits a gradual decrease.47,48 The size distribution study through the Barrett-Joyner-Halenda method defines a narrow and uniform microporous structure with an average pore diameter of 1.80 nm as well as a surface area of ∼20.23 m2/g. The nano-size and high surface area favors that the Mn-P can be an effective photocatalyst with promising light-harvesting properties.
Nitrogen-adsorption (black line) and desorption (red line) isotherms of Mn-P.
UV-visible study
The UV-visible spectra of Mn-TB and Mn-P49 have been recorded in DMF solvent to study their optical properties.50,51 In Figure S5, the Mn-TB spectrum reveals soret bands (V band)52 among them V band at 465 nm shows maximum absorption. Additionally, two Q bands of lower intensity have also been seen which are related to the electronic π to π* transition and show a hyper d-type graph, here LUMO energy is nearly close to metal orbital energy which makes them of great interest to photochemical studies.53 In the case of Mn-P (Figure 7(a)) maximum wavelength can be seen at 470 nm which is red-shifted by 5 nm from the V band of Mn-TB. The other V bands are suppressed in Mn-P due to secondary interactions between 2-D layers whereas the Q bands become broader due to the sulfone conjugation and the delocalization of electrons.54 The optical band gap in Figure S6, for Mn-TB and Mn-P, has also been calculated which is found to be 1.97 eV and 1.78 eV, respectively. The electrochemical band gap analysis supports well with the optical band gap studies. The electrochemical band gap of Mn-TB and Mn-P is found to be 1.97 eV and 1.78 eV, respectively. To perform the electrochemical study, 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) in DMF solution has been used as a supporting electrolyte where Ag/Ag + (reference), platinum (counter) and glassy carbon (working) are used as electrodes35. Through the electrochemical study, the calculated electrochemical data are as follows: For Mn-TB (Eoxidation onset = 1.18 V and Ereduction onset = −0.79 V): HOMO (5.78 eV) and LUMO (3.91 eV) in Figure S5, similarly for Mn-P (Eoxidation onset = 1.00 V and Ereduction onset = −0.78 V): HOMO (5.70 eV) and LUMO (3.92 eV) (Figure 7(b)).
(a) UV-Vis spectrum of Mn-P (1 mg in 10 ml solution in DMF) (b) CV study of Mn-P(0.1 M).
Aggregation-induced emission (AIE) studies of Mn-P
To analyze the electronic property of Mn-P in a mixed-solvent state, the AIE study has been carried out in DMF:H2O mixtures (0–90% water fractions) (Figure 8(a)). The mixtures are consistently maintained at a standard solution of 5 mg Mn-P in 25 ml DMF (1*10−3 M). The UV-Vis spectrum of Mn-P (1*1−3M solution) shows a strong absorption band with a λmax value of 298 nm. On the recorded λmax(298 nm), the emission spectra of Mn-P have been recorded in DMF:H2O mixtures (0–90% water fractions). In a surprising result, in Figure 8(b), it can be seen that 70% DMF (1*10−3M solution of Mn-P) and 30% H2O fractions are a perfect combination witha4.4times a parabolic increment in emission at 337 nm with a red shift of 39 nm. This red shift indicates a J-type of aggregation. In addition to this, in other DMF/H2O mixtures, the increment in H2O percentage results in hypochromic shifts in emission intensity due to the dilution effect.55
(a) UV–visible spectra of Mn-P (5 mg in 25 ml DMF) in varying water fraction (0% to 90%), (b) emission spectra of Mn-P (1 × 10−3 M) in varying H2O fraction (0% to 90%).
To study the H2O dilution effect, DLS data for various DMF:H2O mixtures (90:10, 70:30, 30:70, and 10:90) have been recorded for Mn-Pandit is observed that the highest particle size (9150 nm) with maximum AIE effect is present in the case of DMF:H2O (70:30). On the other hand, other mixtures are showing H2O dilution effect which results in a regular decrease in particle size i.e., 4501 nm, 900.1 nm, and 567.2 nm for 10%, 70%, and 90% H2O fractions, respectively(see Figure S8). Due to the hydrophobic effect, the generation of smaller particle size aggregates is more favoured and well-reported in the literature.56
Oxidative cyclization of thioamide to 1,2,4-thiadiazole
Compounds that contain 1,2,4-thiadiazole derivatives have great significance in biological and pharmaceutical industries, show their promising role in drugs development useful as antibiotic (cefozopram),57 antimicrobial,58 anti-inflammatory,59 antiviral, antineoplastic,60 and antitubercular agents.61 The synthesis of 1,2,4-thiadiazoles derivatives often involves the oxidative cyclization of primary thioamides62 (Scheme 2) in the presence of various oxidizing agents such as DDQ,63 iodate,64 and phosphovanadomolybdic acid.65 In this study, Mn-P has been investigated as a photocatalyst for the oxidative cyclization of thioamide due to its ability to generate O2•– efficiently.66 When a mixture of thioamide (1.0 mmol) and a catalytic amount of Mn-P (4 mg) in 3 mL of DMF has been exposed to an 18 W white LED bulb under ambient conditions produced 1,2,4-thiadiazole derivatives with 96.5% yield. In several experiments, the role of various components has also been investigated, and observed that light, oxygen, and Mn-P all are essential for the completion of this reaction (see Table S2). Furthermore, an experiment in the presence of radical scavenger, ascorbic acid(1.0 mmol) shows no reaction progress and confirms the role of superoxide radical (O2•–) in the cyclization process.67 Various thioamides, including those with electron-donating and electron-withdrawing groups, have been investigated for the generation of derivatives of 1,2,4-thiadiazoles with moderate to good yields under mild conditions. Thioamides with a diverse range of electron-donating subgroups like -OMe, -Cl, and -OH generate products with yield of (Table 1) 96.5%, 94.8%, and 94%, respectively. Among all, it can be seen that the strongest electron-donating group methoxy (-OMe) produces the highest yield (96.5%, Table S1). The authenticity of the product has been validated by 1H NMR (see supporting Figure S9).
Oxidative cyclization of thioamide.
Preferential photocatalytic cyclization reaction with various benzyl thioamide derivatives.
Reaction mechanism
Based on the literature as well as reactions performed herein, the plausible reaction mechanism for the cyclization of thioamide has been proposed in the presence of Mn-P (Scheme 3). Under the irradiation of light, Mn-P is first photo-excited to Mn-P*. The photo-generated electrons in Mn-P* reduce O2 to O2•–. At the same time, the resulting Mn-P+ cyclizes thioamide to thioamide radical cation 2 and regenerates the Mn-P. Two radical isomers 3a and 3b are formed with the proton removal and further dimerize to produce in-situ generated species 4. In the end, the 1,2,4-thiadiazole is obtained through the intramolecular cyclization of 4 and aromatization of 5 with the help of superoxide radical anion.
Plausible photocatalytic mechanism of Mn-P mediated cyclization of thioamide to 1,2,4-thiadiazole.
Conclusion
In the present work, sulfone bridged AIE-active two-dimensional manganese(II) tetraphenylporphyrinCOF(Mn-P) has been generated through C-S coupling as well as in-situ oxidation of sulfide sulfur. In the structural analysis, the polymeric assembly, Mn-P shows a microporous nature with a low optical and electrochemical band gap which makes them a suitable photocatalyst for the efficient generation of 1,2,4-thiadiazole via involvement of O2•–radical. This work opens the path to generate many more sulfone-bridged 2D metalloporphyrin assemblies and their application study in the field of small molecule synthesis. In the future, these 2D materials will be investigated to frame the 3D metalloporphyrin assemblies by using some specific linkers.
Supplemental Material
sj-docx-1-mgc-10.1177_10241221241309241 - Supplemental material for AIE-active sulfone infused two-dimensional manganese(II) porphyrin based covalent organic framework as an effective photocatalytic tool for oxidative construction of N-S bond
Supplemental material, sj-docx-1-mgc-10.1177_10241221241309241 for AIE-active sulfone infused two-dimensional manganese(II) porphyrin based covalent organic framework as an effective photocatalytic tool for oxidative construction of N-S bond by Anshita Nautiyal, Vivek Singh Rana, Renu Devi, Rehana Shahin, David G. Churchill, Rajesh Kumar Yadav and Atul Pratap Singh in Main Group Chemistry
Footnotes
Acknowledgment
The authors are thankful to the Department of Chemistry, Chandigarh University, Punjab for providing the basic instrumental facilities and funding for chemicals for conducting this research project. This work has also been supported by SERB-DST (YSS/2015/001237). We are thankful to IIT Jammu, for providing XPS Data facilities, Punjab University, Chandigarh for NMR, DLS, and BET studies, IIT Roorkee for TGA analysis, and UCRD Chandigarh University for SEM and XRD studies.
ORCID iD
Atul Pratap Singh
Author contributions
The manuscript has been written through the contributions of all authors. All authors have approved the final version of the manuscript.
Funding
The authors received no financial support for the research, authorship, and/or publication of this article.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.
Supplemental material
Supplemental material for this article is available online.
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