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Synthesis, aggregation, photocatalytical and electrochemical properties of axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine
Journal of Molecular Structure 1199 (2020) 126994
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Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, aggregation, photocatalytical and electrochemical properties of axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine Ece Tugba Saka*, Halise Yalazan, Zekeriya Bıyıklıoglu, Halit Kantekin, Kader Tekintas Department of Chemistry, Karadeniz Technical University, 61080, Trabzon, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history: Received 8 May 2019 Received in revised form 24 August 2019 Accepted 26 August 2019 Available online 30 August 2019
Photosensitized catalysis is the initiation of degradation or transformation reactions of molecules using a combination of light and photoactive materials as catalysts. In this work, 1-benzylpiperidin-4-oxy substituted silicone phthalocyanine (SiPc) 3 has been synthesized and characterized with different spectral data and determined catalytic behavior in p-nitrophenol degradation with 1758 turnover number (TON) and 586 turnover frequency (TOF) values. Metallophthalocyanine 3 is soluble in different organic solvents and investigated aggregation behavior in common organic solvents. Electrochemical properties of metallophthalocyanine 3 was defined by using cyclic voltammetry (CV) technique. Silicone phthalocyanine (SiPc) 3 shows one irreversible reduction couple R1 at 0.85 V (DEp ¼ 288 mV), one reversible reduction couple R2 at 1.54 V (DEp ¼ 95 mV) and one quasi-reversible oxidation couple O1 at 1.07 V (DEp ¼ 135 mV). © 2019 Elsevier B.V. All rights reserved.
Keywords: Silicon phthalocyanine Degradation p-Nitrophenol Photocatalyst
1. Introduction Phthalocyanines (Pcs) are a well-established group of synthetic dyes that have received increased attention of researchers in the last decades [1e3]. Their high thermal stability, interesting optical, photophysical, photochemical and electrochemical properties were used for development of photosensitizers in photodynamic therapy [4e6], dye-sensitized solar cells [7,8], fluorescence sensors [9,10], fluorophores [11,12], colorants and materials for optical, electronic and photo-electronic devices [13,14]. In recent years, catalytic degradation of organic pollutants using different metal catalysts is attracting many interests [15e19]. Due to metallophthalocyanines (MPcs) are synthetic molecules and structurally analogous to porphyrin complexes, they show bioinspired chemistry [20,21]. The catalytic properties of metallophthalocyanines depend on the metal atom and structure of the phthalocyanine moiety. Different metals are inserted in the core of the phthalocyanine ring to utilize them in specific reactions. Phthalocyanines show very stinted solubility in most organic solvents and water, a feature which restrains their applications in several areas. However the introduction of various substituents
* Corresponding author. Tel.: þ90 462 377 24 92, Fax: þ90 462 325 29 33. E-mail address: [email protected] (E.T. Saka). https://doi.org/10.1016/j.molstruc.2019.126994 0022-2860/© 2019 Elsevier B.V. All rights reserved.
such as diethylaminophenoxyethoxy, benzyloxy, alkyne, 6hydroxyhexylthio onto the ring system can improve the solubility of phthalocyanines in water or common organic solvents [22e31]. On the other hand, owing to the hydrophobic nature of the phthalocyanine ring, phthalocyanines have a strong tendency to aggregate in solution, which also limits their applications. However axially disubstituted silicon phthalocyanines are non-aggregated due to the non-planar substituents issuing from the center metal atom [32,33]. In order to increase the solubility of silicon phthalocyanines in common organic solvents and applications in different areas, we have synthesized new axially substituted silicon phthalocyanine. In this work, we have synthesized and characterized 1benzylpiperidin-4-oxy substituted silicone phthalocyanine. Axially-substituted silicon phthalocyanines (SiPcs) are of marvelous interest to scientists because they are generally not able to aggregate due to their special structural features [34]. Aggregation behavior of silicon phthalocyanine has been investigated in different organic solvents. Photocatalytic activity of silicon phthalocyanine complex has been investigated in oxidation of p-nitrophenol with different oxygen sources, different amounts of catalyst, TON and TOF values. The electrochemical behavior of silicon phthalocyanine has also been measured with the cyclic voltammetry (CV) and square wave voltammetry (SWV).
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2. Experimental
2.5. General procedure for the photooxidation of substituted phenols
2.1. Materials All reactions were carried under a dry nitrogen atmosphere using Standard Schlenk techniques. All chemicals, solvents, and reagents were of reagent grade quality and were used as purchased from commercial sources. All solvents were dried and purified as described by reported procedure [35]. 4-Nitrophthalonitrile 2 [36] were prepared according to the literature procedure. p-nitrophenol, o-chlorophenol, 2,3-dichlorophenol and p-methoxyphenol were purchased from Sigma-Aldrich and used without further purification and chemical treatment.
Experiments were carried out in a photocatalytic reactor equipped with stirrer and 18 pieces 8W UV lamp. The solution of pnitrophenol compound and catalyst in solvent was degassed. A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) was stirred in a reaction vessel for 1 h at room temperature. The samples (0.5 mL) were taken at certain time intervals. Each sample was injected at least twice in the GC, 1 mL each time. Formation of products and consumption of substrates were monitored by GC. The structure of the reaction products was confirmed by 1H NMR spectroscopy.
2.2. Equipment 3. Results and discussion The IR spectra were recorded on a PerkinElmer 1600 FT-IR spectrophotometer using KBr pellets. 1H NMR and 13C NMR spectra were recorded on a Varian Mercury 400 MHz spectrometer in CDCl3. Chemical shifts were reported (d) relative to Me4Si as internal standard. MALDI-MS of complexes were obtained in dihydroxybenzoic acid as MALDI matrix using nitrogen laser accumulating 50 laser shots using Bruker Microflex LT MALDI-TOF mass spectrometer. Optical spectra in the UVevis region were recorded with a PerkinElmer Lambda 25 spectrophotometer. GC Agilent Technologies 7820A equipment (30 m 0.32 mm x 0.50 mm DB Wax capillary column, FID detector) was used GC measurements. Photocatalytic experiments were carried out in photocatalytic reactor. A UV lamp (18 8W) producing 265 nm near visible light was used for photocatalytic studies. 2.3. Synthesis 2.3.1. 1-benzylpiperidin-4-oxy substituted silicon phthalocyanine (3) SiPcCl2 (150 mg, 0.24 mmol), 1-benzylpiperidin-4-ol (158 mg, 0.83 mmol) and sodium hydride (19.92 mg, 0.48 mmol) were mixed with dry toluene (15 mL) and refluxed for 24 h. The solvent was then removed under reduced pressure. The product was purified by column chromatography on aluminum oxide (CHCl3/MeOH 100:2) to give 3 as a green solid. Yield: 100 mg (34%), m.p. > 300 C. IR (ATR), n/cm1: 3062 (AreH), 2946e2884 (Aliph. CeH), 1586, 1512, 1478, 1458, 1450, 1365, 1287, 1255, 1176, 1118, 1084, 1023, 946, 767, 751.1 H NMR (400 MHz, CDCl3), (d): 8.96e8.88 (m, 8H, Pc-Ha), 8.44e8.36 (m, 8H, Pc-Hb), 7.74e7.58 (m, 5H, AreH), 7.49 (m, 5H, AreH), 4.40 (m, 2H, OeCH-), 3.40 (s, 4H, AreCH2eN), 2.38 (m, 8H, eCH2-), 1.61 (m, 8H, CH2-). 13C NMR (100 MHz, CDCl3), (d): 168.3, 160.8, 155.8, 145.7, 138.0, 133.5, 130.6, 127.3, 124.6, 122.9, 121.3, 120,8, 117.6, 115.6, 113.3, 118.61, 111.90, 81.80, 54.49, 51.30, 47.62, 33.26. UVeVis (DMF) lmax nm (log ε): 674 (5.12), 644 (4.34), 608 (4.78), 349 (4.58). MALDI-TOF-MS m/z calc. 921.13; found: 922.30 [MþH]þ. 2.4. Electrochemical measurements All electrochemical measurements were carried out with Gamry Interface 1000 potentiostat/galvanostat utilizing a three-electrode configuration at 25 C. The working electrode was a Pt disc with a surface area of 0.071 cm2. A Pt wire was served as the counter electrode and saturated calomel electrode (SCE) was employed as the reference electrode and separated from the bulk of the solution by a double bridge. Electrochemical grade tetrabuthylammonium perchlorate (TBAP) in extra pure dichloromethane (DCM) was employed as the supporting electrolyte at a concentration of 0.10 mol dm3.
3.1. Synthesis and characterization The formation of bis(1-benzylpiperidin)-4-oxyphthalocyaninato silicon(IV) 3 was clearly confirmed by the disappearance of the OH band at 3330 cm1 for 2 in the IR spectra of the silicon phthalocyanine 3. On the other hand, the characteristic vibrations corresponding to aliphatic eCH stretching at (2946e2884 cm1) aromatic eCH peaks at (3062 cm1) bands were observed for complex 3. In the 1 H NMR spectra, the phthalocyanine ring proton resonances appeared as multiplets integrating each as 8H at [(8.96e8.88)e(8.44e8.36) ppm] for the a and b protons, respectively. The other aliphatic and aromatic protons appeared at 7.74e7.58, 7.49, 4.40, 3.40, 2.38, 1.61 ppm. The 13C NMR spectra of 3, the aromatic carbon atoms resonated between 168.3 and 111.90 ppm and aliphatic carbon atoms resonated between 81.80 and 33.26 ppm. In the MALDI-TOF mass spectrum of bis(1-benzylpiperidin)-4oxyphthalocyaninato silicon(IV) 3 the molecular ion peak was observed at 922.30 [MþH]þ. The UVeVis absorption spectrum of 3 in CHCl3 is shown in SFig.2. The SiPc 3 shows an intense, sharp Q band at l ¼ 674 nm in CHCl3, a typically non-aggregated form. 3.2. Aggregation studies Due to the interaction between their 18 p-electron systems, phthalocyanines are weak soluble or unsoluble in common organic solvents because of. In this study aggregation behavior of the SiPc 3 was investigated in different solvents such as 1,4-dioxane, acetonitrile, diethyl ether, dichloromethane, dimethyl formamide, dimethyl sulfoxide, ethanol, ethyl acetate, hexane, chloroform and tetrahydrofurane (Fig. 1a). SiPc 3 having Q band in different solvents did not show any aggregation in these solvents suggesting that the substitution effect of the groups as axial substituent on the phthalocyanine ring. We also examined concentration effect on the aggregation of SiPc 3 (ranging from 2.0 106 to 12 106 mol dm3) in CHCl3 (Fig. 1b). As shown in Fig. 1b the intensity of absorption bands increases with increasing concentration and no new bands were observed signifying no aggregation behavior at these concentrations. 3.3. Electrochemical studies Voltammetric analysis of SiPc 3 was performed with CV measurement in dichloromethane (DCM)/tetrabutylammoniumperchlorate (TBAP) electrolyte system on a Pt working electrode. Voltammogram of SiPc 3 was analyzed to derive fundamental electrochemical parameters including the half-wave peak potentials (E1/2), peak to peak potential separations (DEp), the difference between the first oxidation and reduction processes (DE1/2). The
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Fig. 1. a) UVeVis spectrum of SiPc 3 in different solvents. b) UVeVis spectrum of SiPc 3 in CHCl3 at different concentrations (25 C and atmospheric pressure).
results of voltammetric analyses are given in Table 1. As shown in Fig. 2a, SiPc 3 shows one irreversible reduction couple R1 at 0.85 V (DEp ¼ 288 mV), one reversible reduction couple R2 at 1.54 V (DEp ¼ 95 mV) and one quasi-reversible oxidation couple O1 at 1.07 V (DEp ¼ 135 mV). For the reduction couples, DEp values at 0.100 mVs1 scan rate usually ranged from 0.060 to 0.120 V, suggesting reversible behavior [37]. Electrochemical behavior of SiPc 3 is in agreement with the similar SiPc
Table 1 Voltammetric data of the SiPc 3. All voltammetric data were given versus SCE.
DEp (mV)
DE1/2
Phthalocyanine
Redox processes
a
b
c
SiPc
R1 R2 O1
0.85 1.54 1.07
288 95 135
1.92
a b c
E1/2
E1/2 values ((Epa þ Epc)/2) were given versus SCE at 0.100 V-1 scan rate. DEp ¼ Epa-Epc. DE1/2 ¼ E1/2 (first oxidation)- E1/2 (first reduction).
complexes reported in the literature [38], which support the proposed structure of the SiPc synthesized here. Also, HOMO-LUMO gap of SiPc 3 (DE1/2 ¼ 1.92 V) is in compliance with the SiPc reported in the literature [38]. On the other hand, the peak currents increased linearly with the square root of the scan rates for scan rates ranging from 25 to 250 mV s1 for this SiPc 3 (Fig. 2b). 3.4. Catalytic studies The photocatalytic activity of silicon phthalocyanine 3 was investigated in the oxidation of p-nitrophenol compound in dichloromethane. The photocatalytic experiments were repeated in the presence and absence of light and catalyst. It is proved that presence of the light and catalyst are essential for the oxidation. In this work, two fragments were determined due to the attack by catalytically active species. The main product was determined as hydroquinone and the side product was determined as benzoquinone in the oxidation of p-nitrophenol photocatalytic degradation
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Fig. 2. a)CV and SWV of SiPc 3.b) CV of SiPc 3 at various scan rates (ranging from 25 to 250 mV s1) on a Pt working electrode in DCM/TBAP.
Fig. 3. The oxidation products of p-nitrophenol at room temperature.
E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
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nitrophenol, Co is the first concentration and C(t) is the concentration of p-nitrophenol as a function of illumination time. This equation shows a similar profile with the photocatalytic degradation of the other dyestuffs [40,41]. For this purpose, 100 mL of 0.025 M p-nitrophenol solution and 5 mg of solid catalyst and oxidant (H2O2) were reacted in a photoreactor for 3 h under visible light. During the photocatalytic reaction, all samples from taking reaction medium were diluted with dichloromethane and injected into the injection port of a GC apparatus, with phenol being the internal reference in this case. As a result, we have observed that a great portion of p-nitrophenol has been degraded and after 150 min, the degradation rate has been fixed. Data about photocatalytic degradation of p-nitrophenol that was sensitized with silicone phthalocyanine under visible light were presented in Fig. 4. Fig. 5 clearly shows that silicon phthalocyanine is good catalyst for degradation of p-nitrophenol with giving major product (66%) and side product (22%). Table 2 summarizes all photocatalytic results with selectivity, TON and TOF values for complex 3. According to Table 2, silicon phthalocyanine 3 exhibits good catalytic activity for p-nitrophenol degradation with 1758 TON and 586 TOF values. To find the optimal reaction conditions, catalyst/substrate ratio was tested in p-nitrophenol oxidation. When the catalyst/substrate ratio was increased from 0.01/2000 to 1/2000, the rate of the reaction increased. In contrast, while the catalytic oxidation was processing from 1/2000 to 50/2000, the conversion fixed to 88%. In the literature, many reports are available about catalytic activities of phthalocyanine (without support) [42e47] but in few ones visible light was used in catalytic process. Some previously reported catalysts are summarized in Table 3. Different groups substituted cobalt(II), iron(II), aluminium(III), copper(II) and metal free phthalocyanines were investigated on photooxidation of different pollutants [48e54]. Nyokong and co-workers studied photocatalytic activities of seven octasubstituted thio and aryloxy palladium and platinum phthalocyanines in degradation of pnitrophenol [55]. According to kinetic studies of this work, there would be two reaction pathways for degradation of p-nitrophenol with phthalocyanine catalyst (Fig. 6) [55]. In the another research of T. Nyokong, singlet oxygen quantum yields and photodegradation of p-nitrophenol in the presence of zinc tetrasulfophthalocyanine (ZnPcS4), zinc octacarboxyphthalocyanine (ZnPc(COOH)8) as photocatalysts are reported [56]. In this work, it is the first time for investigation of photocatalytic degradation p-nitrophenol with 1benzylpiperidin-4-oxy groups substituted SiPc 3 without any oxygen source. The results of photocatalytic experiments are promising and can be create new researches and micro scale application.
Fig. 4. The photocatalytic oxidation of p-nitrophenol with near visible light irradiation SiPc 3 and in dark. (A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) at 1 h).
Fig. 5. The conversion of p-nitrophenol, hydroquinone, benzoquinone in photocatalytic conditions. (A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) at 1 h and 18 pieces 8W UV lamp).
reaction (Fig. 3). After the degradation studies, the photodegradation amount of p-nitrophenol was calculated with the equation below [39]:
. XðtÞ ¼ Co CðtÞ Co In the equation above, X(t) is the molar fraction of pTable 2 Selective oxidation of p-nitrophenol with catalyst 3.
Selectivitya (%)
TOF (h1)
Subs./Ox./Cat
Oxidant
Temperature (oC)
Conversion (%) SiPc 3
SiPc 3
SiPc 3
SiPc 3
2000/500/1 2000/free/1 2000/500/free 2000/500/1(in dark) 2000/500/0.01 2000/500/0.1 2000/500/10 2000/500/50
H2O2 H2O2 H2O2 H2O2 H2O2 H2O2 H2O2 H2O2
25 25 25 25 25 25 25 25
88 37 e 9 33 46 88 88
75 67 e 45 42 39 75 75
1758 740 e 180 1.65 23 1758 1758
586 246 e 60 0.55 7.67 586 586
All photocatalytic reaction were done in photoreactor with light. TON ¼ mole of product/mole of catalyst. TOF ¼ mole of product/mole of catalyst x time. Conversion was determined by GC. Reaction Conditions: solvent (dichloromethane), p-nitrophenol (10.85 103 mol), catalyst (5.43 106 mol), oxidant (2.71 103 mol). a ¼ Selectivity of benzoquinone Reaction time ¼ 3 h.
TON
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Table 3 Catalytic activities of phthalocyanines towards the photooxidation of different organic compounds in some previously reported catalyst. Catalyst
Substrate
Rxn Time (h)
Rxn Temp. (oC)
Oxidant
Conv. (%)
Ref.
ZnTsPca FePcb CoTNPcc CoPcd Metal free Pcf CuPcg CoPcı ZnPcı
Methyl orange-Orange G Ethyl benzene Malachite green 2-mercaptoethanol Süflide ion 4-nitrophenol 4-chlorophenol
10min 9h 30 min 2 1 5 3
nr rt nr rt rt 27 rt
O2 O2 e e O2 e O2
nr >99 99.2 nre 70 nrh 99.99 97.05
[49] [50] [51] [52] [53] [54] [55]
ZnTs-CoFerritea ¼ 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II). FePc-POFb ¼ four-branched tetra-amine FePc-porous organic framework. CoTNPc/SnIn4S8 c ¼ Tetranitrocobalt phthalocyanine/ternary chalcogenide. CoPcd ¼ Cobaltphthalocyanine/C60. Metal free Pcf ¼ Metal free phthalocyanine/TiO2. CuPcg ¼ Copper phthalocyanine/TiO2. CoPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato cobalt(II)/TiO2. ZnPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato zinc(II)/TiO2. nr ¼ not reported. nre ¼ Turnover number is given as 8.4. nrh ¼ Quantum yield is given as 1.9.
Fig. 6. Mechanism of p-nitrophenol degradation.
4. Conclusion
Acknowledgement
In conclusion, axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine 3 was designed and synthesized. SiPc 3 is highly soluble in most of the organic solvents and are investigated aggregation behavior in different common organic solvents. The photocatalytic activity of SiPc 3 was examined for p-nitrophenol degradation using photochemical reactor. The results indicated that the catalyst showed good activity for p-nitrophenol degradation to the corresponding hydroquinone as major product in 1 h at 25 C. Cyclic voltammetry was used in order to investigate the electrochemical properties of SiPc 3. Electrochemical responses of SiPc 3 support the proposed structure of the complex. Voltammetric studies suggested that SiPc 3 display reversible/quasireversible/ irreversible redox processes, which are the main requirement for the technological usage of this compound.
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Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, aggregation, photocatalytical and electrochemical properties of axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine Ece Tugba Saka*, Halise Yalazan, Zekeriya Bıyıklıoglu, Halit Kantekin, Kader Tekintas Department of Chemistry, Karadeniz Technical University, 61080, Trabzon, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history: Received 8 May 2019 Received in revised form 24 August 2019 Accepted 26 August 2019 Available online 30 August 2019
Photosensitized catalysis is the initiation of degradation or transformation reactions of molecules using a combination of light and photoactive materials as catalysts. In this work, 1-benzylpiperidin-4-oxy substituted silicone phthalocyanine (SiPc) 3 has been synthesized and characterized with different spectral data and determined catalytic behavior in p-nitrophenol degradation with 1758 turnover number (TON) and 586 turnover frequency (TOF) values. Metallophthalocyanine 3 is soluble in different organic solvents and investigated aggregation behavior in common organic solvents. Electrochemical properties of metallophthalocyanine 3 was defined by using cyclic voltammetry (CV) technique. Silicone phthalocyanine (SiPc) 3 shows one irreversible reduction couple R1 at 0.85 V (DEp ¼ 288 mV), one reversible reduction couple R2 at 1.54 V (DEp ¼ 95 mV) and one quasi-reversible oxidation couple O1 at 1.07 V (DEp ¼ 135 mV). © 2019 Elsevier B.V. All rights reserved.
Keywords: Silicon phthalocyanine Degradation p-Nitrophenol Photocatalyst
1. Introduction Phthalocyanines (Pcs) are a well-established group of synthetic dyes that have received increased attention of researchers in the last decades [1e3]. Their high thermal stability, interesting optical, photophysical, photochemical and electrochemical properties were used for development of photosensitizers in photodynamic therapy [4e6], dye-sensitized solar cells [7,8], fluorescence sensors [9,10], fluorophores [11,12], colorants and materials for optical, electronic and photo-electronic devices [13,14]. In recent years, catalytic degradation of organic pollutants using different metal catalysts is attracting many interests [15e19]. Due to metallophthalocyanines (MPcs) are synthetic molecules and structurally analogous to porphyrin complexes, they show bioinspired chemistry [20,21]. The catalytic properties of metallophthalocyanines depend on the metal atom and structure of the phthalocyanine moiety. Different metals are inserted in the core of the phthalocyanine ring to utilize them in specific reactions. Phthalocyanines show very stinted solubility in most organic solvents and water, a feature which restrains their applications in several areas. However the introduction of various substituents
* Corresponding author. Tel.: þ90 462 377 24 92, Fax: þ90 462 325 29 33. E-mail address: [email protected] (E.T. Saka). https://doi.org/10.1016/j.molstruc.2019.126994 0022-2860/© 2019 Elsevier B.V. All rights reserved.
such as diethylaminophenoxyethoxy, benzyloxy, alkyne, 6hydroxyhexylthio onto the ring system can improve the solubility of phthalocyanines in water or common organic solvents [22e31]. On the other hand, owing to the hydrophobic nature of the phthalocyanine ring, phthalocyanines have a strong tendency to aggregate in solution, which also limits their applications. However axially disubstituted silicon phthalocyanines are non-aggregated due to the non-planar substituents issuing from the center metal atom [32,33]. In order to increase the solubility of silicon phthalocyanines in common organic solvents and applications in different areas, we have synthesized new axially substituted silicon phthalocyanine. In this work, we have synthesized and characterized 1benzylpiperidin-4-oxy substituted silicone phthalocyanine. Axially-substituted silicon phthalocyanines (SiPcs) are of marvelous interest to scientists because they are generally not able to aggregate due to their special structural features [34]. Aggregation behavior of silicon phthalocyanine has been investigated in different organic solvents. Photocatalytic activity of silicon phthalocyanine complex has been investigated in oxidation of p-nitrophenol with different oxygen sources, different amounts of catalyst, TON and TOF values. The electrochemical behavior of silicon phthalocyanine has also been measured with the cyclic voltammetry (CV) and square wave voltammetry (SWV).
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2. Experimental
2.5. General procedure for the photooxidation of substituted phenols
2.1. Materials All reactions were carried under a dry nitrogen atmosphere using Standard Schlenk techniques. All chemicals, solvents, and reagents were of reagent grade quality and were used as purchased from commercial sources. All solvents were dried and purified as described by reported procedure [35]. 4-Nitrophthalonitrile 2 [36] were prepared according to the literature procedure. p-nitrophenol, o-chlorophenol, 2,3-dichlorophenol and p-methoxyphenol were purchased from Sigma-Aldrich and used without further purification and chemical treatment.
Experiments were carried out in a photocatalytic reactor equipped with stirrer and 18 pieces 8W UV lamp. The solution of pnitrophenol compound and catalyst in solvent was degassed. A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) was stirred in a reaction vessel for 1 h at room temperature. The samples (0.5 mL) were taken at certain time intervals. Each sample was injected at least twice in the GC, 1 mL each time. Formation of products and consumption of substrates were monitored by GC. The structure of the reaction products was confirmed by 1H NMR spectroscopy.
2.2. Equipment 3. Results and discussion The IR spectra were recorded on a PerkinElmer 1600 FT-IR spectrophotometer using KBr pellets. 1H NMR and 13C NMR spectra were recorded on a Varian Mercury 400 MHz spectrometer in CDCl3. Chemical shifts were reported (d) relative to Me4Si as internal standard. MALDI-MS of complexes were obtained in dihydroxybenzoic acid as MALDI matrix using nitrogen laser accumulating 50 laser shots using Bruker Microflex LT MALDI-TOF mass spectrometer. Optical spectra in the UVevis region were recorded with a PerkinElmer Lambda 25 spectrophotometer. GC Agilent Technologies 7820A equipment (30 m 0.32 mm x 0.50 mm DB Wax capillary column, FID detector) was used GC measurements. Photocatalytic experiments were carried out in photocatalytic reactor. A UV lamp (18 8W) producing 265 nm near visible light was used for photocatalytic studies. 2.3. Synthesis 2.3.1. 1-benzylpiperidin-4-oxy substituted silicon phthalocyanine (3) SiPcCl2 (150 mg, 0.24 mmol), 1-benzylpiperidin-4-ol (158 mg, 0.83 mmol) and sodium hydride (19.92 mg, 0.48 mmol) were mixed with dry toluene (15 mL) and refluxed for 24 h. The solvent was then removed under reduced pressure. The product was purified by column chromatography on aluminum oxide (CHCl3/MeOH 100:2) to give 3 as a green solid. Yield: 100 mg (34%), m.p. > 300 C. IR (ATR), n/cm1: 3062 (AreH), 2946e2884 (Aliph. CeH), 1586, 1512, 1478, 1458, 1450, 1365, 1287, 1255, 1176, 1118, 1084, 1023, 946, 767, 751.1 H NMR (400 MHz, CDCl3), (d): 8.96e8.88 (m, 8H, Pc-Ha), 8.44e8.36 (m, 8H, Pc-Hb), 7.74e7.58 (m, 5H, AreH), 7.49 (m, 5H, AreH), 4.40 (m, 2H, OeCH-), 3.40 (s, 4H, AreCH2eN), 2.38 (m, 8H, eCH2-), 1.61 (m, 8H, CH2-). 13C NMR (100 MHz, CDCl3), (d): 168.3, 160.8, 155.8, 145.7, 138.0, 133.5, 130.6, 127.3, 124.6, 122.9, 121.3, 120,8, 117.6, 115.6, 113.3, 118.61, 111.90, 81.80, 54.49, 51.30, 47.62, 33.26. UVeVis (DMF) lmax nm (log ε): 674 (5.12), 644 (4.34), 608 (4.78), 349 (4.58). MALDI-TOF-MS m/z calc. 921.13; found: 922.30 [MþH]þ. 2.4. Electrochemical measurements All electrochemical measurements were carried out with Gamry Interface 1000 potentiostat/galvanostat utilizing a three-electrode configuration at 25 C. The working electrode was a Pt disc with a surface area of 0.071 cm2. A Pt wire was served as the counter electrode and saturated calomel electrode (SCE) was employed as the reference electrode and separated from the bulk of the solution by a double bridge. Electrochemical grade tetrabuthylammonium perchlorate (TBAP) in extra pure dichloromethane (DCM) was employed as the supporting electrolyte at a concentration of 0.10 mol dm3.
3.1. Synthesis and characterization The formation of bis(1-benzylpiperidin)-4-oxyphthalocyaninato silicon(IV) 3 was clearly confirmed by the disappearance of the OH band at 3330 cm1 for 2 in the IR spectra of the silicon phthalocyanine 3. On the other hand, the characteristic vibrations corresponding to aliphatic eCH stretching at (2946e2884 cm1) aromatic eCH peaks at (3062 cm1) bands were observed for complex 3. In the 1 H NMR spectra, the phthalocyanine ring proton resonances appeared as multiplets integrating each as 8H at [(8.96e8.88)e(8.44e8.36) ppm] for the a and b protons, respectively. The other aliphatic and aromatic protons appeared at 7.74e7.58, 7.49, 4.40, 3.40, 2.38, 1.61 ppm. The 13C NMR spectra of 3, the aromatic carbon atoms resonated between 168.3 and 111.90 ppm and aliphatic carbon atoms resonated between 81.80 and 33.26 ppm. In the MALDI-TOF mass spectrum of bis(1-benzylpiperidin)-4oxyphthalocyaninato silicon(IV) 3 the molecular ion peak was observed at 922.30 [MþH]þ. The UVeVis absorption spectrum of 3 in CHCl3 is shown in SFig.2. The SiPc 3 shows an intense, sharp Q band at l ¼ 674 nm in CHCl3, a typically non-aggregated form. 3.2. Aggregation studies Due to the interaction between their 18 p-electron systems, phthalocyanines are weak soluble or unsoluble in common organic solvents because of. In this study aggregation behavior of the SiPc 3 was investigated in different solvents such as 1,4-dioxane, acetonitrile, diethyl ether, dichloromethane, dimethyl formamide, dimethyl sulfoxide, ethanol, ethyl acetate, hexane, chloroform and tetrahydrofurane (Fig. 1a). SiPc 3 having Q band in different solvents did not show any aggregation in these solvents suggesting that the substitution effect of the groups as axial substituent on the phthalocyanine ring. We also examined concentration effect on the aggregation of SiPc 3 (ranging from 2.0 106 to 12 106 mol dm3) in CHCl3 (Fig. 1b). As shown in Fig. 1b the intensity of absorption bands increases with increasing concentration and no new bands were observed signifying no aggregation behavior at these concentrations. 3.3. Electrochemical studies Voltammetric analysis of SiPc 3 was performed with CV measurement in dichloromethane (DCM)/tetrabutylammoniumperchlorate (TBAP) electrolyte system on a Pt working electrode. Voltammogram of SiPc 3 was analyzed to derive fundamental electrochemical parameters including the half-wave peak potentials (E1/2), peak to peak potential separations (DEp), the difference between the first oxidation and reduction processes (DE1/2). The
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3
Fig. 1. a) UVeVis spectrum of SiPc 3 in different solvents. b) UVeVis spectrum of SiPc 3 in CHCl3 at different concentrations (25 C and atmospheric pressure).
results of voltammetric analyses are given in Table 1. As shown in Fig. 2a, SiPc 3 shows one irreversible reduction couple R1 at 0.85 V (DEp ¼ 288 mV), one reversible reduction couple R2 at 1.54 V (DEp ¼ 95 mV) and one quasi-reversible oxidation couple O1 at 1.07 V (DEp ¼ 135 mV). For the reduction couples, DEp values at 0.100 mVs1 scan rate usually ranged from 0.060 to 0.120 V, suggesting reversible behavior [37]. Electrochemical behavior of SiPc 3 is in agreement with the similar SiPc
Table 1 Voltammetric data of the SiPc 3. All voltammetric data were given versus SCE.
DEp (mV)
DE1/2
Phthalocyanine
Redox processes
a
b
c
SiPc
R1 R2 O1
0.85 1.54 1.07
288 95 135
1.92
a b c
E1/2
E1/2 values ((Epa þ Epc)/2) were given versus SCE at 0.100 V-1 scan rate. DEp ¼ Epa-Epc. DE1/2 ¼ E1/2 (first oxidation)- E1/2 (first reduction).
complexes reported in the literature [38], which support the proposed structure of the SiPc synthesized here. Also, HOMO-LUMO gap of SiPc 3 (DE1/2 ¼ 1.92 V) is in compliance with the SiPc reported in the literature [38]. On the other hand, the peak currents increased linearly with the square root of the scan rates for scan rates ranging from 25 to 250 mV s1 for this SiPc 3 (Fig. 2b). 3.4. Catalytic studies The photocatalytic activity of silicon phthalocyanine 3 was investigated in the oxidation of p-nitrophenol compound in dichloromethane. The photocatalytic experiments were repeated in the presence and absence of light and catalyst. It is proved that presence of the light and catalyst are essential for the oxidation. In this work, two fragments were determined due to the attack by catalytically active species. The main product was determined as hydroquinone and the side product was determined as benzoquinone in the oxidation of p-nitrophenol photocatalytic degradation
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Fig. 2. a)CV and SWV of SiPc 3.b) CV of SiPc 3 at various scan rates (ranging from 25 to 250 mV s1) on a Pt working electrode in DCM/TBAP.
Fig. 3. The oxidation products of p-nitrophenol at room temperature.
E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
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nitrophenol, Co is the first concentration and C(t) is the concentration of p-nitrophenol as a function of illumination time. This equation shows a similar profile with the photocatalytic degradation of the other dyestuffs [40,41]. For this purpose, 100 mL of 0.025 M p-nitrophenol solution and 5 mg of solid catalyst and oxidant (H2O2) were reacted in a photoreactor for 3 h under visible light. During the photocatalytic reaction, all samples from taking reaction medium were diluted with dichloromethane and injected into the injection port of a GC apparatus, with phenol being the internal reference in this case. As a result, we have observed that a great portion of p-nitrophenol has been degraded and after 150 min, the degradation rate has been fixed. Data about photocatalytic degradation of p-nitrophenol that was sensitized with silicone phthalocyanine under visible light were presented in Fig. 4. Fig. 5 clearly shows that silicon phthalocyanine is good catalyst for degradation of p-nitrophenol with giving major product (66%) and side product (22%). Table 2 summarizes all photocatalytic results with selectivity, TON and TOF values for complex 3. According to Table 2, silicon phthalocyanine 3 exhibits good catalytic activity for p-nitrophenol degradation with 1758 TON and 586 TOF values. To find the optimal reaction conditions, catalyst/substrate ratio was tested in p-nitrophenol oxidation. When the catalyst/substrate ratio was increased from 0.01/2000 to 1/2000, the rate of the reaction increased. In contrast, while the catalytic oxidation was processing from 1/2000 to 50/2000, the conversion fixed to 88%. In the literature, many reports are available about catalytic activities of phthalocyanine (without support) [42e47] but in few ones visible light was used in catalytic process. Some previously reported catalysts are summarized in Table 3. Different groups substituted cobalt(II), iron(II), aluminium(III), copper(II) and metal free phthalocyanines were investigated on photooxidation of different pollutants [48e54]. Nyokong and co-workers studied photocatalytic activities of seven octasubstituted thio and aryloxy palladium and platinum phthalocyanines in degradation of pnitrophenol [55]. According to kinetic studies of this work, there would be two reaction pathways for degradation of p-nitrophenol with phthalocyanine catalyst (Fig. 6) [55]. In the another research of T. Nyokong, singlet oxygen quantum yields and photodegradation of p-nitrophenol in the presence of zinc tetrasulfophthalocyanine (ZnPcS4), zinc octacarboxyphthalocyanine (ZnPc(COOH)8) as photocatalysts are reported [56]. In this work, it is the first time for investigation of photocatalytic degradation p-nitrophenol with 1benzylpiperidin-4-oxy groups substituted SiPc 3 without any oxygen source. The results of photocatalytic experiments are promising and can be create new researches and micro scale application.
Fig. 4. The photocatalytic oxidation of p-nitrophenol with near visible light irradiation SiPc 3 and in dark. (A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) at 1 h).
Fig. 5. The conversion of p-nitrophenol, hydroquinone, benzoquinone in photocatalytic conditions. (A mixture of p-nitrophenol compounds (10.85 103 mol), catalyst (5.43 106 mol, oxidant (2.71 103 mol) and solvent (0.01 L) at 1 h and 18 pieces 8W UV lamp).
reaction (Fig. 3). After the degradation studies, the photodegradation amount of p-nitrophenol was calculated with the equation below [39]:
. XðtÞ ¼ Co CðtÞ Co In the equation above, X(t) is the molar fraction of pTable 2 Selective oxidation of p-nitrophenol with catalyst 3.
Selectivitya (%)
TOF (h1)
Subs./Ox./Cat
Oxidant
Temperature (oC)
Conversion (%) SiPc 3
SiPc 3
SiPc 3
SiPc 3
2000/500/1 2000/free/1 2000/500/free 2000/500/1(in dark) 2000/500/0.01 2000/500/0.1 2000/500/10 2000/500/50
H2O2 H2O2 H2O2 H2O2 H2O2 H2O2 H2O2 H2O2
25 25 25 25 25 25 25 25
88 37 e 9 33 46 88 88
75 67 e 45 42 39 75 75
1758 740 e 180 1.65 23 1758 1758
586 246 e 60 0.55 7.67 586 586
All photocatalytic reaction were done in photoreactor with light. TON ¼ mole of product/mole of catalyst. TOF ¼ mole of product/mole of catalyst x time. Conversion was determined by GC. Reaction Conditions: solvent (dichloromethane), p-nitrophenol (10.85 103 mol), catalyst (5.43 106 mol), oxidant (2.71 103 mol). a ¼ Selectivity of benzoquinone Reaction time ¼ 3 h.
TON
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E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
Table 3 Catalytic activities of phthalocyanines towards the photooxidation of different organic compounds in some previously reported catalyst. Catalyst
Substrate
Rxn Time (h)
Rxn Temp. (oC)
Oxidant
Conv. (%)
Ref.
ZnTsPca FePcb CoTNPcc CoPcd Metal free Pcf CuPcg CoPcı ZnPcı
Methyl orange-Orange G Ethyl benzene Malachite green 2-mercaptoethanol Süflide ion 4-nitrophenol 4-chlorophenol
10min 9h 30 min 2 1 5 3
nr rt nr rt rt 27 rt
O2 O2 e e O2 e O2
nr >99 99.2 nre 70 nrh 99.99 97.05
[49] [50] [51] [52] [53] [54] [55]
ZnTs-CoFerritea ¼ 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II). FePc-POFb ¼ four-branched tetra-amine FePc-porous organic framework. CoTNPc/SnIn4S8 c ¼ Tetranitrocobalt phthalocyanine/ternary chalcogenide. CoPcd ¼ Cobaltphthalocyanine/C60. Metal free Pcf ¼ Metal free phthalocyanine/TiO2. CuPcg ¼ Copper phthalocyanine/TiO2. CoPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato cobalt(II)/TiO2. ZnPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato zinc(II)/TiO2. nr ¼ not reported. nre ¼ Turnover number is given as 8.4. nrh ¼ Quantum yield is given as 1.9.
Fig. 6. Mechanism of p-nitrophenol degradation.
4. Conclusion
Acknowledgement
In conclusion, axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine 3 was designed and synthesized. SiPc 3 is highly soluble in most of the organic solvents and are investigated aggregation behavior in different common organic solvents. The photocatalytic activity of SiPc 3 was examined for p-nitrophenol degradation using photochemical reactor. The results indicated that the catalyst showed good activity for p-nitrophenol degradation to the corresponding hydroquinone as major product in 1 h at 25 C. Cyclic voltammetry was used in order to investigate the electrochemical properties of SiPc 3. Electrochemical responses of SiPc 3 support the proposed structure of the complex. Voltammetric studies suggested that SiPc 3 display reversible/quasireversible/ irreversible redox processes, which are the main requirement for the technological usage of this compound.
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