Peripherally 1,2-dinaphthyl ethanediol substituted phthalocyanine complexes: synthesis, characterization, aggregation, and application in benzyl alcohol oxidation at room temperature
Peripherally 1,2-dinaphthyl ethanediol substituted phthalocyanine complexes: synthesis, characterization, aggregation, and application in benzyl alcohol oxidation at room temperature
In this study, the synthesis of a novel 1,2-dinaphthyl ethanediol substituted phthalonitrile (2) together withtetra-substituted zinc(II) phthalocyanine (Pc) (3) and cobalt(II) Pc (4) bearing 1,2-dinaphthyl ethanediol at peripheral positions was described. The aggregation behaviors of metallophthalocyanines 3 and 4 in solution were investigated by carrying out Beer–Lambert experiments at different concentrations. In addition, the catalytic activity of new cobalt(II) Pc 4 was investigated for benzyl alcohol oxidation. Benzyl alcohol was converted to benzaldehyde using cobalt(II) Pc 4 as a catalyst by a conversion of 99% with selectivity of 100% at room temperature in 1 h. Several spectroscopic techniques such as FT-IR, UV-Vis, 1 H and 13 C NMR, and MALDI-TOF MS were used for the characterization of the newly synthesized compounds.
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- 1. Leznoff DCC, Lever ABP. Phthalocyanines: Properties and Applications, Vols. 1-4. Weinheim, Germany: WileyVCH, 1998.
- 2. Gök Y, Gök HZ. Synthesis, characterization and spectral properties of novel zinc phthalocyanines derived from C2
symmetric diol. Journal of Molecular Structure 2014; 1067: 169-176. doi: 10.1016/j.molstruc.2014.03.037
- 3. Bilgin A, Mendi A, Yıldız U. Novel phthalocyanine polymers with very flexible pentathiatetraethylene units.
Polymer 2006; 47 (26): 8462-8473. doi: 10.1016/j.polymer.2006.10.018
- 4. Bilgin A, Yağcı Ç, Mendi A, Yıldız U. Novel network polymeric phthalocyanines: synthesis and characterization.
Macromolecular Chemistry and Physics 2005; 206 (22): 2257-2268. doi: 10.1002/macp.200500341
- 5. Zalomaeva OV, Ivanchikova ID, Kholdeeva OA, Sorokin AB. Kinetics and mechanism of the oxidation of alkyl
substituted phenols and naphthols with tBuOOH in the presence of supported iron phthalocyanine. New Journal
of Chemistry 2009; 33: 1031-1037. doi: 10.1039/B821534K
- 6. Gök HZ, Gök Y. A novel polymeric phthalocyanines bridged flexible 1,5-pentanedithiol unit for metal ions
extraction: synthesis, characterization and evaluation, Journal of Inclusion Phenomena and Macrocyclic Chemistry
2019; 94: 55-63. doi: 10.1007/s10847-019-00901-1
- 7. Cho KT, Trukhina O, Roldán-Carmona C, Ince M, Gratia P et al. Molecularly engineered phthalocyanines as holetransporting materials in perovskite solar cells reaching power conversion efficiency of 17.5%. Advanced Energy
Materials 2017; 7: 1601733. doi: 10.1002/aenm.201601733
- 8. Sorokin AB. Phthalocyanine metal complexes in catalysis. Chemical Reviews 2013; 113: 8152-8191. doi: 10.1021/
cr4000072
- 9. Aktaş A, Acar İ, Saka ET, Bıyıklıoğlu Z. Synthesis of polyfluoro substituted Co(II), Fe(II) phthalocyanines and
their usage as catalysts for aerobic oxidation of benzyl alcohol. Journal of Organometallic Chemistry 2016; 815-816:
1-7. doi: 10.1016/j.jorganchem.2016.04.025
- 10. Matlou GG, Kobayashi N, Kimura M, Nyokong T. Physicochemical properties of water soluble unsymmetrical
phthalocyaninefolic acid conjugates. Dyes and Pigments 2018; 149: 393-398. doi: 10.1016/j.dyepig.2017.10.030
- 11. Winckel E, David B, Moreno MS, Gonzalez-Delgado JA, Escosura A et al. Octacationic and axially di-substituted
silicon (IV) phthalocyanines for photodynamic inactivation of bacteria. Dyes and Pigments 2017; 145: 239-245.
doi: 10.1016/j.dyepig.2017.06.004
- 12. Günsel A, Beylik S, Bilgiçli AT, Atmaca GY, Erdoğmuş A. Peripherally and non-peripherally tetra-HBME (4-
hydroxybenzyl methyl ether) substituted metal-free and zinc(II) phthalocyanines: synthesis, characterization, and
investigation of photophysical and photochemical properties. Inorganica Chimica Acta 2018; 477: 199-205. doi:
10.1016/j.ica.2018.03.026
- 13. Gök HZ. Synthesis of metal-free and metallophthalocyanines containing 18- and 21-membered macrocycles with
mixed donor atoms and their metal-ion binding properties. Turkish Journal of Chemistry 2015; 39: 750-763. doi:
10.3906/kim-1501-54
- 14. Gök HZ, Kantekin H, Gök Y, Herman G. The synthesis and characterization of new metal-free and metallophthalocyanines containing four 27-membered diazaheptathia macrocycles. Dyes and Pigments 2007; 75: 606-611.
doi: 10.1016/j.dyepig.2006.07.008
- 15. Brewis M, Clarkson GJ, Humberstone P, Makhseed S, McKeown NB. The synthesis of some phthalocyanines and
napthalocyanines derived from sterically hindered phenols. Chemistry European Journal 1998; 4 (9): 1633-1640.
doi: 10.1002/(SICI)1521-3765(19980904)4:9<1633::AID-CHEM1633>3.0.CO;2-O
- 16. Gök HZ, Kantekin H, Gök Y, Herman G. The synthesis and characterization of novel metal-free and metallophthalocyanines bearing four 27-membered dioxadiazapentathia macrocycles. Dyes and Pigments 2007; 75: 699-705.
doi: 10.1016/j.dyepig.2006.05.002
- 17. Tillo A, Stolarska M, Kryjewski M, Popenda L, Sobotta L et al. Phthalocyanines with bulky substituents at
non-peripheral positions: synthesis and physico-chemical properties. Dyes and Pigments 2016; 127: 110-115. doi:
10.1016/j.dyepig.2015.12.017
- 18. Gök Y, Gök HZ, Yılmaz MK, Farsak M, Karayiğit IU. Novel peripherally and non-peripherally hydrobenzoin
substituted optically active phthalocyanines: synthesis, characterization, aggregation, electrochemical properties
and catalytic applications. Polyhedron 2018; 153: 128-138. doi: 10.1016/j.poly.2018.06.053
- 19. Rosini C, Scamuzzi S, Uccello-Barretta G, Salvadori P. Synthesis and stereochemical characterization of some optically active 1,2-dinaphthylethane-1,2-diol. Journal of Organic Chemistry 1994; 59: 7395-7400. doi: 10.1021/jo00103a035
- 20. Young JG, Onyebuagu W. Synthesis and characterization of di-disubstituted phthalocyanines. Journal of Organic
Chemistry 1990; 55: 2155-2159. doi: 10.1021/jo00294a03
- 21. Perrin DD, Armarego WFL. Purification of Laboratory Chemicals. 2nd ed. Oxford, UK: Pergamon, 1989.
- 22. Sen SP, Yildiz SZ. The investigation of oxidative bleaching performance of peripherally Schiff base substituted trinuclear cobalt-phthalocyanine complexes. Inorganica Chimica Acta 2017; 462: 30-39. doi: 10.1016/j.ica.2017.02.030
- 23. Takahashi K, Kawashima M, Tomita Y, Itoh M. Synthesis and spectral and electrochemical properties of 2,3,9,10,
16,17,23,24-octabutylthiophthalocyaninatozinc(II). Inorganica Chimica Acta 1995; 232: 69-73. doi: 10.1016/0020-
1693(94)04385-9
- 24. Tian M, Wada T, Sasabe H. Syntheses of new unsymmetrically dodecakis(trifluoroethoxy)-substituted metallophthalocyanines by a palladium-catalayzed cross-coupling reaction. Journal of Heterocyclic Chemistry 2000; 37: 1193-1202. doi: 10.1002/jhet.5570370528
- 25. Moeno S, Nyokong T. Solvent and central metal effects on the photophysical and photochemical properties of
peripherally tetra mercaptopyridine substituted metallophthalocyanines. Journal of Photochemistry and Photobiology A 2009; 203: 204-210. doi: 10.1016/j.jphotochem.2009.01.021
- 26. Ogunbayo T, Nyokong T. Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalocyanines. Polyhedron 2009; 28: 2710-2718. doi: 10.1016/j.poly.2009.05.026
- 27. Engelkamp H, Nolte RJM. Molecular materials based on crown ether functionalized phthalocyanines, Journal of
Porphyrins and Phthalocyanines. 2000; 4: 454-459. doi: 10.1002/1099-1409(200008)4:5<454::AID-JPP261>3.0.CO;
2-D
- 28. Yanık H, Aydın D, Durmuş M, Ahsen V. Peripheral and non-peripheral tetrasubstituted aluminium, gallium and
indium phthalocyanines: synthesis, photophysics and photochemistry. Journal of Photochemistry and Photobiology
A 2009; 206: 18-26. doi: 10.1016/j.jphotochem.2009.05.005
- 29. Kurt Ö, Özçeşmeci İ, Koca A, Gül A, Koçak MB. Synthesis, photophysical and electrochemical properties of
novel hexadeca-substituted phthalocyanines bearing naphthoxy groups. Dyes and Pigments 2017; 137: 236-243.
doi: 10.1016/j.dyepig.2016.10.014
- 30. Çakır V, Saka ET, Bıyıklıoglu Z, Kantekin H. Highly selective oxidation of benzyl alcohol catalyzed by new
peripherally tetra-substituted Fe(II) and Co(II) phthalocyanines. Synthetic Metals 2014; 197: 233-239. doi: 10.1016/
j.synthmet.2014.09.022
- 31. Saka ET, Bıyıklıoglu Z, Kantekin H, Kani I. Synthesis, characterization and catalytic activity of peripherally
tetra-substituted Co (II) phthalocyanines for cyclohexene oxidation. Applied Organometallic Chemistry 2013; 27:
59-67. doi: 10.1002/aoc.2939
- 32. Acar I, Bayrak R, Saka ET, Biyiklioglu Z, Kantekin H. Novel metal-free, metallophthalocyanines and their
quaternized derivatives: synthesis, spectroscopic characterization and catalytic activity of cobalt phthalocyanine
in 4-nitrophenol oxidation. Polyhedron 2013; 50: 345-353. doi: 10.1016/j.poly.2012.11.032
- 33. Saka ET, Acar I, Biyiklioglu Z, Kantekin H. Synthesis and characterization of peripheral and non-peripheral
substituted Co (II) phthalocyanines and their catalytic activity in styrene oxidation. Synthetic Metals 2013; 169:
12-17. doi: 10.1016/j.synthmet.2013.02.029
- 34. Gökce S, Saka ET, Biyıklioglu Z, Kantekin H. Synthesis, characterization of metal-free, metallophthalocyanines
and catalytic activity of cobalt phthalocyanine in cyclohexene oxidation. Synthetic Materials 2013; 176: 108-115.
doi: 10.1016/j.synthmet.2013.05.028
- 35. Aktas S, Saka ET, Biyıklioglu Z, Acar I, Kantekin H. Investigation of catalytic activity of new Co (II) phthalocyanine complexes in cyclohexene oxidation using different type of oxidants. Journal of Organometallic Chemistry
2013; 745-746: 18-24. doi: 10.1016/j.jorganchem.2013.07.013
- 36. Saka ET, Biyiklioglu Z. Co(II) and Fe(II) phthalocyanines: synthesis, characterization and catalytic activity on
cyclohexene oxidation with different oxygen source. Journal of Organometallic Chemistry 2013; 745-746: 50-56.
doi: 10.1016/j.jorganchem.2013.07.018
- 37. Özer M, Yılmaz F, Erer H, Kani İ, Bekaroğlu Ö. Synthesis, characterization and catalytic activity of novel
Co(II) and Pd(II)-perfluoroalkylphthalocyanine in fluorous biphasic system; benzyl alcohol oxidation. Applied
Organometallic Chemistry 2009; 23: 55-61. doi: 10.1002/aoc.1471
- 38. Kamiloğlu AA, Acar İ, Biyiklioğlu Z, Saka ET. Peripherally tetra-{2-(2,3,5,6-tetrafluorophenoxy)ethoxy} substituted
cobalt(II), iron(II) metallophthalocyanines: synthesis and their electrochemical, catalytic activity studies.
Journal of Organometallic Chemistry 2017; 828: 59-67. doi: 10.1016/j.jorganchem.2016.11.022
- 39. Kasuga K, Tsuboi K, Handa M, Sugimori T, Sogabe K. Oxygen-oxygenation of cyclohexene catalyzed by manganese(III), iron(III) and cobalt(II) complexes of tetra-tert-butylphthalocyanine in the presence of iso-butyraldehyde. Inorganic Chemistry Communications 1999; 2: 507-509. doi: 10.1016/S1387-7003(99)00135-5