Abstract
In the present work, 4-(4′-dodecyloxycarbonyl) phenoxy phthalonitrile was synthesized and then this phthalonitrile derivative was cyclotetramerized in dodecanol resulting a new metal-free phthalocyanine. The optical properties of this phthalocyanine were investigated. Novel metal-free phthalocyanine thin films were deposited on indium tin oxide-coated glass substrates by spinning method. Surface and microstructural properties of the films were characterized by atomic force microscopy and scanning electron microscopy. Both the transmittance and reflectance spectra of the deposited films were recorded using an NKD analyser. The optical band gap energy, the thickness of thin films, refractive index (n) and extinction coefficient (k) were calculated as 2.7 eV, 300 nm, 1.47 and 0.02, respectively.
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References
Assour JM, Harrison SE (1965) On the optical absorptions of phthalocyanines. J Am Chem Soc 87:651–652. doi:10.1021/ja01081a044
Azim-Araghi ME, Baedi J, Moazzami L (2012) Electrical and optical properties of an organic semiconductor metal-free phthalocyanine (C32H18N8). Eur Phys J Appl Phys 58:30201. doi:10.1051/epjap/2012120062
Bao D, Yang H, Zhan L, Yao X (1998) Structure and optical properties of SrTiO3 thin films prepared by a sol–gel technique. Phys Status Solidi A 169:227–233. doi:10.1002/(SICI)1521-396X(199810)169:2<227:AID-PSSA227>3.0.CO;2-R
Bayda M, Dumoulin F, Hug GL, Koput J, Gorniak R, Wojcik A (2017) Fluorescent H-aggregates of an asymmetrically substituted mono-amino Zn(II) phthalocyanine. Dalton Trans 46:1914–1926. doi:10.1039/C6DT02651F
Bayliss SM, Heutz S, Rumbles G, Jones TS (1999) Thin film properties and surface morphology of metal-free phthalocyanine films grown by organic molecular beam deposition. Phys Chem Chem Phys 1:3673–3676. doi:10.1039/a904089g
Bhaskar S, Majumder SB, Jain M, Dobal PS, Katiyar RS (2001) Studies on the structural, microstructural and optical properties of sol–gel derived lead lanthanum titanate thin films. Mat Sci Eng B 87:178–190. doi:10.1016/S0921-5107(01)00739-5
Born M, Wolf E (1999) Principles of optics, 7th edn. Cambridge University Press, Cambridge
Cocchi C, Prezzi D, Ruini A, Molinari E, Rozzi CA (2014) Ab initio simulation of optical limiting: the case of metal-free phthalocyanine. Phys Rev Lett 112:198303. doi:10.1103/PhysRevLett.112.198303
Cook MJ (1999) Phthalocyanine thin films. Pure Appl Chem 71:2145–2151
Demirkapı D, Şirin A, Turanlı-Yıldız B, Çakar ZP, Sesalan BŞ (2014) The synthesis of new silicon phthalocyanines and analysis of their photochemical and biological properties. Synth Met 187:152–159. doi:10.1016/j.synthmet.2013.11.001
Gürek AG, Bekaroğlu Ö (1997) Tetrathia macrocycle-bridged dimeric with hexakis (alkylthio) substituents and network polymer phthalocyanines. J Porphyr Phthalocyanines 1:227–237. doi:10.1002/(SICI)1099-1409(199707)1:3<227:AID-JPP17>3.0.CO;2-K
Hofman JW, Zeeland FV, Turker S, Talsma H, Lambrechts SAG, Sakharov DV, Hennink WE, Nostrum CFV (2007) Peripheral and axial substitution of phthalocyanines with Solketal Groups: synthesis and in vitro evaluation for photodynamic therapy. J Med Chem 50:1485–1494. doi:10.1021/jm061136w
Huang KJ, Hsiao YS, Huang JS, Chu CW, Chen P, Wang WT (2012) Controlling vertical alignment of phthalocyanine nanofibers on transparent graphene-coated ITO electrodes for organic field emitters. J Mater Chem 22:7837–7844. doi:10.1039/C2JM30383C
Khan SA, Zulfequar M, Husain M (2005) Optical band gap and optical constants in a-Se80Te20 − xPbx thin films. Curr Appl Phys 5:583–587. doi:10.1016/j.cap.2004.07.002
Kobayashi N, Ogata H, Nonaka N, Luk’yanets EA (2003) Effect of peripheral substitution on the electronic absorption and fluorescence spectra of metal-free and zinc phthalocyanines. Chemistry 9(20):5123–5134. doi:10.1002/chem.200304834
Kodolbas AO (2003) Empirical calibration of the optical gap in a-Si1 − xCx: H (x < 0.20) alloys. Mater Sci Eng B98:161–166. doi:10.1016/S0921-5107(03)00046-1
Kudrik EV, Smirnova AI, Maizlish VE, Tararykina TV, Shaposhnikov GP, Usol’tseva NV (2006) Copper 2,9(10),16(17),23(24)- and 1,8(11),15(18),22(25)-tetra-(4-carboxyphenoxy) phthalocyanines and their esters: the synthesis and liquid–crystalline properties. Russ Chem Bull 55:1028–1037. doi:10.1007/s11172-006-0372-2
Kurt Ö, Özçeşmeci İ, Sesalan BŞ, Burkut-Koçak M (2015) The synthesis and investigation of binding properties of a new water soluble hexadeca zinc(II) phthalocyanine with bovine serum albumin and DNA. New J Chem 39:5767–5775. doi:10.1039/c5nj00933b
Lucia EA, Marino CP, Verderame FD (1968) Absorption of phthalocyanines in thermoplastic media in the 0.5 to 0.8 μ region. J Mol Spectr 26(1):133–136. doi:10.1016/0022-2852(68)90150-1
Lyubimtsev A, Iqbal Z, Crucius G, Crucius S, Taraymovich ES, Ziegler T, Hanack M (2011) Aggregation behavior and UV–vis spectra of tetra- and octaglycosylated zinc phthalocyanines. J Porphyrins Phthalocyanines 15:39–46. doi:10.1142/S1088424611002891
McKeown NB (1998) Phthalocyanine materials. Cambridge University Press, Cambridge, UK
Miller JS (1990) Molecular materials. 2.C. Molecular electronics. Adv Mater 2:601–603
Naitoh Y, Matsumoto T, Sugiura K, Sakata Y, Kawai T (2001) Self-assembled stripe structure of zinc–phthalocyanine on graphite surfaces. Surf Sci 487:L534–L540. doi:10.1016/S0039-6028(01)01156-6
Narayanan Unni KN, Menon CS (2001) Electrical and optical studies on metal-free phthalocyanine thin films. J Mater Sci Lett 20:1207–1209. doi:10.1023/A:1010928817316
Nespurek S, Podlesak H, Hamann C (1994) Structure and photoelectrical behavior of vacuum-evaporated metal-free phthalocyanine films. Thin Solid Films 249:230–235. doi:10.1016/0040-6090(94)90767-6
Perrin DD, Armarego WLF, Perrin DR (1985) In: Purification of laboratory chemicals, 2nd edn. Pergamon Press, New York
Rajesh KR, Menon CS (2001) Optical studies of manganese phthalocyanine thin films. Mat Lett 51:266–269. doi:10.1016/S0167-577X(01)00302-0
Rieke PC, Linkous CL, Armstrong NR (1984) Chlorogallium phthalocyanine thin-film photoelectrochemistry. Effect of surface coverage and physical distribution of microcrystallites on the photoelectrochemical response. J Phys Chem 88:1351–1357. doi:10.1021/j150651a023
Sindu Lois J, Lehmann D, Friedrich M, Zahn DRT (2007) Study of dependence of molecular orientation and optical properties of zinc phthalocyanine grown under two different pressure conditions. J Appl Phys doi 10(1063/1):2403845
Sleven J, Görller-Walrand C, Binnemans K (2001) Synthesis, spectral and mesomorphic properties of octa-alkoxy substituted phthalocyanine ligands and lanthanide complexes. Mater Sci Eng 18:229–238. doi:10.1016/S0928-4931(01)00365-4
Tikhomirova TV, Maizlish VE, Shaposhnikov GP (2011) Phthalonitriles containing ester groups and copper phthalocyanines based on them. Russ J Gen Chem 81:768–772. doi:10.1134/S1070363211040268
Unni KNN, Menon CS (2000) Electrical and optical studies on nickel phthalocyanine thin films. Mater Lett 45:326–330. doi:10.1016/S0167-577X(00)00127-0
Uslan C, Sesalan BŞ (2012) Synthesis of novel DNA-interacting phthalocyanines. Dyes Pigments 94:127–135. doi:10.1016/j.dyepig.2011.12.003
Uslan C, Sesalan BŞ (2013) The synthesis, photochemical and biological properties of new silicon phthalocyanines. Inorg Chim Acta 394:353–362. doi:10.1016/j.ica.2012.08.004
Uslan C, Sesalan BŞ, Durmuş M (2012) Synthesis of new water soluble phthalocyanines and investigation of their photochemical, photophysical and biological properties. J Photoch Photobio A 235:56–64. doi:10.1016/j.jphotochem.2012.03.010
Uslan C, Oppelt KT, Reith LM, Sesalan BŞ, Knör G (2013) Characterization of a non-aggregating silicon(IV) phthalocyanine in aqueous solution: toward red-light-driven photocatalysis based on earth-abundant materials. Chem Commun 49:8108–8110. doi:10.1039/c3cc44674c
Van Dijken JG, Brett MJ (2012) Dry etching of copper phthalocyanine thin films: effects on morphology and surface stoichiometry. Molecules 17:10119–10130. doi:10.3390/molecules170910119
Verma D, Dash R, Katti KS, Schulz DL, Caruso AN (2008) Role of coordinated metal ions on the orientation of phthalocyanine based coatings. Spectrochim Acta Part A 70:1180–1186. doi:10.1016/j.saa.2007.10.050
Wicht G, Ferrini R, Schuettel S, Zuppiroli L (2010) Nanoporous films with low refractive index for large-surface broad-band anti-reflection coatings. Macromol Mater Eng 295:628–636. doi:10.1002/mame.201000045
Yakuphanoglu F, Durmuş M, Okutan M, Köysal O, Ahsen V (2006) The refractive index dispersion and the optical constants of liquid crystal metal-free and nickel(II) phthalocyanines. Phys B 373:262–266. doi:10.1016/j.physb.2005.11.153
Yakuphanoğlu F, Barim G, Erol I (2007) The effect of FeCl3 on the optical constants and optical band gap of MBZMA-co-MMA polymer thin films. Phys B 391:136–140. doi:10.1016/j.physb.2006.09.009
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This study was acknowledged by Istanbul Technical University project (BAP: 33851).
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Şirin, A., Zayim, E.Ö. & Sesalan, B.Ş. The optical properties of a novel metal-free phthalocyanine. Chem. Pap. 71, 2107–2115 (2017). https://doi.org/10.1007/s11696-017-0203-y
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DOI: https://doi.org/10.1007/s11696-017-0203-y