Mehmet Salih AĞIRTAŞ, Ümit YILDIKO, Derya GÜNGÖRDÜ SOLĞUN, Abdullah ÖZKARTAL

Design of novel substituted phthalocyanines; synthesis and fluorescence, DFT, photovoltaic properties

The 4-(2-[3,4-dimethoxyphenoxy] phenoxy) phthalonitrile was synthesized as the starting material of new syntheses. Zinc, copper, and cobalt phthalocyanines were achieved by reaction of starting compound with $Zn(CH_3 COO)_2, CuCl_2, and CoCl_2$ metal salts. Basic spectroscopic methods such as nuclear magnetic resonance electronic absorption, mass and infrared spectrometry were used in the structural characterization of the compounds. Absorption, excitation, and emission measurements of the fluorescence zinc phthalocyanine compound were also investigated in THF. Then, structural, energy, and electronic properties for synthesized metallophthalocyanines were determined by quantum chemical calculations, including the DFT method. The bandgap of HOMO and LUMO was determined to be chemically active. Global reactivity (I, A, η, s, μ, χ, ω) and nonlinear properties were studied. In addition, molecular electrostatic potential (MEP) maps were drawn to identify potential reactive regions of metallophthalocyanine (M-Pc) compounds. Photovoltaic performances of phthalocyanine compounds for dye sensitive solar cells were investigated. The solar conversion efficiency of DSSC based on copper, zinc, and cobalt phthalocyanine compounds was 1.69%, 1.35%, and 1.54%, respectively. The compounds have good solubility and show nonlinear optical properties. Zinc phthalocyanine gave fluorescence emission.

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1. Braika M, Dridia C, Ali MB, Ali A, Abbas MN et al. Investigation of structural, optical and electrical properties of a new cobalt phthalocyanine thin films with potential applications in perchlorate sensor. Synthetic Metals 2015; 209: 135-142.
2. Urbani M, Ragoussi ME, Nazeeruddin MK, Torres T. Phthalocyanines for dye-sensitized solar cells. Coordination Chemistry Reviews 2019; 381: 1-64.
3. Sfyri G, Vamshikrishna N, Kumar CV, Giribabu L, Lianos P. Synthesis and characterization of tetratriphenylamine Zn phthalocyanine as hole transporting material for perovskite solar cells. Solar Energy 2016; 140: 60-65.
4. Ali HEA, Altındal A, Altun S, Odabas Z. Highly efficient dye-sensitized solar cells based on metal-free and copper(II) phthalocyanine bearing 2-phenylphenoxy moiety. Dyes and Pigments 2016; 124: 180-187.
5. Savelyev MS, Gerasimenko AY, Podgaetskii VM, Tereshchenko SA, Selishchev SV et al. Conjugates of thermally stable phthalocyanine J-type dimers with single-walled carbon nanotubes for enhanced optical limiting applications. Optics & Laser Technology 2019; 117: 272- 279.
6. Basova TV, Mikhaleva NS, Hassan AK, Kiselev VG. Thin films of fluorinated 3d-metal phthalocyanines as chemical sensors of ammonia: an optical spectroscopy study. Sensors and Actuators B: Chemical 2016; 227: 634-642.
7. Kong S, Wang X, Bai L, Song Y, Meng F. Multi-arm ionic liquid crystals formed by pyridine-mesophase and copper phthalocyanine. Journal of Molecular Liquids 2019; 288: 111012.
8. Lin KC, Doane T, Wang L, Li P, Pejic S et al. Laser spectroscopic assessment of a phthalocyanine-sensitized solar cell as a function of dye loading. Solar Energy Materials and Solar Cells 2014; 126: 155-162.
9. Yin S, Chen Y, Hu Q, Li M, Ding Y et al. In-situ preparation of iron(II) phthalocyanine modified bismuth oxybromide with enhanced visible-light photocatalytic activity and mechanism insight. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2019; 575: 336-345.
10. Kheirjou S, Kheirjou R, Rezayan AH, Shakourian-Fard M, Mahmoudi Hashemi M. Selective aqueous oxidation of alcohols catalyzed by copper (II) phthalocyanine nanoparticles. Comptes Rendus Chimie 2016; 19: 314-319.
11. Ağırtaş MS. Synthesis and characterization of novel symmetrical phthalocyanines substituted with four benzo [d] [1,3] dioxol-5-ylmethoxy groups. Inorganica Chimica Acta 2007; 360: 2499-2502.
12. Hagen JP, Becerra I, Drakulich D, Dillon RO. Effect of antenna porphyrins and phthalocyanines on the photochromism of benzospiropyrans in poly(methyl methacrylate) films. Thin Solid Films 2001; 398-399: 104-109.
13. Afshari R, Ghasemi V, Shaabani S, Shaabani A, Aladaghlo Z et al. Post‐modification of phthalocyanines via isocyanide-based multicomponent reactions: Highly dispersible peptidomimetic metallophthalocyanines as potent photosensitizers. Dyes and Pigments 2019; 166: 49-59.
14. Güzel E, Atsay A, Nalbantoglu S, Şaki N, Dogan AL et al. Synthesis, characterization and photodynamic activity of a new amphiphilic zinc phthalocyanine. Dyes and Pigments 2013; 97: 238-243.
15. Ağırtaş MS. Highly soluble phthalocyanines with hexadeca tert-butyl substituents. Dyes and Pigments 2008; 79: 247-251.
16. Roguin LP, Chiarante N, García Vior MC, Marino J. Zinc(II) phthalocyanines as photosensitizers for antitumor photodynamic therapy. The International Journal of Biochemistry & Cell Biology 2019; 114: 105575.
17. Sodeifian G, Saadati Ardestani N, Sajadian SA. Solubility measurement of a pigment (Phthalocyanine green) in supercritical carbon dioxide: Experimental correlations and thermodynamic modeling. Fluid Phase Equilibria 2019; 494: 61-73.
18. Sen P, Yasa Atmaca G, Erdogmus A, Demir Kanmazalp S, Dege N et al. Peripherally tetra-benzimidazole units-substituted zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysical and photochemical properties. Journal of Luminescence 2018; 194: 123-130.
19. Demirol M, Sirka L, Çalışkan E, Biryan F, Koran K et al. Synthesis and photodiode properties of chalcone substituted metallophthalocyanine. Journal of Molecular Structure 2020; 1219: 128571.
20. Cabir B, Ağırtaş MS, Duygulu E, Yuksel F. Synthesis of some metallophthalocyanines bearing 9-phenyl-9Hfluoren-9-yl) oxy functional groups and investigation of their photophysical properties. Journal of Molecular Structure 2017; 1142: 194-199.
21. Khezami K, Harmandar K, Bağda E, Bağda E, Şahin G. The new water soluble zinc(II) phthalocyanines substituted with morpholine groups- synthesis and optical properties. Journal of Photochemistry & Photobiology A: Chemistry 2020; 401: 112736.
22. Frisch GWTMJ, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR et al. Gaussian 09, Revision A.02. Wallingford, CT, USA: Gaussian, Inc., 2016.
23. Ağırtaş MS, Güven ME, Gümüş S, Özdemir S, Dündar A. Metallo and metal free phthalocyanines bearing (4-(1(4-phenoxyphenyl)-1- phenylethyl) phenol substituents: Synthesis, characterization, aggregation behavior, electronic, antioxidant and antibacterial properties. Synthetic Metals 2014; 195: 177-184.
24. Prabhaharan M, Prabakaran AR, Gunasekaran S, Srinivasan S. DFT studies on vibrational spectra, HOMO–LUMO, NBO and thermodynamic function analysis of cyanuric fluoride. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015; 136: 494-503.
25. Attia MS, Ali K, El-Kemary M, Darwishd WM. Phthalocyanine-doped polystyrene fluorescent nanocomposite as a highly selective biosensor for quantitative determination of cancer antigen 125. Talanta 2019; 201: 185-193.
26. Wong RCH, Lo PC, Ng DKP. Stimuli responsive phthalocyanine-based fluorescent probes and photosensitizers. Coordination Chemistry Reviews 2019; 379: 30-46.
27. McRae EKS, Nevonen DE, McKennaSA, Nemykin VN. Binding and photodynamic action of the cationic zinc phthalocyanines with different types of DNA toward understanding of their cancer therapy activity. Journal of Inorganic Biochemistry 2019; 199: 110793.
28. Liu TM, Conde J, Lipinski T, Bednarkiewicz A, Huang CC. Smart NIR linear and nonlinear optical nanomaterials for cancer theranostics: prospects in photomedicine. Progress in Materials Science 2017; 88: 89-135.
29. Mantareva V, Angelov I, Kussovski V, Dimitrov R, Lapok L et al. Photodynamic efficacy of water-soluble Si(IV) and Ge(IV) phthalocyanines towards Candida albicans planktonic and biofilm cultures. European Journal of Medicinal Chemistry 2011; 46: 4430-4440.
30. Lapshina M, Ustyugov A, Baulin V, Terentiev A, Tsivadze A et al. Crown- and phosphoryl-containing metal phthalocyanines in solutions of poly(N-vinylpyrrolidone): Supramolecular organization, accumulation in cells, photo-induced generation of reactive oxygen species, and cytotoxicity. Journal of Photochemistry and Photobiology B: Biology 2020; 202: 111722.
31. Liu S, Liu C, Luan X, Yao R, Feng Y. Facile fabrication of dual emissive nanospheres via the self-assembling of CdSe@CdS and zinc phthalocyanine and their application for silver ion detection. Chemical Physics Letters 2017; 684: 321-327.
32. Singh S, Aggarwal A, Bhupathiraju NVSDK, Jovanovic IR, Landress M et al. Comparing a thioglycosylated chlorin and phthalocyanine as potentialtheranostic agents. Bioorganic & Medicinal Chemistry 2020; 28:115259.
33. Komori T, Amao Y. Dye-sensitized solar cell with the near-infrared sensitization of aluminum phthalocyanine. Journal of Porphyrins and Phthalocyanines 2003; 07: 131-136.
34. Ağırtaş MS, Cabir B, Özdemir S. Novel metal (II) phthalocyanines with 3,4,5-trimethoxybenzyloxy-substituents: synthesis, characterization, aggregation behaviour and antioxidant activity. Dyes and Pigments 2013; 96: 152-157.
35. Siddiqui N, Javed S. Quantum computational, spectroscopic investigations on ampyra (4-aminopyridine) by DFT/TD-DFT with different solvents and molecular docking studies. Journal of Molecular Structure 2021; 1224: 129021.
36. Shehab OR, Mansour AM. Exploring electronic structure, and substituent effect of some biologically active benzimidazole derivatives: experimental insights and DFT calculations. Journal of Molecular Structure 2021; 1223: 128996.
37. Kanagathara N, MaryAnjalin F, Ragavendran V, Dhanasekaran D, Usha R et al. Experimental and theoretical (DFT) investigation of crystallographic, spectroscopic and Hirshfeld surface analysis of anilinium arsenate. Journal of Molecular Structure 2021; 1223: 128965.
38. Krishna Kumar V, Sangeetha R, Barathi D, Mathammal R, Jayamani N. Vibrational assignment of the spectral data, molecular dipole moment, polarizability, first hyperpolarizability, HOMO–LUMO and thermodynamic properties of 5-nitoindan using DFT quantum chemical calculations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014; 118: 663-671.
39. Becker HGO. Jan Fleming, Frontier Orbitals and Organic Chemical Reactions, 1976 (book reviews). Advanced Synthesis & Catalysis 1978; 320 (5): 879-880.
40. Zhong L, Li Y, Bin H, Zhang M, Huang H et al. Ternary polymer solar cells based-on two polymer donors with similar HOMO levels and an organic acceptor with absorption extending to 850 nm. Organic Electronics 2018; 62: 89-94.
41. Barim E, Akman F. Synthesis, characterization and spectroscopic investigation of N-(2-acetylbenzofuran-3-yl)acrylamide monomer: molecular structure, HOMO–LUMO study, TD-DFT and MEP analysis. Journal of Molecular Structure 2019; 1195: 506-513.
42. Ogunsipe A, Maree D, Nyokong T. Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives. Journal of Molecular Structure 2003; 650: 131-140.
43. Mumit MA, Pal TK, Alam MA, Islam MAAAA, Paul S et al. DFT studies on vibrational and electronic spectra, HOMO–LUMO, MEP, HOMA, NBO and molecular docking analysis of benzyl-3-N-(2,4,5-trimethoxyphenylmethylene)hydrazinecarbodithioate. Journal of Molecular Structure 2020; 1220: 128715.
44. Grobosch M, Schmidt C, Kraus R, Knupfer M. Electronic properties of transition metal phthalocyanines: the impact of the central metal atom (d5–d10). Organic Electronics 2010; 11: 1483-1488.
45. Güngördü Solğun D, Horoz S, Ağırtaş MS. Synthesis of novel tetra (4-tritylphenoxy) substituted metallophthalocyanines and investigation of their aggregation, photovoltaic, solar cell properties. Inorganic And Nano-Metal Chemistry 2018; 48 (10): 508-514.
46. Ağırtaş MS, Güngördü Solğun D, Özdemir S, İzgi MS. Synthesis of tetra 3,4-dimethoxyphenethoxy peripheral substituted metallophthalocyanines and investigation of some properties. ChemistrySelect 2018; 3: 3523-3528.
47. Huang H, Cao Z, Li X, Zhang L, Liu X et al. Synthesis and photovoltaic properties of two new unsymmetricalzinc-phthalocyanine dyes. Synthetic Metals 2012; 162: 2316-2321.
48. Karaoğlan GK, Gümrükçü G, Gördük S, Can N, Gül A. Novel homoleptic, dimeric zinc(II) phthalocyanines as gate dielectric for OFET device. Synthetic Metals 2017; 230: 7-11.
49. Mathew S, Yella A, Gao P, Humphry-Baker R, Curchod BFE et al. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nature Chemistry 2014; 6: 242-247.
50. Bignozzi CA, Argazzi R, Boaretto R, Busatto E, Carli S et al. The role of transition metal complexes in dye sensitized solar devices.Coordination Chemistry Reviews 2013; 257: 1472-1492.