Novel lanthanide metallophthalocyanines bearing iodine group and their singlet oxygen generation ability

Abstract

In this study, five novel mono rare earth metallo phthalocyanine derivatives (1a-e) were synthesized by cyclotetramerization of 4-iodophthalonitrile and corresponding metal salts. These novel compounds were characterized by IR, elemental analyses, UV–vis, and MALDI-TOF spectral data. Moreover, the ability of singlet oxygen generation and aggregation behaviour of these phthaloyanines were investigated in dimethyl sulfoxide using UV-Vis spectroscopy. Gadolinium metallo phthalocyanine has the best singlet oxygen quantum yield and it can be a potential candidate for the photodynamic therapy (PDT) of cancer.

Keywords

• Phthalocyanine
• Iodine
• Lanthanide
• Singlet Oxygen

Thanks

Synthesis and measurements were performed at Gebze Technical University, and I want to thank Prof. Dr. Mahmut DURMUŞ.

References

1. 1. Hosseini H, Mahyari M, Bagheri A, Shaabani A. A novel bioelectrochemical sensing platform based on covalently attachment of cobalt phthalocyanine to graphene oxide. Biosensors and Bioelectronics. 2014 Feb;52:136–42.
2. 2. Fogel R, Mashazi P, Nyokong T, Limson J. Critical assessment of the Quartz Crystal Microbalance with Dissipation as an analytical tool for biosensor development and fundamental studies: Metallophthalocyanine–glucose oxidase biocomposite sensors. Biosensors and Bioelectronics. 2007 Aug;23(1):95–101.
3. 3. Basova T, Hassan A, Durmuſ M, Gürek AG, Ahsen V. Liquid crystalline metal phthalocyanines: Structural organization on the substrate surface. Coordination Chemistry Reviews. 2016 Mar;310:131–53.
4. 4. Urbani M, de la Torre G, Nazeeruddin MK, Torres T. Phthalocyanines and porphyrinoid analogues as hole- and electron-transporting materials for perovskite solar cells. Chem Soc Rev. 2019;48(10):2738–66.
5. 5. Güzel E. Dual-purpose zinc and silicon complexes of 1,2,3-triazole group substituted phthalocyanine photosensitizers: synthesis and evaluation of photophysical, singlet oxygen generation, electrochemical and photovoltaic properties. RSC Adv. 2019;9(19):10854–64.
6. 6. Singh S, Aggarwal A, Bhupathiraju NVSDK, Arianna G, Tiwari K, Drain CM. Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics. Chem Rev. 2015 Sep 23;115(18):10261–306.
7. 7. Jia X, Jia L. Nanoparticles Improve Biological Functions of Phthalocyanine Photosensitizers Used for Photodynamic Therapy. CDM. 2012 Sep 1;13(8):1119–22.
8. 8. Wong RCH, Lo PC, Ng DKP. Stimuli responsive phthalocyanine-based fluorescent probes and photosensitizers. Coordination Chemistry Reviews. 2019 Jan;379:30–46.

9. 9. Sorokin AB. Phthalocyanine Metal Complexes in Catalysis. Chem Rev. 2013 Oct 9;113(10):8152–91.
10. 10. Köksoy B, Durmuş M, Bulut M. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties. Journal of Luminescence. 2015 May;161:95–102.
11. 11. Ghazal B, Husain A, Ganesan A, Durmuş M, Zhang XF, Makhseed S. Exceptionally effective generation of singlet oxygen in aqueous media via iodinated zinc-phthalocyanine. Dyes and Pigments. 2019 May;164:296–304.
12. 12. Bıyıklıoğlu Z, Acar I. Peripheral and non-peripheral long-chain tetrasubstituted phthalocyanines: Synthesis, spectroscopic characterization and aggregation properties. Synthetic Metals. 2012 Aug;162(13–14):1156–63.
13. 13. Gao Z, Tao X, Cui Y, Satoh T, Kakuchi T, Duan Q. Synthesis of end-functionalized poly(N-isopropylacrylamide) with group of asymmetrical phthalocyanine via atom transfer radical polymerization and its photocatalytic oxidation of Rhodamine B. Polym Chem. 2011;2(11):2590.
14. 14. Bakboord JV, Cook MJ, Hamuryudan E. Non-uniformly substituted phthalocyanines and related compounds: alkylated tribenzo-imidazolo[4,5]- porphyrazines. J Porphyrins Phthalocyanines. 2000 Aug;04(05):510–7.
15. 15. George RD, Snow AW. Synthesis of 3-nitrophthalonitrile and tetra-α-substituted phthalocyanines. Journal of Heterocyclic Chemistry. 1995 Mar;32(2):495–8.
16. 16. Cook MJ, McMurdo J, Miles DA, Poynter RH, Simmons JM, Haslam SD, et al. Monolayer behaviour and Langmuir–Blodgett film properties of some amphiphilic phthalocyanines: factors influencing molecular organisation within the film assembly. J Mater Chem. 1994;4(8):1205–13.
17. 17. George RD, Snow AW, Shirk JS, Barger WR. The Alpha Substitution Effect on Phthalocyanine Aggregation. J Porphyrins Phthalocyanines. 1998 Jan;02(01):1–7.
18. 18. Esenpınar AA, Durmuş M, Bulut M. Photophysical, photochemical and BSA binding/BQ quenching properties of quaternizable coumarin containing water soluble zinc phthalocyanine complexes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2011 Aug;79(3):608–17.
19. 19. Taştemel A, Karaca BY, Durmuş M, Bulut M. Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups. Journal of Luminescence. 2015 Dec;168:163–71.
20. 20. Güzel E, Günsel A, Bilgiçli AT, Atmaca GY, Erdoğmuş A, Yarasir MN. Synthesis and photophysicochemical properties of novel thiadiazole-substituted zinc (II), gallium (III) and silicon (IV) phthalocyanines for photodynamic therapy. Inorganica Chimica Acta. 2017 Oct;467:169–76.
21. 21. 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: Chemistry. 2009 Jul;206(1):18–26.
22. 22. Ceyhan T, Altındal A, Özkaya AR, Erbil MK, Bekaroğlu Ö. Synthesis, characterization, and electrochemical, electrical and gas sensing properties of a novel tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine. Polyhedron. 2007 Jan;26(1):73–84.
23. 23. Pushkarev VE, Shulishov EV, Tomilov YV, Tomilova LG. The development of highly selective approaches to sandwich-type heteroleptic double- and triple-decker lutetium(III) and europium(III) phthalocyanine complexes. Tetrahedron Letters. 2007 Jul;48(30):5269–73.
24. 24. Pushkarev VE, Tolbin AYu, Borisova NE, Trashin SA, Tomilova LG. A 3 B‐Type Phthalocyanine‐Based Homoleptic Lanthanide(III) Double‐Decker π‐Radical Complexes Bearing Functional Hydroxy Groups: Synthetic Approach, Spectral Properties and Electrochemical Study. Eur J Inorg Chem. 2010 Nov;2010(33):5254–62.
25. 25. Ren B, Sheng N, Gu B, Wan Y, Rui G, Lv C, et al. Changing optical nonlinearities of homoleptic bis(phthalocyaninato) rare earth praseodymium double-decker complexes by the redox reaction. Dyes and Pigments. 2017 Apr;139:788–94.
26. 26. Nekelson F, Monobe H, Shiro M, Shimizu Y. Liquid crystalline and charge transport properties of double-decker cerium phthalocyanine complexes. J Mater Chem. 2007;17(25):2607.
27. 27. Ke XS, Ning Y, Tang J, Hu JY, Yin HY, Wang GX, et al. Gadolinium(III) Porpholactones as Efficient and Robust Singlet Oxygen Photosensitizers. Chem Eur J. 2016 Jul 4;22(28):9676–86.
28. 28. Galindev O, Dalantai M, Ahn WS, Shim YK. Gadolinium complexes of chlorin derivatives applicable for MRI contrast agents and PDT. J Porphyrins Phthalocyanines. 2009 Jul;13(07):823–31.