Novel BODIPY-bridged cyclotriphosphazenes

Three new 2-component unsubstituted (4P), diiodo- (5P), and dibromo- (6P) distyryl-BODIPY-bridged cyclotriphosphazene dimers were designed and synthesized. The newly synthesized BODIPY-cyclotriphosphazene systemswere characterized by 1 H, 13 C, and 31P NMR spectroscopy. The photophysical properties of the distryl-BODIPYs(4–6) and BODIPY-cyclotriphosphazene dyads (4P–6P) were studied by UV-Vis absorption and fluorescence emissionspectroscopy. In these derivatives, the bino-type cyclotriphosphazene derivative bearing unsubstituted BODIPY unit 4P exhibited high fluorescence and no singlet oxygen generation due to the lack of spin converter. The attachment of heavyatoms (iodine and bromine) enabled the production of singlet oxygen. The bino-type BODIPY-cyclotriphosphazenes (5Pand 6P) were also used as triplet photosensitizers in the photooxidation of 1,3-diphenylisobenzofuran to endoperoxidevia generation of the singlet oxygen in dichloromethane. The singlet oxygen production of these compounds was alsoinvestigated via a direct method and produced a singlet oxygen phosphorescence peak at 1270 nm.

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1. Allen CW. Regiochemical and stereochemical control in substitution-reactions of cyclophosphazenes. Chemical Reviews 1991; 91 (2): 119-135. doi: 10.1021/cr00002a002
2. Ozturk E, Okumus A, Kilic Z, Kilic A, Kayalak H et al. Phosphorus-nitrogen compounds. Part 44. The syntheses of N,N-spiro bridged cyclotriphosphazene derivatives with (4-fluorobenzyl) pendant arms: structural and stereogenic properties, DNA interactions, antimicrobial and cytotoxic activities. Inorganica Chimica Acta 2019; 486: 172-184. doi: 10.1016/j.ica.2018.10.028
3. Asmafiliz N, Kilic Z, Civan M, Avci O, Gonder LY et al. Phosphorus-nitrogen compounds. Part 36. Syntheses, Langmuir-Blodgett thin films and biological activities of spiro-bino-spiro trimeric phosphazenes. New Journal of Chemistry 2016; 40 (11): 9609-9626. doi: 10.1039/c6nj02052f
4. Akbas H, Karadag A, Destegul A, Cakirlar C, Yerli Y et al. Synthesis, and spectroscopic, thermal and dielectric properties of phosphazene based ionic liquids: OFET application and tribological behavior. New Journal of Chemistry 2019; 43 (5): 2098-2110. doi: 10.1039/c8nj04948c
5. Allcock HR. Chemistry and Applications of Polyphosphazenes. Hoboken, NJ, USA: Wiley-Interscience, 2003.
6. Okutan E, Eserci H, Senkuytu E. New perylenebisimide decorated cyclotriphosphazene heavy atom free conjugate as singlet oxygen generator. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2019; 222: 117232. doi: 10.1016/j.saa.2019.117232
7. Caminade AM, Hameau A, Majoral JP. The specific functionalization of cyclotriphosphazene for the synthesis of smart dendrimers. Dalton Transactions 2016; 45 (5): 1810-1822. doi: 10.1039/c5dt03047a
8. Chandrasekhar V, Nagendran S. Phosphazenes as scaffolds for the construction of multi-site coordination ligands. Chemical Society Reviews 2001; 30 (3): 193-203. doi: 10.1039/b004872k
9. Rao MR, Gayatri G, Kumar A, Sastry GN, Ravikanth M. Cyclotriphosphazene ring as a platform for multiporphyrin assemblies. Chemistry - A European Journal 2009; 15 (14): 3488-3496. doi: 10.1002/chem.200802413
10. Van der Huizen AA, Van de Grampel JC, Rusch JW, Wilting T, Van Bolhuis F et al. Aziridinolysis patterns of (NPCl2)3 and (NPCl2)4; crystal structures of trans-N3P3(NC2H4)2Cl4 and 2,trans-4-N4P4(NC2H4)2Cl6. Journal of the Chemical Society, Dalton Transactions 1986; (7): 1317-1327. doi: 10.1039/DT9860001317
11. Van der Huizen AA, Wilting T, Van de Grampel JC, Lelieveld P, Van der Meer-Kalverkamp A et al. Isomerdependent cytostatic activity of bis(1-aziridinyl)cyclophosphazenes. Journal of Medicinal Chemistry 1986; 29 (8): 1341-1345. doi: 10.1021/jm00158a003
12. Ibisoglu H, Besli S, Yuksel F, Un I, Kilic A. Investigation of nucleophilic substitution pathway for the reactions of 1,4-benzodioxan-6-amine with chlorocyclophosphazenes. Inorganica Chimica Acta 2014; 409: 216-226. doi: 10.1016/j.ica.2013.09.030
13. Uslu A, Ozcan E, Dural S, Yuksel F. Synthesis and characterization of cyclotriphosphazene derivatives bearing azole groups. Polyhedron 2016; 117: 394-403. doi: 10.1016/j.poly.2016.06.009
14. Besli S, Coles SJ, Davies DB, Kilic A, Okutan E et al. A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes. Inorganic Chemistry Communications 2009; 12 (8): 773-777. doi: 10.1016/j.inoche.2009.06.014
15. Qian YC, Huang XJ, Xu ZK. Synthesis of polyphosphazene derivatives via thiol-ene click reactions in an aqueous medium. Macromolecular Chemistry and Physics 2015; 216 (6): 671-677. doi: 10.1002/macp.201400545
16. Sarikaya SY, Yesilot S, Kilic A, Okutan E. NIR BODIPY-cyclotriphosphazene-fullerene assemblies: photophyisical properties and photosensitized generation of singlet oxygen. Dyes and Pigments 2019; 162: 734-740. doi: 10.1016/j.dyepig.2018.11.011
17. Senkuytu E, Ecik ET. Octa-BODIPY derivative dendrimeric cyclotetraphosphazenes; photophysical properties and fluorescent chemosensor for Co2+ ions. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2017; 173: 863-870. doi: 10.1016/j.saa.2016.10.052
18. Sarikaya SY, Yesilot S, Kilic A, Okutan E. Novel BODIPY-cyclotriphosphazene-fullerene triads: synthesis, characterization and singlet oxygen generation efficiency. Dyes and Pigments 2018; 153: 26-34. doi: 10.1016/j.dyepig.2018.02.001
19. Loudet A, Burgess K. BODIPY dyes and their derivatives: Syntheses and spectroscopic properties. Chemical Reviews 2007; 107 (11): 4891-4932. doi: 10.1021/cr078381n
20. Huang L, Yu XR, Wu WH, Zhao JZ. Styryl BODIPY-C-60 dyads as efficient heavy-atom-free organic triplet photosensitizers. Organic Letters 2012; 14 (10): 2594-2597. doi: 10.1021/ol3008843
21. Kamkaew A, Lim SH, Lee HB, Kiew LV, Chung LY et al. BODIPY dyes in photodynamic therapy. Chemical Society Reviews 2013; 42 (1): 77-88. doi: 10.1039/c2cs35216h
22. Zhao JZ, Wu WH, Sun JF, Guo S. Triplet photosensitizers: from molecular design to applications. Chemical Society Reviews 2013; 42 (12): 5323-5351. doi: 10.1039/c3cs35531d
23. Senkuytu E, Cebesoy Z, Ciftci GY, Ecik ET. Study on the synthesis, photophysical properties and singlet oxygen generation behavior of BODIPY-functionalized cyclotriphosphazenes. Journal of Fluorescence 2017; 27 (2): 595- 601. doi: 10.1007/s10895-016-1987-9
24. Ecik ET, Senkuytu E, Cebesoy Z, Ciftci GY. BODIPY decorated dendrimeric cyclotriphosphazene photosensitizers: synthesis and efficient singlet oxygen generators. RSC Advances 2016; 6 (53): 47600-47606. doi: 10.1039/c6ra07171f
25. Fery-Forgues S, Lavabre D. Are fluorescence quantum yields so tricky to measure? A demonstration using familiar stationery products. Journal of Chemical Education 1999; 76 (9): 1260-1264. doi: 10.1021/ed076p1260
26. Brouwer AM. Standards for photoluminescence quantum yield measurements in solution (IUPAC technical report). Pure and Applied Chemistry 2011; 83 (12): 2213-2228. doi: 10.1351/Pac-Rep-10-09-31
27. Okutan E, Tumay SO, Yesilot S. Colorimetric fluorescent sensors for hemoglobin based on BODIPY dyes. Journal of Fluorescence 2016; 26 (6): 2333-2343. doi: 10.1007/s10895-016-1929-6
28. Song F, Zhang H, Wang DG, Chen T, Yang S et al. Imine-linked porous organic polymers showing mesoporous microspheres architectures with tunable surface roughness. Journal of Polymer Science Part A: Polymer Chemistry 2018; 56 (3): 319-327. doi: 10.1002/pola.28902
29. Gao HC, Gao Y, Wang C, Hu DH, Xie ZQ et al. Anomalous effect of intramolecular charge transfer on the light emitting properties of BODIPY. ACS Applied Materials & Interfaces 2018; 10 (17): 14956-14965. doi: 10.1021/acsami.7b13444
30. Zhao JZ, Xu KJ, Yang WB, Wang ZJ, Zhong FF. The triplet excited state of BODIPY: formation, modulation and application. Chemical Society Reviews 2015; 44 (24): 8904-8939. doi: 10.1039/c5cs00364d
31. Yogo T, Urano Y, Ishitsuka Y, Maniwa F, Nagano T. Highly efficient and photostable photosensitizer based on BODIPY chromophore. Journal of the American Chemical Society 2005; 127 (35): 12162-12163. doi: 10.1021/ja0528533
32. DeRosa MC, Crutchley RJ. Photosensitized singlet oxygen and its applications. Coordination Chemistry Reviews 2002; 233: 351-371. doi: 10.1016/S0010-8545(02)00034-6