The Synthesis of New Aryl Boron-Dipyrromethene Compounds: Photophysical and pH Responsive Properties

Abstract

In this work, a convenient protocol enabled the synthesis of novel Arylated Borondipyrromethene (BODIPY) compounds was applied that synthesis yields found to be higher than classical alkyl substituted analogue. Arylated chromophores exhibited the broader red-shifted absorption and fluorescence bands with higher stokes shifts with regard to reference Borondipyrromethene compound (4,4’-difluoro-8-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene,). We interested in the electron transfer mechanism of compound BDPNH₂ which have amine subunit to alkyl substituted reference. The fluorescence enhancement of this compound in acidic media was associated with the inactivation of the acceptor type photoinduced electron transfer mechanism by fluorimetric measurements. Our results are helpful for designing new photosensitizers and for applications in the study of the molecular photochemistry.

Keywords

• Aryl Borondipyrromethene,Pentaaryldipyrrin,BODIPY,pH Sensor

References

1. 1. Chen YT, Wang HL, Wan L, Bian YZ, Jiang JZ. 8-Hydroxyquinoline-Substituted Boron-Dipyrromethene Compounds: Synthesis, Structure, and OFF-ON-OFF Type of pH-Sensing Properties. J Org Chem. 2011 May 20;76(10):3774-81. DOI: 10.1021/jo200050a
2. 2. Gawley RE, Mao H, Haque MM, Thorne JB, Pharr JS. Visible fluorescence chemosensor for saxitoxin. J Org Chem. 2007 Mar 16;72(6):2187-91. DOI: 10.1021/jo062506r
3. 3. Gee KR, Rukavishnikov A, Rothe A. New Ca2+ fluoroionophores based on the BODIPY fluorophore. Comb Chem High T Scr. 2003 Jun;6(4):363-6. DOI: 10.2174/138620703106298455
4. 4. Guo HM, Jing YY, Yuan XL, Ji SM, Zhao JZ, Li XH, et al. Highly selective fluorescent OFF-ON thiol probes based on dyads of BODIPY and potent intramolecular electron sink 2,4-dinitrobenzenesulfonyl subunits. Org Biomol Chem. 2011;9(10):3844-53. DOI: 10.1039/c0ob00910e
5. 5. Han JY, Burgess K. Fluorescent Indicators for Intracellular pH. Chem Rev. 2010 May;110(5):2709-28. DOI: 10.1021/cr900249z
6. 6. Namkung W, Padmawar P, Mills AD, Verkman AS. Cell-based fluorescence screen for K(+) channels and transporters using an extracellular triazacryptand-based K(+) sensor. J Am Chem Soc. 2008 Jun 25;130(25):7794-+. DOI: 10.1021/ja8014499
7. 7. Sevinc G, Kucukoz B, Yilmaz H, Sirikci G, Yaglioglu HG, Hayvali M, et al. Explanation of pH probe mechanism in borondipyrromethene-benzimidazole compound using ultrafast spectroscopy technique. Sensor Actuat B-Chem. 2014 Mar;193:737-44. DOI: 10.1016/j.snb.2013.12.043
8. 8. Son H, Lee HY, Lim JM, Kang D, Han WS, Lee SS, et al. A Highly Sensitive and Selective Turn-On Fluorogenic and Chromogenic Sensor Based on BODIPY-Functionalized Magnetic Nanoparticles for Detecting Lead in Living Cells. Chem-Eur J. 2010;16(38):11549-53. DOI: 10.1002/chem.201001772

9. 9. Teknikel E, Unaleroglu C. Colorimetric and fluorometric pH sensor based on bis(methoxycarbonyl)ethenyl functionalized BODIPY. Dyes Pigments. 2015 Sep;120:239-44. DOI: 10.1016/j.dyepig.2015.04.021
10. 10. Awuah SG, You Y. Boron dipyrromethene (BODIPY)-based photosensitizers for photodynamic therapy. Rsc Adv. 2012;2(30):11169-83. DOI: 10.1039/c2ra21404k
11. 11. Kamkaew A, Lim SH, Lee HB, Kiew LV, Chung LY, Burgess K. BODIPY dyes in photodynamic therapy. Chem Soc Rev. 2013;42(1):77-88. DOI: 10.1039/c2cs35216h 12. Turan IS, Yildiz D, Turksoy A, Gunaydin G, Akkaya EU. A Bifunctional Photosensitizer for Enhanced Fractional Photodynamic Therapy: Singlet Oxygen Generation in the Presence and Absence of Light. Angew Chem Int Edit. 2016 Feb 18;55(8):2875-8. DOI: 10.1002/anie.201511345
12. 13. Wang WQ, Wang L, Li ZS, Xie ZG. BODIPY-containing nanoscale metal-organic frameworks for photodynamic therapy. Chem Commun. 2016;52(31):5402-5. DOI: 10.1039/c6cc01048b
13. 14. Zhang T, Lan RF, Gong LL, Wu BY, Wang YZ, Kwong DWJ, et al. An Amphiphilic BODIPY-Porphyrin Conjugate: Intense Two-Photon Absorption and Rapid Cellular Uptake for Two-Photon-Induced Imaging and Photodynamic Therapy. Chembiochem. 2015 Nov 2;16(16):2357-64. DOI: 10.1002/cbic.201500349
14. 15. Didier P, Ulrich G, Mely Y, Ziessel R. Improved push-pull-push E-Bodipy fluorophores for two-photon cell-imaging. Org Biomol Chem. 2009;7(18):3639-42. DOI: 10.1039/b911587k
15. 16. Kasischke KA, Vishwasrao HD, Fisher PJ, Zipfel WR, Webb WW. Neural activity triggers neuronal oxidative metabolism followed by astrocytic glycolysis. Science. 2004 Jul 2;305(5680):99-103. DOI: DOI 10.1126/science.1096485
16. 17. Kim B, Yue XL, Sui BL, Zhang XF, Xiao Y, Bondar MV, et al. Near-Infrared Fluorescent 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene Probes for One- and Two-Photon Fluorescence Bioimaging. Eur J Org Chem. 2015 Sep(25):5563-71. DOI: 10.1002/ejoc.201500664
17. 18. Chen JJ, Conron SM, Erwin P, Dimitriou M, McAlahney K, Thompson ME. High-Efficiency BODIPY-Based Organic Photovoltaics. Acs Appl Mater Inter. 2015 Jan 14;7(1):662-9. DOI: 10.1021/am506874k
18. 19. Economopoulos SP, Chochos CL, Ioannidou HA, Neophytou M, Charilaou C, Zissimou GA, et al. Novel BODIPY-based conjugated polymers donors for organic photovoltaic applications. Rsc Adv. 2013;3(26):10221-9. DOI: 10.1039/c3ra40957k
19. 20. Poe AM, Della Pelle AM, Subrahmanyam AV, White W, Wantz G, Thayumanavan S. Small molecule BODIPY dyes as non-fullerene acceptors in bulk heterojunction organic photovoltaics. Chem Commun. 2014;50(22):2913-5. DOI: 10.1039/c3cc49648a
20. 21. Squeo BM, Gasparini N, Ameri T, Palma-Cando A, Allard S, Gregoriou VG, et al. Ultra low band gap alpha,beta-unsubstituted BODIPY-based copolymer synthesized by palladium catalyzed cross-coupling polymerization for near infrared organic photovoltaics. J Mater Chem A. 2015;3(31):16279-86. DOI: 10.1039/c5ta04229a
21. 22. Duan X, Li PM, Li P, Xie T, Yu FBA, Tang B. The synthesis of polarity-sensitive fluorescent dyes based on the BODIPY chromophore. Dyes Pigments. 2011 Jun;89(3):217-22. DOI: 10.1016/j.dyepig.2010.03.007
22. 23. Kucukoz B, Sevinc G, Yildiz E, Karatay A, Zhong F, Yilmaz H, et al. Enhancement of two photon absorption properties and intersystem crossing by charge transfer in pentaaryl boron-dipyrromethene (BODIPY) derivatives. Phys Chem Chem Phys. 2016 May 21;18(19):13546-53. DOI: 10.1039/c6cp01266c
23. 24. Wakamiya A, Sugita N, Yamaguchi S. Red-emissive Polyphenylated BODIPY Derivatives: Effect of Peripheral Phenyl Groups on the Photophysical and Electrochemical Properties. Chem Lett. 2008 Oct 5;37(10):1094-5. DOI: 10.1246/cl.2008.1094