BODIPY Compounds Substituted on Boron

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2024 Nov 9

PMID 39519798

Authors

Marko Bogomolec

Mladena Glavas

Irena Skoric

Affiliations

Soon will be listed here.

Abstract

BODIPY compounds are important organic dyes with exceptional spectral and photophysical properties and numerous applications in different scientific fields. Their widespread applications have flourished due to their easy structural modifications, which enable the preparation of different molecular structures with tunable spectral and photophysical properties. To date, researchers have mostly devoted their efforts to modifying BODIPY -position or pyrrole rings, whereas the substitution of fluorine atoms remains largely unexplored. However, chemistry of the boron atom is possible, and it enables tuning of the photophysical properties of the dyes, without tackling their spectral properties. Furthermore, modifications of boron affect the solubility and aggregation propensity of the molecules. This review article highlights methods for the preparation of 4-substituted compounds and the most important reactions on the boron of the BODIPY dyes. They were divided into reactions promoted by Lewis acid (AlCl or BCl), or bases such as alkoxides and organometallic reagents. By using these two methodologies, it is possible to cleave B-F bonds and substitute them with B-C, B-N, or B-O bonds from different nucleophiles. A special emphasis in this review is given to still underdeveloped photochemical reactions of the boron atom of BODIPY dyes. These reactions have the potential to be used in the development of a new line of BODIPY photo-cleavable protective groups (also known as photocages) with bio-medicinal and photo-pharmacological applications, such as drug delivery.

References

Bonardi L, Ulrich G, Ziessel R . Tailoring the properties of boron-dipyrromethene dyes with acetylenic functions at the 2,6,8 and 4-B substitution positions. Org Lett. 2008; 10(11):2183-6. DOI: 10.1021/ol800560b. View

Lundrigan T, Crawford S, Cameron T, Thompson A . Cl-BODIPYs: a BODIPY class enabling facile B-substitution. Chem Commun (Camb). 2011; 48(7):1003-5. DOI: 10.1039/c1cc16351e. View

Umeda N, Takahashi H, Kamiya M, Ueno T, Komatsu T, Terai T . Boron dipyrromethene as a fluorescent caging group for single-photon uncaging with long-wavelength visible light. ACS Chem Biol. 2014; 9(10):2242-6. DOI: 10.1021/cb500525p. View

Stachelek P, Alsimaree A, Alnoman R, Harriman A, Knight J . Thermally-Activated, Delayed Fluorescence in O,B,O- and N,B,O-Strapped Boron Dipyrromethene Derivatives. J Phys Chem A. 2017; 121(10):2096-2107. DOI: 10.1021/acs.jpca.6b11131. View

Tahtaoui C, Thomas C, Rohmer F, Klotz P, Duportail G, Mely Y . Convenient method to access new 4,4-dialkoxy- and 4,4-diaryloxy-diaza-s-indacene dyes: Synthesis and spectroscopic evaluation. J Org Chem. 2006; 72(1):269-72. DOI: 10.1021/jo061567m. View

Hayashi Y, Yamaguchi S, Cha W, Kim D, Shinokubo H . Synthesis of directly connected BODIPY oligomers through Suzuki-Miyaura coupling. Org Lett. 2011; 13(12):2992-5. DOI: 10.1021/ol200799u. View

Kee H, Kirmaier C, Yu L, Thamyongkit P, Youngblood W, Calder M . Structural control of the photodynamics of boron-dipyrrin complexes. J Phys Chem B. 2006; 109(43):20433-43. PMC: 1513631. DOI: 10.1021/jp0525078. View

Goze C, Ulrich G, Mallon L, Allen B, Harriman A, Ziessel R . Synthesis and photophysical properties of borondipyrromethene dyes bearing aryl substituents at the boron center. J Am Chem Soc. 2006; 128(31):10231-9. DOI: 10.1021/ja062405a. View

Goze C, Ulrich G, Ziessel R . Unusual fluorescent monomeric and dimeric dialkynyl dipyrromethene-borane complexes. Org Lett. 2006; 8(20):4445-8. DOI: 10.1021/ol061601j. View

10.

Kawatani M, Kamiya M, Takahashi H, Urano Y . Factors affecting the uncaging efficiency of 500 nm light-activatable BODIPY caging group. Bioorg Med Chem Lett. 2017; 28(1):1-5. DOI: 10.1016/j.bmcl.2017.11.030. View

11.

Ragab S, Swaminathan S, Deniz E, Captain B, Raymo F . Fluorescence photoactivation by ligand exchange around the boron center of a BODIPY chromophore. Org Lett. 2013; 15(12):3154-7. DOI: 10.1021/ol401380n. View

12.

Rohand T, Baruah M, Qin W, Boens N, Dehaen W . Functionalisation of fluorescent BODIPY dyes by nucleophilic substitution. Chem Commun (Camb). 2006; (3):266-8. DOI: 10.1039/b512756d. View

13.

Jiao L, Pang W, Zhou J, Wei Y, Mu X, Bai G . Regioselective stepwise bromination of boron dipyrromethene (BODIPY) dyes. J Org Chem. 2011; 76(24):9988-96. DOI: 10.1021/jo201754m. View

14.

Slanina T, Shrestha P, Palao E, Kand D, Peterson J, Dutton A . In Search of the Perfect Photocage: Structure-Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups. J Am Chem Soc. 2017; 139(42):15168-15175. DOI: 10.1021/jacs.7b08532. View

15.

Lundrigan T, Thompson A . Conversion of F-BODIPYs to Cl-BODIPYs: enhancing the reactivity of F-BODIPYs. J Org Chem. 2012; 78(2):757-61. DOI: 10.1021/jo302277d. View

16.

Courtis A, Santos S, Guan Y, Hendricks J, Ghosh B, Szantai-Kis D . Monoalkoxy BODIPYs--a fluorophore class for bioimaging. Bioconjug Chem. 2014; 25(6):1043-51. PMC: 4215867. DOI: 10.1021/bc400575w. View

17.

Jagtap K, Shivran N, Mula S, Naik D, Sarkar S, Mukherjee T . Change of boron substitution improves the lasing performance of Bodipy dyes: a mechanistic rationalisation. Chemistry. 2012; 19(2):702-8. DOI: 10.1002/chem.201202699. View

18.

Banuelos J . BODIPY Dye, the Most Versatile Fluorophore Ever?. Chem Rec. 2016; 16(1):335-48. DOI: 10.1002/tcr.201500238. View

19.

Dent M, Lopez-Duarte I, Dickson C, Geoghegan N, Cooper J, Gould I . Imaging phase separation in model lipid membranes through the use of BODIPY based molecular rotors. Phys Chem Chem Phys. 2015; 17(28):18393-402. DOI: 10.1039/c5cp01937k. View

20.

Ellis-Davies G . Reverse Engineering Caged Compounds: Design Principles for their Application in Biology. Angew Chem Int Ed Engl. 2023; 62(9):e202206083. PMC: 10015297. DOI: 10.1002/anie.202206083. View