Design and Synthesis of Alkyne-Substituted Boron in Dipyrromethene Frameworks

Abstract

4,4-Difluoro-3a,4a-diaza-4-bora-s-indacenes, commonly named boron dipyrromethene dyes (F-Bodipy), were utilized as precusors to 4,4-diethynyl-3a,4a-diaza-4-bora-s-indacenes. Symmetrically substituted 4,4-diethynyl-3a,4a-diaza-4-bora-s-inda­cenes were synthesized using substituted ethynyllithium reagents, while the use of a 1:1 mixture of two different ethynyl Grignard reagents gave dissymmetric products. Using (trialkylsilyl)ethynyllithiums (alkyl = Me, Et) gave 4,4-bis[(trialkylsilyl)ethynyl]-3a,4a-diaza-4-bora-s-indacenes, that in the case of the trimethylsilyl derivative could be deprotected to give the mono- or dideprotected product. The dideprotected 4,4-diethynyl-3a,4a-diaza-4-bora-s-indacene was coupled with bromopyrene, -anthracene, or -terpyridine to give the corresponding 4,4-bis(arylethynyl)-3a,4a-diaza-4-bora-s-indacenes. The monodeprotected 4-ethynyl-4-[(trimethylsil­yl)ethynyl]-3a,4a-diaza-4-bora-s-indacenes were either coupled with bromopyrene and then deprotected and oxidatively homocoupled or directly oxidatively homocoupled to give the 1,4-bis(3a,4a-diaza-4-bora-s-indacen-4-yl)butadiyne products. The synthesis of disymmetric 3a,4a-diaza-4-bora-s-indacenes allows the design of fluorescent dyes bearing various functionalities including an oxazol­ine ring. All the dyes synthesized are strongly fluorescent and redox active and cascade energy transfer is evidenced when excited in the pyrene fragment.

Key words

bodipy - alkynes - boron - luminescence - energy transfer

References

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