Charge-Transfer Transitions Govern the Reactivity and Photophysics of Vicinally Diphosphanyl-Substituted Diborapentacenes.

ABSTRACT: 2,3-Difluoro-5,14-dihydro-5,14-diborapentacene (DBP) was endowed with two vicinal Ph₂ P groups by an S_N Ar reaction at both CF sites using Ph₂ PSiMe₃ . Computations reveal the ambipolar product P to undergo P-to-B charge transfer under ambient light irradiation. Consequently, P is prone to photooxidation by air, yielding the Ph₂ P(O) species PO. With S₈ or [Me₃ O][BF₄ ], P furnishes the Ph₂ P(S) or Ph₂ P(Me)⁺ derivatives PS or [PMe][BF₄ ]₂ . Along the series P, PO, PS, and [PMe][BF₄ ]₂ , the redox potentials shift anodically from E_1/2 =-1.89 V to -1.02 V (CH₂ Cl₂ ). Thus, derivatization of the P

SUBMITTER: Jin T 

PROVIDER: S-EPMC9826252 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature