Synthesis, Redox, and Spectroscopic Properties of Pd(II) 10,10-Dimethylisocorrole Complexes Prepared via Bromination of Dimethylbiladiene Oligotetrapyrroles.

Abstract

Two brominated 10,10-dimethylisocorrole (10-DMIC) derivatives containing Pd(II) centers have been prepared and characterized. These compounds were prepared via bromination of 10,10-dimethylbiladiene-based oligotetrapyrroles. Bromination of free base 10,10-dimethylbiladiene (DMBil1) followed by metalation with Pd(OAc)2, as well as bromination of the corresponding Pd(II) dimethylbiladiene complex (Pd[DMBil1]) provide routes to Pd(II) hexabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br6]) and Pd(II) octabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br8]). The solid-state structures of the two brominated isocorrole complexes are presented, as is that for a new decabrominated dimethylbiladiene derivative (DMBil-Br10). The electronic and spectroscopic properties of the brominated biladiene and isocorrole derivatives were probed using a combination of voltammetric methods and steady-state UV-vis absorption and emission experiments. Data obtained from these experiments allow the properties of the brominated biladiene and isocorrole derivatives to be compared to previously studied biladiene derivatives (i.e., DMBil1 and Pd[DMBil1]). CV and DPV experiments demonstrate that Pd[10-DMIC-Br6] and Pd[10-DMIC-Br8] support well-behaved multielectron redox chemistry, similar to that which has been observed for other nonaromatic tetrapyrroles containing sp3-hybridized meso-carbons. Spectroscopic experiments reveal that bromination of the dimethylbiladiene core shifts this system's UV-vis absorption profile to lower energy and that the dimethylisocorrole complexes support panchromatic absorption profiles that extend across the UV-vis and into the near-IR region. Photosensitization experiments demonstrate that unlike previously studied Pd(II) biladiene constructs, DMBil-Br10, Pd[10-DMIC-Br6], and Pd[10-DMIC-Br8] support limited triplet excited state chemistry with O2, indicating that the novel nonaromatic tetrapyrrole derivatives described in this work may be best suited for applications other than singlet oxygen sensitization.