Beschreibung:
<jats:title>Abstract</jats:title><jats:p>In the context of solar‐to‐chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron‐transfer processes of three novel zinc(II)‐gold(III) bis(porphyrin) dyads [Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>III</jats:sup>(P)]<jats:sup>+</jats:sup> are presented (P: tetraaryl porphyrin). Time‐resolved spectroscopic studies indicated ultrafast dynamics (<jats:italic>k</jats:italic><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/chem201900050-math-0001.png" xlink:title="urn:x-wiley:09476539:media:chem201900050:chem201900050-math-0001" />
>10<jats:sup>10</jats:sup> s<jats:sup>−1</jats:sup>) after visible‐light excitation, which finally yielded a charge‐shifted state [Zn<jats:sup>II</jats:sup>(P<jats:sup><jats:bold>⋅</jats:bold>+</jats:sup>)–Au<jats:sup>II</jats:sup>(P)]<jats:sup>+</jats:sup> featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (<jats:italic>k</jats:italic><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/chem201900050-math-0002.png" xlink:title="urn:x-wiley:09476539:media:chem201900050:chem201900050-math-0002" />
≈3×10<jats:sup>8</jats:sup> s<jats:sup>−1</jats:sup>). The [Zn<jats:sup>II</jats:sup>(P<jats:sup><jats:bold>⋅</jats:bold>+</jats:sup>)–Au<jats:sup>II</jats:sup>(P)]<jats:sup>+</jats:sup> charge‐shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)–gold(II) bis(porphyrin) Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>II</jats:sup>(P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X‐band EPR, gold L<jats:sub>3</jats:sub>‐edge X‐ray absorption near edge structure (XANES) and paramagnetic <jats:sup>1</jats:sup>H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>II</jats:sup>(P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple.</jats:p>