Synthesis and Electronic Properties of 3‐Acceptor‐Substituted and 3,7‐Bisacceptor‐Substituted Phenothiazines

3-Acceptor-substituted and 3,7-bisacceptor-substituted phenothiazines can be synthesized in moderate to excellent yields through Suzuki cross-coupling reactions between phenothiazin-3-yl pinacolyl boronates or phenothiazin-3,7-diyl bis(pinacolyl boronates) and electron-deficient (hetero)aryl halides. The electronic properties of (hetero)aryl-substituted N-methyl phenothiazines (UV/Vis absorption, fluorescence, redox potentials) can be correlated with the computed energies of the frontier molecular orbitals. Nitro-substituted derivatives reveal electronically amphoteric behavior, displaying both reversible oxidations and reversible reductions. X-ray structure analysis of the phenothiazinyl p-(2,5-dinitro)phenylene-bridged dyad 13 revealed donor–acceptor interactions between the molecules. Pyridyl and pyrimidyl derivatives fluoresce with quantum yields (Φf) of up to 49 % and can be regarded as redox-active fluorophores. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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