The first examples of pyrrole- and thiophenebridged 5,15-diazaporphyrin (DAP) dimers are prepared through Stille coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl = 2,4,6-trimethylphenyl) with the respective 2,5-bis-(tributylstannyl)heteroles. The effects of the heterole spacers and meso nitrogen atoms on the optical, electrochemical, and magnetic properties of the DAP dimers are investigated by UV/Vis absorption spectroscopy, density functional theory calculations, magnetic circular dichroism spectroscopy, cyclic voltammetry, and EPR spectroscopy. The heterole spacers are found to have a significant impact on the electronic transitions over the entire p-system. In particular, the pyrrolebridged DAP dimers exhibit high light-harvesting potential in the low-energy visible/near-infrared region owing to the intrinsic charge-transfer character of the lowest excitation.
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