RESUMEN
An N-confused hexapyrrolic phlorinoid 1 and its isomer N-fused hexapyrrolic phlorinoid 2 were synthesized through [4 + 2] condensation. Both 1 and 2 can be readily transformed into N-confused hexapyrrolic phlorinone 3 under aerobic conditions. Coordination of 1 with Cu(acac)2 afforded two different mono-Cu(II) complexes 4 and 5 with CNNN and ONNN coordination environments, respectively. The NIR absorption bands can be effectively modulated up to 1265 nm through the oxidation, fusion, and metalation reactions.
RESUMEN
An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring (1) was synthesized. PdII and BIII coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the PdII -coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3-Ag and 5-Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.
