Fused Hybrids of a [22]Smaragdyrin BF2 Complex with a Ni-II Porphyrin

[22]Smaragdyrin BF2 complex (S)-Ni-II porphyrin (P) fused hybrids were synthesized through Suzuki-Miyaura coupling of brominated S with borylated P and subsequent oxidative fusion reaction with FeCl3 as the first example of directly fused porphyrinoids bearing cycloheptatriene linkage. These fused hybrids have been fully characterized, including their X-ray structural analysis. Owing to the cycloheptatriene linkage, these fused hybrids adopt waving structures. These fused hybrids display red-shifted and enhanced Q-like bands and characteristic redox potentials, depending upon the constitution and the linking position.