Anion and Cation Complexes of Expanded Porphyrins

Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion

“…The methoxy-attached pyrrolic α-carbon ( i.e. , C20) for 2A is sp 3 hybridized, which can be evidenced by the C20–C21, C20–C19, C20–O, and C20–N distances of 1.495(8), 1.536(7), 1.410(6), and 1.498(7) Å, respectively, typical values for C–C, C–O, and C–N single bonds. 13 Similar bond lengths around C20 were also observed in 2B and the rough crystal structure of 1 (Fig.…”

“… 2 In some cases, topologically twisted metallo-porphyrinoids serve as chiral sensing components. 3 The metalation-induced switchable function of expanded porphyrinoids (such as changes in stereoisomeric structures) should be fascinating for applications in environmentally-responsive molecular machines. 4 …”

A chromophore-supported structural and functional model of dinuclear copper enzymes, for facilitating mechanism of action studies

“…[36][37][38][39] What is more, bimetallic sapphyrins with metalmetal distances of about 3.3 Å have been reported by Sessler, Neya and our group, but only for heavy (4d and 5d) metal ions-Rh, Ir, and Pd. [40][41][42][43][44][45][46] We now report the first fully characterized 3d complexes of sapphyrins, leading to systems with highly relevant biomimetic Cu2O2 and Cu4O4 clusters, supported by a heme-like chromophore that assists the investigation of catalytic catechol oxidation reactions.…”

Expanding the Porphycene Core: Modification and Metalation

“…The increased internal lacuna also facilitate the coordination of larger cations (i.e., lanthanides and actinides), as well as multiple metal ions providing synthetic species with unique features that are not typically recapitulated in the case of porphyrin-based systems. [29][30][31][32][33][34] While considerable effort has been made in the case of porphyrin-type expanded porphyrins, attempts to modify the porphycene core and access larger analogues of Vogel's original porphyrin isomer have been limited. 12,14,[35][36][37][38][39] We have recently encountered success in this arena as detailed below.…”