The synthesis and characterization of some new binuclear copper (II) complexes, based on the use of large, pyrole-containing macrocycles, the so called "expanded porphyrins", [Cu2(macrocycle)]+4 is described. Electron Spin Resonance (ESR) studies indicate a weak "half-field line", which is characteristic of the Cu(II)-Cu(II) dimer, is observed at about 1600G. The obser...

Expanded porphyrins are synthetic analogues of porphyrins consisting of at least 17 atoms in a cyclic conjugated framework that contains at least three pyrrole or pyrrole-like heterocyclic subunits. These macrocyclic systems have aroused great interest as near-IR-absorbing or -emitting chromophores and as two-photon dyes; their cavities are large enough to function as anion-recognition systems,...

Two types of interaction of expanded porphyrins and nucleic acids are discussed. The first involves the specific chelation of the anionic phosphate diester backbone of DNA by the monoprotonated form of the water soluble sapphyrin 2. Support for the proposed binding mode derives from a variety of spectroscopic and biochemical studies, including visible absorption spectroscopy, circular dichroism...

The synthesis and characterization of the first examples of singly and doubly fused expanded porphyrins containing dithienothiophene (DTT) cores are reported.

Over the last 2 decades, the rapid development of new synthetic routes for the preparation of expanded porphyrin macrocycles has allowed for the exploration of a new frontier consisting of "porphyrin-like" coordination chemistry. In this Account, we summarize our exploratory forays into the still relatively poorly explored area of oligopyrrolic macrocycle metalation chemistry. Specifically, we ...

The conformational flexibility of the expanded porphyrins allows them to achieve different topologies with distinct aromaticities and nonlinear optical properties (NLOP). For instance, it is possible to switch between Möbius and Hückel topologies applying only small changes in the external conditions or in the structure of the ring. In this work, we evaluate the electronic and vibrational contr...