Strongly coupled porphyrin arrays featuring both, π-cofacial and linear-π-conjugative interactions

A combination of metal-catalyzed cross-coupling and metal-templated cycloaddition reactions have, been 'utilized to establish multiporphyrin compounds 5-(5'-[15',15-bis(10,20-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphiniato)zinc(II)]ethyne)-6-[(5'-10', 20'-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1) and 5,6-bis(5'-15',15-bis[(10',20'-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II) ethyne)indane. (2). Compounds 1 and 2 feature a covalently bridged cofacial bis(porphinato) metal core; ethyne bridging moieties conjugate directly one and two respective peripheral (porphinato)zinc(II) substituents to the macrocyclic framework of their corresponding face-to-face porphyrin units. Optical spectroscopy and electrochemical, studies demonstrate substantive electronic interactions between the porphyrin subunits of these compounds. Notably, structural and H-1 NMR analyses verify that 1 and 2 possess open conformations necessary for binding small molecules within their respective cofacial (porphinato)metal cores.