Enhanced catalytic decomposition of a phosphate triester by modularly accessible bimetallic porphyrin dyads and dimersElectronic supplementary information (ESI) available: Complete experimental details of syntheses; compound characterization data and spectra; NMR/titration experimental methods, spectra, and data analysis; as well as detailed description of catalytic conditions and results of the methanolysis. See DOI: 10.1039/c2cc17568a

A series of metalloporphyrin dimers were modularly prepared and shown to catalyze the methanolysis of a phosphate triester, yielding rates that are large compared to the rate of the uncatalyzed reaction. Up to 1300-fold rate acceleration can be achieved via a combination of cavity-localized Lewis-acid activation and methoxide-induced methanolysis. Cofacial metalloporphyrin dimers featuring Zn( ii ) and Al( iii ) sites can catalyze the methanolysis of a phosphate triester with high rate enhancements.