Self-Organization of Porphyrin-POM Dyads: Nonplanar Diacids and Oxoanions in Low-Dimensional H-Bonding Networks.

Coordinating the spatial arrangement of electroactive partners is crucial to designable molecular electronics and photonics. Porphyrins are ubiquitous reaction centers in nature; synthetic porphyrins, in the crystallographic solid state, are often coerced into monolithic stacks, inhibiting reactivity. Using the principles of self-organization, and by exploiting charge-balance principles, we can manipulate nonplanar porphyrins into one- and two-dimensional hydrogen-bonded polymers, with polyoxometalate (POM) and bifunctional counter-anions serving as linkers. Herein, we report 11 crystal structures as a systematic study of the interactions between dodecasubstituted porphyrin acids and nonstandard counterions, as well as the induced conformations in the porphyrin core. We can show that this hydrogen bond chelate is a viable method of organizing electroactive centers into filaments and monolayers for surface deposition and ultrathin devices.