Structural analysis of porphyrin molecular squares using molecular mechanics and density-functional methods

"Molecular squares" formed from Re(CO)(3)Cl corners and porphyrin sides have potential applications as hosts for catalytic sites and as building blocks for membranes. In these materials, knowledge of the conformations of the squares is important. Molecular-mechanics (MM) and density-functional (DF) calculations have been used iteratively in this work to find the minimum-energy configurations of several porphyrin molecular squares. MM predicts that the steric and torsional interactions at connecting junctures of the square framework determine the overall geometry. Torsional degrees of freedom around these junctures were therefore analyzed using DF methods, giving further insight and helping choose among MM force-field options. Single-point DF calculations on the entire squares showed that the energy and conformation of the entire square could be reliably obtained by performing DF calculations on the critical elements of the square and then piecing them together. This "piecewise" strategy allows for both the major torsional motions and the most important local relaxations of large supramolecular species such as molecular squares.