Self-assembly driven supramolecular chemistry has led to a vast array of molecules with unusual geometries and diverse applications.  In this project, molecular squares of +12 charge are synthesized using Rh(III)-thiacrown vertices.  The rigid octahedral geometry of Rh(III) provides the initial template for square synthesis.  Four of the coordination sites are occupied with the tetrathiacrown, 1,4,7,10-tetrathiacylcanonane (12S4), which acts as a capping ligand.   The remaining two cis coordination sites in the [Rh(12S4)(H2O)2]3+ vertex can then be used to assemble the squares.  In this investigation, 4,4'-bipyridine and 1,2-bis-(4-pyridyl)-ethylene are utilized  as linker ligands because their ability to form a linear bridge should lead to square formation.  Self-assembly of the rhodium(III) squares is confirmed by simple proton NMR spectra.  The overall +12 charge of the square is a desirable quality as it could have the ability to reduce in one-electron increments, which has potential application in the field of nanoelectronics.

Self-assembly of molecular squares containing Rh(III)-thiacrown vertices

245th National Meeting (2013)

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