Stimuli-Responsive Reversible Assembly of 2D and 3D Metallosupramolecular Architectures
摘要:
The discovery of interconvertible platinum coordination modes, which reveals and masks cis coordinating groups upon addition of acid and base, respectively, has been exploited to facilitate stimuli-responsive assembly and disassembly of both two- and three-dimensional metallosupramolecular architectures. Treatment of a binclear platinum complex with acid along with ditopic and tritopic donor ligands generated a molecular square and a trigonal prism, respectively, in good to high yield. These complexes were unambiguously identified using electrospray mass spectrometry, H-1 NMR spectroscopy, and X-ray crystallography. Both assemblies can be disassembled into their constituent parts simply by treatment with base, and the prism can be cycled between the assembled and disassembled states by the alternate addition of acid and base.
The exchange between different equilibrium and out-of-equilibrium platinum coordination modes can be orthogonally controlled thermodynamically with a proton input and kinetically using light.