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In supramolecular architectures, the interactions between host and guest molecules are governed by non-covalent forces such as hydrogen (H) bonding, hydrophobic and electrostatic interactions. We alter here the cavity microenvironment to control the interactions between guest and host molecules and study the effects of introducing axial chlorido ligands through the use of an octahedral building block in M(μ-L)M' architectures. We prepared the heterodimetallic Pd(μ-L)Pt C and Pd(μ-L)RuClC architectures and demonstrated the role of 'classic' non-covalent forces in their host-guest chemistry with anionic and neutral molecules, while the cages also underwent disassembly and reassembly upon addition of external stimuli.

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