Probing the dimensions of semi-rigid inner functionalised U-shaped 'bis'-porphyrin cavities

The synthesis of a series of open U-shaped 'bis'-porphyrin cavity molecules is described, with bridged bicyclic backbones to confer rigidity, and a pendant substituted aromatic probe unit suspended on the inside of the cavity. The dimensions and flexibility of the 'bis'-zincporphyrin cavity were probed using several different techniques. Initially the molecular ruler concept was employed, using flexible bidentate ligands as guests with a range of possible linear dimensions. Secondly, NMR methods were employed with rigid bidentate ligand guests of fixed lengths, and thirdly diffusion based NMR methods were utilised. The range of inter-porphyrin distances estimated by these methods suggests that these types of open-cavity systems have a surprising degree of flexibility.