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Structure property relationships in calamitic metalloporphyrins


It was first discovered in Sheffield that disc-like metalloporphyrins can show fluid, rod-like mesophases by suitable synthetic modification and that unfavourable intermolecular Pi-Pi interactions, which led to high melting points, could be suppressed. The mixture of rod- and disc-like features in these molecules makes them attractive in the search for biaxial nematic mesophases, where very fast switching times are predicted.
A systematic evaluation of the way in which the structure of these porphyrins determines both the mesophases formed and the temperature at which they exist is proposed. It is intended to study the effect of the terminal groups in the 5- and 15- positions which lend the porphyrins their rod-like character, the peripheral groups which exert some control over both the disc-like nature of the core and over the melting point, and ortho groups which appear to hold the key to low-melting points.


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