![]() ![]() ![]() If you are an author contributing to an RSC publication, you do not need to request permission Please go to the Copyright Clearance Center request page. To request permission to reproduce material from this article in a commercial publication, Provided that the correct acknowledgement is given and it is not used for commercial purposes. This article in other publications, without requesting further permission from the RSC, García-Rodríguez,Ĭreative Commons Attribution-NonCommercial 3.0 Unported Licence. Structural and dimensional control of porphyrin capsules using Group 15 tris(3-pyridyl) linkers By providing simple tools for modulating the chemical and steric properties of the capsules this work should have direct applications for the tuning of the activity and specificity of a range of catalytic systems based on main-group-based capsules of this type. The subtle changes in the dimensions and Lewis acidity of the encapsulates have a dramatic effect on the rate and selectivity of the catalytic oxidative cleavage of organic diols and catalytic oxidation of α-hydroxyketones. The increase in C–E bond length in the E(3-py) 3 linkers moving down Group 15 (from E = P, to Sb, to Bi) can be used to alter the dimensions and structural preference of the capsules, as can oxidation of the Group 15 bridgehead atoms themselves. The formation of molecular and extended 2D capsule arrangements between the heavier Group 15 tris(3-pyridyl) linkers Sb(3-py) 3 and Bi(3-py) 3 and the metallo-porphyrins MTPP (M = Zn, Mg TPP = tetraphenylporphyrin, 3-py = 3-pyridyl) is the first study involving heavier Group 15 pyridyl linkers. In this paper we show how periodic trends in the p-block can provide the means for systematic size and structural control in an important class of supramolecular porphyrin-based capsules. While supramolecular chemistry involving organic and metallo-organic host assemblies is a well-established and important field with applications in gas-storage, drug-delivery and the regio- and stereo-control of organic reactions, the use of main group elements in this setting (beyond the second row of the p-block) has been little explored. ![]()
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