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Structural and dimensional control of porphyrin capsules using Group 15 tris(3-pyridyl) linkers.

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García-Romero, Álvaro  ORCID logo
Álvarez, Celedonio M  ORCID logo
García-Rodríguez, Raúl  ORCID logo


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. 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. 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. 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 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. 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.


Acknowledgements: We thank the Spanish Ministry of Science and Innovation (MCIN) (RG-R, PID2021-124691NB-I00, funded by MCIN/AEI/10.13039/501100011033/FEDER, UE) for funding. A. G.-R. acknowledges the University of Valladolid and Santander Bank for a Fellowship. We thank Dr Angel E. Lozano for insightful discussions and generous support and assistance.


3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 3405 Organic Chemistry, 34 Chemical Sciences

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Chem Sci

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Royal Society of Chemistry (RSC)
Ministerio de Ciencia e Innovación (PID2021-124691NB-I00)