Issue 24, 2023

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

Abstract

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
27 apr 2023
Accepted
16 mai 2023
First published
06 jun 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 6522-6530

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

Á. García-Romero, D. Miguel, D. S. Wright, C. M. Álvarez and R. García-Rodríguez, Chem. Sci., 2023, 14, 6522 DOI: 10.1039/D3SC02151C

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