RT info:eu-repo/semantics/article
T1 Structural and dimensional control of porphyrin capsules using group 15 tris(3-pyridyl) linkers
A1 García Romero, Álvaro
A1 Miguel San José, Daniel
A1 Wright, Dominic Simon
A1 Álvarez González, Celedonio Manuel
A1 García Rodríguez, Raúl
K1 2210 Química Física
K1 2303 Química Inorgánica
AB 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.
PB Royal Society of Chemistry
SN 2041-6539
YR 2023
FD 2023
LK https://uvadoc.uva.es/handle/10324/59799
UL https://uvadoc.uva.es/handle/10324/59799
LA eng
NO Chemical Science, 2023
NO Producción Científica
DS UVaDOC
RD 01-jun-2024