Sb- and Bi-Based Salphen Capsules: Pnictogen Bonding, Macrocycle Formation, and ON/OFF Catalysis.
- 1GIR MIOMeT-IU Cinquima-Química Inorgánica Facultad de Ciencias, Universidad de Valladolid, Campus Miguel Delibes, 47011Valladolid, Spain.
Abstract
In this work, we explore the use of heavier tris(3-pyridyl) pnictogen linkers E(3-py)3 (E = Sb, Bi) with metallosalphen building blocks for the construction of supramolecular capsules and macrocycles. The incorporation of these heavier pnictogen centers has a pronounced influence on both self-assembly and reactivity. Depending on the substitution pattern of the salphen and the nature of the metal center (M = Zn, Mg), 1D coordination polymers, discrete 1:3 supramolecular capsule-like assemblies or hierarchically assembled multicapsule macrocycles can be formed. Combining Bi(3-py)3 with unsubstituted Zn-salphen gives an unprecedented polymeric architecture supported by synergistic pyridyl coordination and intermolecular Bi···O pnictogen bonding (PnB). In contrast, Zn salphens with bulky substituents suppress PnB-mediated aggregation and favor capsule formation. Replacing Zn(II) with Mg(II) in the salphen unit redirects the assembly toward heterobimetallic macrocycles {[E(3-py)3]6·(MgSal-tBu)10} derived from capsule-like subunits. Finally, we show that encapsulation of Sb and Bi within Zn-salphen capsules modulates Sb- and Bi-mediated catalytic oxidation of α-hydroxyketones and organic diols, and the reversible encapsulation of Sb(3-py)3 enables supramolecular ON/OFF control of the catalysis.
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BibTeX
@article{garrielmunoz2026bibased,
title = {{Sb- and Bi-Based Salphen Capsules: Pnictogen Bonding, Macrocycle Formation, and ON/OFF Catalysis.}},
author = {Lara Garriel-Muñoz and Héctor Barbero and Álvaro García-Romero and Raúl García-Rodríguez},
journal = {Inorganic chemistry},
year = {2026},
month = oct,
doi = {10.1021/acs.inorgchem.6c03201},
url = {https://europepmc.org/article/MED/42916929},
note = {CC BY},
}
RIS
TY - JOUR
TI - Sb- and Bi-Based Salphen Capsules: Pnictogen Bonding, Macrocycle Formation, and ON/OFF Catalysis.
AU - Lara Garriel-Muñoz
AU - Héctor Barbero
AU - Álvaro García-Romero
AU - Raúl García-Rodríguez
PY - 2026
DA - 2026/10/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c03201
UR - https://europepmc.org/article/MED/42916929
AB - In this work, we explore the use of heavier tris(3-pyridyl) pnictogen linkers E(3-py)3 (E = Sb, Bi) with metallosalphen building blocks for the construction of supramolecular capsules and macrocycles. The incorporation of these heavier pnictogen centers has a pronounced influence on both self-assembly and reactivity. Depending on the substitution pattern of the salphen and the nature of the metal center (M = Zn, Mg), 1D coordination polymers, discrete 1:3 supramolecular capsule-like assemblies or hierarchically assembled multicapsule macrocycles can be formed. Combining Bi(3-py)3 with unsubstituted Zn-salphen gives an unprecedented polymeric architecture supported by synergistic pyridyl coordination and intermolecular Bi···O pnictogen bonding (PnB). In contrast, Zn salphens with bulky substituents suppress PnB-mediated aggregation and favor capsule formation. Replacing Zn(II) with Mg(II) in the salphen unit redirects the assembly toward heterobimetallic macrocycles {[E(3-py)3]6·(MgSal-tBu)10} derived from capsule-like subunits. Finally, we show that encapsulation of Sb and Bi within Zn-salphen capsules modulates Sb- and Bi-mediated catalytic oxidation of α-hydroxyketones and organic diols, and the reversible encapsulation of Sb(3-py)3 enables supramolecular ON/OFF control of the catalysis.
SN - 0020-1669
SN - 1520-510X
ER -