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oai:figshare.com:article/34027231 2026-09-29T18:14:20Z category_4 category_146 category_24 category_873 category_734 portal_63 item_type_6 month_year_09_2026

Sb- and Bi-Based Salphen Capsules: Pnictogen Bonding, Macrocycle Formation, and ON/OFF Catalysis Lara Garriel-Muñoz (25138513) Héctor Barbero (1672510) Álvaro García-Romero (8764449) Raúl García-Rodríguez (1371201) Biochemistry Space Science Evolutionary Biology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified py )< sub metallosalphen building blocks bu )< sub mediated catalytic oxidation salphen unit redirects synergistic pyridyl coordination heavier pnictogen centers favor capsule formation intermolecular bi ··· based salphen capsules pnictogen linkers e 3 </ sub bi within zn 3 supramolecular capsule supramolecular capsules pnictogen bonding mediated aggregation macrocycle formation heavier tris enables supramolecular salphen gives zn salphens unsubstituted zn substitution pattern replacing zn pronounced influence pnb ). organic diols metal center like subunits like assemblies discrete 1 ></ sup 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-^<i>t</i>Bu)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. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/acs.inorgchem.6c03201.s001 https://figshare.com/articles/journal_contribution/Sb-_and_Bi-Based_Salphen_Capsules_Pnictogen_Bonding_Macrocycle_Formation_and_ON_OFF_Catalysis/34027231 CC BY-NC 4.0