Orientational Compatibility Modulation of Ligands in Low‐Symmetry Multi‐Cavity Discrete Coordination Cages by Neighbouring Cage Participation

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 19, 2024

Abstract Complexation of Pd(II) with a designer unsymmetrical bis‐monodentate ligand (2 : 4 ratio) yielded specific Pd 2 L type “single‐cavity discrete coordination cage” (SCDCC), from pool isomeric structures. The observed selctivity is attributed to inherent orientational preference the strands around metal centers. Crafting short coordinating arm at either ends (i.e longer‐arm) produced pair tris‐monodentate ligands; whereas crafting same short‐arm both gives an tetrakis‐monodentate ligand. tris‐monodenate ligands (3 resulted in corresponding low‐symmetry “multi‐cavity MCDCC having two conjoined cavities, though relative longer arms not achievable these cages. enforced orientation sustained by “Neighbouring Cage Participation” (NCP). However, one‐pot combination Pd(II), mixture 3 ratio integratively self‐sorted mixed‐ligated 31 Also, mixing three cavities. longer‐arm retained double‐cavity and homo‐ligated triple cavity

Language: Английский

A Lantern‐Shaped Pd(II) Cage Constructed from Four Different Low‐Symmetry Ligands with Positional and Orientational Control: An Ancillary Pairings Approach

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(49)

Published: Oct. 11, 2023

Abstract One of the key challenges metallo‐supramolecular chemistry is to maintain ease self‐assembly but, at same time, create structures increasingly high levels complexity. In palladium(II) quadruply stranded lantern‐shaped cages, this has been achieved through either 1) formation heteroleptic (multi‐ligand) assemblies, or 2) homoleptic assemblies from low‐symmetry ligands. Heteroleptic cages formed ligands, a hybid these two approaches, would add an additional rich level complexity but no examples have reported. Here we use system ancillary complementary ligand pairings termini cage ligands target assemblies: pairs can only interact (through coordination single Pd(II) metal ion) between in cis position on cage. Complementarity each pair (and orthogonality other pairs) controlled by denticity (tridentate monodentate bidentate bidentate) and/or hydrogen‐bonding capability (AA DD AD DA). This allows positional and orientational control over with different sites. By using approach, successfully used synthesise complex including example four

Language: Английский