Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups

Abstract

The two-step synthesis of large, heterometallic coordination cages based on ditopic 3-pyridyl ligands is described.

A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

“…Like 4-pyridyl linkers, 3-pyridyl substituents can act as metal-bridging ligandsb ut give rise to different supramolecular architectures as ad irect result of the different disposition of the N-donor atoms within the ligand nodes.T he comparativea bsence of ligandsb ased on 3-pyridyl donor sets has been ascribed to inherent synthetic difficulties [1] and also to their conformational flexibility,w hich entropically favours formationo fs mall aggregates. [2] Severin and co-workersh ave overcome this tendency by incorporatinga dditional steric groups into bis(3-pyridyl) Fe clathrochelate ligandst op roduce Pd 6 L 12 12 + cages, [2] and have found that tuningt he sterics alters the size of the cage. [3] This metalloligand strategy for the construction of heterometallic supramolecular architectures has been successfully enacted for av ariety of mixed transition metals ystems, for example, Fe/Pd, [2,[4][5][6] Fe/Ru, [7] Fe/Co, [8,9] Co/ Mn [5] and Ru/Pd.…”

“…[2] Severin and co-workersh ave overcome this tendency by incorporatinga dditional steric groups into bis(3-pyridyl) Fe clathrochelate ligandst op roduce Pd 6 L 12 12 + cages, [2] and have found that tuningt he sterics alters the size of the cage. [3] This metalloligand strategy for the construction of heterometallic supramolecular architectures has been successfully enacted for av ariety of mixed transition metals ystems, for example, Fe/Pd, [2,[4][5][6] Fe/Ru, [7] Fe/Co, [8,9] Co/ Mn [5] and Ru/Pd. [10,11] However,t he use of main group metalloligands to createmixed main group/transitionmetal heterometallic systems is rare.…”

DSR: enhanced modelling and refinement of disordered structures with SHELXL

“…a high degree of structural flexibility paired with a limited resolution of the experimental data. DSR has already been successfully employed in that context Wise et al, 2015;Wood et al, 2015).…”

Schaltbare Wirt‐Gast‐Systeme

“…In den letzten Jahren entstand der Trend, die Komplexität der modular passgenauen Bausteine zu erhöhen und so Form und Topologie des Käfigs sowie dessen Funktion zu verändern 3. Orthogonale Donoren in multifunktionellen Liganden erlauben es, gezielt heteronukleare Strukturen zu synthetisieren, meist auf Basis des HSAB‐Prinzips (harte und weiche Säuren und Basen; Abbildung 2) 4,5…”