Strategies for the construction of supramolecular assemblies from poly-NHC ligand precursors

Abstract

The field of supramolecular assemblies has developed rapidly in the last few decades, thanks in a large part to their diverse applications. These assemblies have been mostly based on Werner-type coordination motifs in which metal centres are coordinated by nitrogen or oxygen donors. Recently, N-heterocyclic carbene (NHC) ligands have been employed as carbon donors not only because of their appealing structures but also due to the extensive applications in catalysis, biomedicine and material science of the resulting assemblies. During the last decade, NHC-based supramolecular assemblies have witnessed rapid growth and extensive application in molecular recognition, luminescent materials and catalysis. For different topological systems, a diverse selection of poly-NHC precursors and synthetic strategies is crucial to precisely control the synthesis of supramolecular architectures. Several synthetic strategies have been developed to synthesise two-dimensional (2D) molecular metallacycles and three-dimensional (3D) metallacages from a wide range of poly-NHC precursors, including a straightforward one-pot strategy, supramolecular transmetalation, stepwise synthesis, an improved one-pot strategy involving self-sorting behaviour of 3D metallacages and a subtle variation strategy of poly-NHC ligand precursors. This review offers a summary of the synthetic strategies applied for the construction of different poly-NHC-based supramolecular assemblies, particularly emphasizes recent progress in the synthesis of large and complex supramolecular assemblies from poly-NHC precursors, and further attention is given to their application in postsynthetic modifications (PSMs), host-guest chemistry, luminescent properties and biomedical applications.

Terpyridine‐Based 3D Discrete Metallosupramolecular Architectures

“…Despite the challenges, supramolecular chemists have endeavored to push the limit of coordination‐driven self‐assembly by advancing the ligand synthesis and self‐assembly strategies, [ 30,47,61,62,66,72–74 ] producing diverse 3D metallosupramolecular architectures, such as Platonic solids, Archimedean solids, prims as well as Johnson solids. Therefore, in this review, we would like to summarize the recent progress on tpy‐based discrete 3D metallosupramolecular architectures constructed by different self‐assembly strategies, with the focus on the control over the size and shape of 3D metallosupramolecules by tuning the geometry and angle of the multitopic tpy‐based ligands.…”

Anthracene-Containing Metallacycles and Metallacages: Structures, Properties, and Applications

“…The construction of discrete supramolecular metallacycles and metallacages with well-defined sizes, shapes, and geometries has attracted considerable attention [1][2][3][4][5][6]. Based on the coordination-driven self-assembly strategy, the spontaneous formation of metalligand coordination bonds between Lewis-basic organic donor and Lewis-acidic metal acceptor fabricates a large number of two-dimensional (2D) and three-dimensional (3D) metallasupramolecular architectures, such as molecular triangles, squares, hexagons, polygons, polyhedrons, etc., [7][8][9][10][11]. The high directionality and relative strong strength of coordination bonds offer the possibility of introducing multiple functional units into metallasupramolecular structures with precise stoichiometric and spatial arrangement of individual moieties [12,13].…”

Bis-Pyridine-Based Organogel with AIE Effect and Sensing Performance towards Hg2+

“…In the past thirty years, supramolecular chemistry has become even more sophisticated and quickly developed due to its applications in a variety of disciplines and fields [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. As a typical supramolecular material, low-molecular-weight gels (LMWGs) are a kind of soft material between a solid and liquid which have been developed rapidly and widely used in electrolyte materials [ 12 ], sensors [ 13 , 14 ], drug delivery systems [ 15 ], liquid crystal [ 16 ], supramolecular chirality [ 17 , 18 , 19 ], light-harvesting systems [ 20 , 21 ], surfactants [ 22 ] and other fields [ 23 , 24 , 25 , 26 , 27 , 28 ].…”