Self‐Assembly Methods for Recently Reported Discrete Supramolecular Structures Based on Terpyridine

Abstract

In this Review, self-assembly methods of discrete metallo-supramolecules based on 2,2' : 6',2''-terpyridine (tpy) are comprehensively summarized. With the development of self-assembly, strategies for discrete 2D and 3D supramolecular architectures have boomed, including the geometry-directed method, template-driven method, and stepwise method. Ligand geometry-directed method mainly depends on the geometry of ligands (i. e., angle, geometric strain, and rigidity), and it is suitable for dual-component systems, while the template-driven method can guide the self-assembly of predesigned supramolecules by the introduction of specific templates. Meanwhile, stepwise method, breaking the inherent self-sorting of ligands and reducing the probability of mismatch, is suitable for multicomponent systems to yield predesigned supramolecules. This review focuses on self-assembly methods and aims to provide a guideline for constructing supramolecular architectures using a suitable approach.

Terpyridine‐Based 3D Discrete Metallosupramolecular Architectures

“…Due to the directional, predictable and reversible nature of metalligand interactions, coordination-driven self-assembly has been intensely applied in the construction of a myriad of metallosupramolecules with well-defined structures and desired functions over the past few decades. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] A series of N-heteroaromatic ligands, such as pyridine, [15][16][17] 2,2ʹ-bipyridine, [9,[18][19][20] 1,10phenanthroline, [21][22][23][24] salen, [25,26] tetrazole, [27,28] and 2,2ʹ:6ʹ,2ʹʹterpyridine (tpy), [11,13,[29][30][31] have been widely employed to assemble metallo-supramolecules via coordination with metal ions.…”

“…[29,[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69] The syntheses, characterizations, properties, and applications of such constructs have been summarized in several reviews, which have provided profound insights into further syntheses and applications of the 2D metallosupramolecular family. [11,13,[29][30][31]70,71] Inspired by the aesthetic structures of various viral capsids and fascinating polyhedra in biological and mineral worlds, construction of 3D molecular mimics using the tpy-M(II)-tpy connectivity has also drawn significant attention. However, assembly of such 3D metallosupramolecular architectures remains a formidable synthetic challenge.…”

“…[ 29,55–69 ] The syntheses, characterizations, properties, and applications of such constructs have been summarized in several reviews, which have provided profound insights into further syntheses and applications of the 2D metallosupramolecular family. [ 11,13,29–31,70,71 ]…”

Synthesis of an Fe(terpy-cage)2 dumbbell

“…Terpyridine motifs are often applied for the synthesis of complex supramolecular species. 12 As such, they have been used to construct macrocyclic and cage type compounds. 13,14 Furthermore, they have been used to design molecular machines and metallo-helicoids.…”

Construction of metallo-triangles with cis-TPE motifs and fluorescence properties

“…[6][7][8][9] Among various and diverse organic ligands, 2,2 0 ,6 0 ,2 00 -terpyridine has been extensively used as the coordination motif thanks to the prominent chelating ability and outstanding coordination ability with diverse metal ions. [10][11][12][13] With the aim of improving their functionality, SCCs incorporated with chromophores have evolved to be one of the most attractive topics on account of their broad applications in light-emitting diodes, 14 sensors, 15 photoelectric devices, 16 bioimaging, 17,18 etc. Among various chromophores, as classical AIE gens, tetraphenylethylene (TPE) was modified in ligands to explore fluorescence properties in the aggregated state.…”