Functional Supramolecular Architectures of Dipyrrin Complexes

Abstract

Dynamic formation of self-assemblies from molecular components is a useful and efficient way to produce molecular and supramolecular architectures with sophisticated functions. The labile coordination bond and dynamic covalent bond as a reversible bond have often been used to create a well-organized supramolecular self-assembly. In order to realize sophisticated novel functions of the supramolecular self-assemblies, dipyrrin complexes have recently been employed as a functional unit and incorporated into the supramolecular architectures because of their outstanding properties and functions such as a high photostability and strong light absorption/emission. This review article summarizes recent development in functional supramolecular architectures of the dipyrrin complexes produced by coordination to a metal ion and dynamic covalent bond formation. We first describe the synthesis and unique functions of a series of discrete supramolecular architectures: helicates, macrocycles, and cages. The polymeric supramolecular self-assemblies with 1D, 2D, and 3D structures are then introduced as a functional infinite supramolecular architecture.

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

“…H 4 L26 exhibited an efficient photoluminescence in toluene and chloroform, which was not observed in other macrocyclic dipyrrinzinc(II) complexes. 76,77,79,80 The emission quantum yield in toluene (Φ F = 0.61) is comparable to those of other efficiently luminescent mono(dipyrrinato)zinc(II) complexes. The DFT calculations suggested that the complex features characteristic of nondegenerate frontier orbitals reflecting its unsymmetrical structure might contribute to the effi- 81 In fact, the complexes exhibited a unique cationbinding affinity toward various cations with colorimetric and fluorometric changes (vide infra).…”

“…[73][74][75] As is the case with the BODIPY oligomers, transition-metal complexes of the oligodipyrrins often show unique structures and properties that are difficult to be achieved by the corresponding monomeric complexes. 76,77 In particular, conformationally flexible macrocyclic oligodipyrrin ligands produced uniquely shaped multinuclear complexes having characteristic properties such as helical-chirality induction by a chiral guest molecule 78 and a temperature-dependent springlike conformational change. 79, 80 Nabeshima and coworkers employed the metaphenylene-linked macrocyclic dipyrrin tetramer H 4 L26 as a conformationally flexible ligand for zinc(II).…”

Dipyrromethene‐Triazolylidene Silver Complexes: Synthesis, Structure and Opportunities

“…[ 3 ] DPMs present a strong affinity for a large variety of metals, and can be functionalized to afford metallocomplexes displaying original structures with applications in catalysis, [ 4–8 ] luminescence [ 9,10 ] or in the construction of supramolecular assemblies. [ 11–13 ]…”

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

“…The incorporation of functional moieties into pre-existing cage molecules and macrocycles represents a powerful strategy to tailor their architectural, inclusion, self-assembling, stimulus responsiveness and biorecognition properties (Sansone and Casnati, 2013; Shetty et al, 2015; Gropp et al, 2017; Liu et al, 2017; Matsuoka and Nabeshima, 2018). A range of sophisticated molecular machines with programmed supramolecular behaviors have been designed by implementing this strategy, with applications in the fields of sensors, electronic or optical devices, natural ligand mimics, artificial catalysts or (bio) molecular carriers, among others (Jiménez Blanco et al, 2017; Webber and Langer, 2017; Yin et al, 2017; Guo et al, 2018; van Dijk et al, 2018; Yu et al, 2018; Zeng et al, 2018).…”