Metallacyclic assembly of interlocked superstructures

Abstract

Interlocked molecules are a type of supramolecules whose sub-components are held together not by covalent bonds but non-covalent interactions. Examples include rotaxanes, catenanes, Solomon links, ring-in-ring complexes, molecular Borromean rings, molecular knots and interlocked cages. The design and manufacture of these architectures is mainly based on self-assembly and templatedirected methodologies. Inspired by the successful utilization of coordination-driven assembly in metallasupramolecular systems, the metallacyclic assembly of interlocked superstructures is developing rapidly and as such makes a fascinating topic for reviewing. In this review we will focus on the metal-directed synthesis of the different types of interlocked superstructures, as well as their functional applications.

Dynamic Behavior of Covalent Organic Cages

“…For this dimerization, enthalpy gain is required because interlocking processes are entropically unfavorable. [10] In 2010, the group of Cooper reported the transformation of monomeric imine cage 1 mono in solution into triply interlocked imine cage 1 di through ac rystallization process. [4,11] If cage 1 mono ,w hich was prepared from triformylbenzene and 1,2-diaminoethane, wasd issolved in am ixture of dichloromethane and p-xylene, the interlocked cage 1 di ·3 p-xylene was obtained as crystalso ver 50 days (Figure 2a).…”

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

“…The development of angle-strained alkyne-containing macrocyclesh as been described in several excellent reviews. [31][32][33][34][35][36][37][38][39][40] For alkynecontaining shape-persistent macrocycles withouts train [41][42][43][44][45][46][47] and macrocyclic metal complexes, [48][49][50] refer to other reviews.…”

Tuning of the Self‐Threading of Ring‐in‐Ring Structures in Aqueous Media

“…[3] In this context, metal-directeds elf-assembly is aw ell-established and reliable tool for guiding the spatially controlled self-organisation of organic molecules, [4] enabling the construction, under thermodynamic conditions, of innumerabled iscrete structurally complex aggregates (metallocyclophanes, cages or self-assembled metal-organic mechanicallyi nterlocked molecules). [5,6] Nevertheless, there is still an otably absence of work focused on the dynamic/temporalfeatures of the strategy, [7] especially taking into account that the application of metal-directed self-assembly in the designo fn ew constitutionally dynamic systems [8] would certainly help the development of functional instructed matter. [1,2] Following our ongoing interesti nt he metal-directed self-assembly of 4,4'-bipyridinium-based salts into metallacyclic molecular receptors, [9,10] their implementation into novel metal-organic mechanically interlockedm olecules, [11] andi nt he development of new constitutionally dynamic systems, [12] in ap revious communication, [13] we reported the self-assembly around metal centres (en)M(NO 3 ) 2 (M = Pd II /Pt II ;e n = ethylenediamine) of ab iphenyl-containing N-monoalkyl-4,4'-bipyridinium-based ligand (L b ;S cheme 1).…”