Terpyridine-Based, Flexible Tripods: From a Highly Symmetric Nanosphere to Temperature-Dependent, Irreversible, 3D Isomeric Macromolecular Nanocages

Abstract

A three-dimensional, highly symmetric sphere-like nanocage was synthesized using a terpyridine (tpy)-based, flexible tris-dentate ligand and characterized by single crystal X-ray analysis. To introduce more rigidity, one of the tpy units of the tris-dentate ligand was preblocked by stable <tpy-Ru-tpy> connectivity to form the corresponding Ru-dimer. The complexation between Ru-dimer and Fe demonstrates an unexpected temperature-dependent assembly between two irreversible isomeric 3D nanocages. Investigation of the coordination process and structural configurations of the metal-ligand framework, affected by the introduction of rigidity and in the presence of external stimuli (temperature), is reported.

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

“…The formation of tailored self‐assemblies can be provided by a suitable terpyridine construction strategy, where the coordination process and structural configuration of the metal‐ligand complexes might be affected by the rigidity of the self‐assembled system . Terpyridines moieties can be linked via a rigid spacer, forming a predictable structure, or by flexible units, yielding a random architecture , . The possibility to combine various bridging ligands drives different physics and geometry of self‐assembling multinuclear complexes, offering diverse supramolecular architectures including grids and racks, macrocycles or metal coordination polymers (Figure ).…”

From Dendrimers to Macrocycles: 80 Years George R. Newkome—Milestones of a Gentleman Scientist

“…Besides the molecular design in 2D, it was also possible to construct 3D molecules ( Figure ) . For this purpose, a molecule containing three terpyridine moieties was prepared and complexed using ruthenium(II) ions.…”

“…Schematic representation of a ruthenium‐terpyridine assembly into a 3D molecule structures and its analysis using mass spectrometry as well as ESI‐TWIM‐MS. Reproduced with permission . Copyright 2017, ACS.…”

Platinum(II)-Based Convex Trigonal-Prismatic Cages via Coordination-Driven Self-Assembly and C60 Encapsulation

“…Inspired by this, supramolecular coordination complexes (SCCs) 1 with well-defined shapes and geometries have been prepared via coordination-driven self-assembly. To date, various SCCs with different 2D 2 (triangles, rectangles, pentagons, hexagons, etc) and 3D geometries 3 (tetrahedrons, cages, prisms, etc) have been constructed via the directional bonding approach. 4 In this regard, Fujita et al prepared a suite of M n L 2n polyhedra via the self-assembly of Pd(II) ions and dipyridyl ligands and explored them as molecular flasks for chemical reactions.…”