Chiral macrocyclic terpyridine complexes

Abstract

Interlinking of two terpyridine ligands results in mononuclear chiral metal complexes (Fe and Ru) which were separated into their enantiomers.

A Chiral Macrocyclic Oligothiophene with Broken Conjugation – Rapid Racemization through Internal Rotation

“…All spectra were recorded in dichloromethane at room temperature. The emission spectra were exited at 438 nm (22), 413 nm (23), and 420 nm (1).…”

“…[20] More recently, our focus moved to axial chiral systems like bicyclic 'Geländer'-type structures [21] or the macrocyclization of the ligands assembled in a M(II) terpyridine complex resulting in a helical macrocycle with an arrangement resembling a propeller. [22] Cyclo[n]thiophenes are an interesting class of conjugated macrocycles; they are model compounds for polythiophenes, with well-defined self-assembling and electronic features. [23] Initially, the synthesis of macrocyclic oligothiophenes was performed by reacting on both sides ethynyl-terminated ter-and quinquethiophenes under oxidative acetylene coupling conditions in the presence of a copper catalyst.…”

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

“…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 ).…”

Improved Photostability of a CuI Complex by Macrocyclization of the Phenanthroline Ligands

“…Recently we reported an approach to interlink coordinated terpyridine (tpy) ligands to a macrocycle, not only to improve the stability of the complex, but also to provide a chiral ligand sphere . Herein, we report a similar strategy (Figure ) to macrocyclize Cu I phenantroline complexes in order to tightly fix their ligand sphere with the intention to increase their structural integrity.…”

“…Recently we reported an approach to interlink coordinated terpyridine (tpy) ligands to a macrocycle, not only to improve the stability of the complex, [30] but also to provide a chiral ligand sphere. [31] Herein, we report a similar strategy ( Figure 1) to macrocyclize Cu I phenantroline complexes in order to tightly fix their ligand sphere with the intention to increase their structural integrity. The macrocyclization is again based on Glaser-Hay-type oxidative acetylene coupling, [32] forming, similar to the approach of Heuft and Fallis, [33] the complexes 2 and 3 with different strain upon macrocyclization.…”