Modular Synthesis of Linear Bis‐ and Tris‐monodentate Fused [6]Polynorbornane‐Based Ligands and their Assembly into Coordination Cages

Abstract

A modular approach has been developed for the synthesis of rigid linear di- and tritopic ligands based on a fused [6]polynorbornane scaffold. The design provides up to three sites for installing functionality, including both "ends" and a "central" position with the advantage that each region can be independently addressed during synthesis. To illustrate the utility of the approach, both pyridyl and picolyl units were incorporated to provide six new ligands, with centers and ends either matched or mismatched. Indeed, both [M2L4] cages with endohedral functionality and [M3L4] complexes were cleanly produced from these ligands with assembled structures confirmed by using (1)H NMR spectroscopy, HRMS, and molecular modelling.

Double‐Decker Coordination Cages

“…In 2014 we successfully demonstrated the construction of this long‐awaited architecture by using a newly designed ligand and named the self‐assembled Pd 3 L 4 ‐type coordination complex a “double‐decker” cage (Figure ) . In addition, Clever and co‐workers utilized a rigid tridentate ligand for the construction of an elegant Pd 3 L 4 ‐type double‐decker in 2015 …”

Synthesis of Polycycles by Single or Double Domino Nucleophilic Substitution/Diels–Alder Reaction

“…[1][2][3][4] In connection with this potential application, we recently described the synthesis of a 2,8ethanonoradamantane derivative. Polytwistanes [7,8] are being studied as chiral hydrocarbon nanotubes, and polynorbornane derivatives [9] have been used to prepare coordination cages ( Figure 1). Polytwistanes [7,8] are being studied as chiral hydrocarbon nanotubes, and polynorbornane derivatives [9] have been used to prepare coordination cages ( Figure 1).…”

Solid-state NMR as a probe of anion binding: molecular dynamics and associations in a [5]polynorbornane bisurea host complexed with terephthalate

“…Highly pre-organised, fused [n]polynorbornane frameworks have been used in a number of supramolecular settings [32][33][34][35][36][37][38][39][40] and hosts such as 1 (Fig. 1) are well suited for study by NMR techniques as they are symmetric (C 2V and s), and their binding behaviour with a range of guest anions in solution has been studied in depth.…”