A Journey from Supramolecular Chemistry to Nanoscale Networks

Abstract

The use of the coordination properties of metal centres to organise organic ligands in space is a concept that dates back to the seminal work of Alfred Werner that was recognised by the award of the first Nobel Proze for Chemistry in inorganic chemistry 100 years ago. Metal ions may be used to control the assembly of one-, two-or three-dimensional structures by matching the coordination number and geometry with the number and arrangement of donor atoms within ligands. These so-called coordination polymers have recently emerged from the category of unwanted insoluble side-products to materials of high scietrific interest and economic potential. This short article presents the simple design principles that lie behind the synthesis of materials possessing useful properties and, often stunningly attractive structural motifs.

Trinodal Self-Penetrating Nets from Reactions of 1,4-Bis(alkoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene Ligands with Cobalt(II) Thiocyanate

“…As Scheme 1 shows, tridentate bonding by 2,2':6',2"-tpy is synonymous with binding one metal ion and the ligand is classed as monotopic (having a single metal-binding domain) [4]. The incorporation of two or more 2,2':6',2"-tpy units into a single organic molecule leads to a multitopic ligand [2,[5][6][7] and is a design strategy that has been used to access high nuclearity coordination assemblies [8][9][10]. An alternative approach is to use isomers of terpyridine, such as 3,2':6',3"-tpy (PIN 1 3 ,2 2 :2 6 ,3 3 -terpyridine) and 4,2':6',4"-tpy (PIN 1 4 ,2 2 :2 6 ,3 4 -terpyridine), in which chelation is not possible (Scheme 1).…”

4,2′:6′,4′′-Terpyridines: diverging and diverse building blocks in coordination polymers and metallomacrocycles

“…With the correct choice of substituent X, octahedral {M(4′-Xtpy) 2 } complexes (Scheme 2) are ideal building blocks for the assembly of coordination polymers. 10,11 Whereas tpy is typically a 'convergent' ligand (i.e. the chelate effect favours a cis,cis-conformation when tpy binds a metal ion), 4,2′:6′,4″-tpy presents a divergent set of donor atoms.…”

Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry

“…Some representative examples of metal‐containing bipyridyl ligands are depicted in Figure 1. Complexes of type A have mainly been used as “expanded ligands” for structural investigations 4a,e. Metallaporphyrins of type B 4d,f and salen‐type complexes of type C possess accessible metal sites, which can be used for molecular recognition (for example, in sensing applications)5 or for catalysis 6.…”