Macrocyclic vs. [2]catenane btp structures: influence of (aryl) substitution on the self templation of btp ligands in macrocyclic synthesis.

The synthesis of four 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) olefin based ligands 3, 4, 11 and 12 is described and their attempted use to form mechanically interlocked molecules using ring closing metatheses (RCM) reactions. The btp ligands were modified in two ways, in 3 and 4 the aryl substitution pattern was changed from 4th position to 3rd position and in the case of 11 and 12, the arms were replaced with aliphatic chains. Our study demonstrates that for all four ligands, the RCM reactions only result in the formation of macrocyclic structures, which in three of the cases, were structurally characterised in both solution (using NMR and HRMS) and in the solid-state using X-ray crystallography. NMR studies were also carried out to investigate if these ligands could preorganise in solution via hydrogen bonding interactions. This study provides a handle of how such precursor substitution can be used to direct the formation of macrocycles or mechanically interlocked structures.

Mechanically Interlocked Chiral Self-Templated [2]Catenanes from 2,6-Bis(1,2,3-triazol-4-yl)pyridine (btp) Ligands.

We report the efficient self-templated formation of optically active 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) derived homocircuit [2]catenane enantiomers. This represents the first example of the enantiopure formation of chiral btp homocircuit [2]catenanes from starting materials consisting of a classical chiral element; X-ray diffraction crystallography enabled the structural characterization of the [2]catenane. The self-assembly reaction was monitored closely in solution facilitating the characterization of the pseudo-rotaxane reaction intermediate prior to mechanically interlocking the pre-organised system via ring-closing metathesis.

A Lanthanide Luminescent Cation Exchange Material Derived from a Flexible Tricarboxylic Acid 2,6-Bis(1,2,3-triazol-4-yl)pyridine (btp) Tecton.

The synthesis of the three-dimensional metal-organic framework material, [Zn7L6]·(H2NMe2)4·(H2O)45 (1), derived from a flexible tricarboxylic acid 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligand, is presented. The btp ligand, H3L, adopts a three-dimensional hydrogen bonding network in the crystalline state through a combination of carboxylic acid dimer and syn-anti-btp/carboxylic acid hydrogen bonding synthons. The Zn(II) species 1 exhibits a three-dimensional framework structure with the rare crs topology and contains linear and undulated solvent channels extending in three dimensions. The guest exchange and gas adsorption properties of 1 were investigated; herein we demonstrate the exchange of dimethylammonium cations from the as-synthesized material with cationic guest molecules in the form of dyes and luminescent Ln(III) ions. Sensitization of Eu(III) and Tb(III) inside the porous network of 1 was achieved upon cation exchange, with a view toward developing functional luminescent materials.

Synthesis and structural studies of 1,4-di(2-pyridyl)-1,2,3-triazole and its transition metal complexes; a versatile and subtly unsymmetric ligand.

The synthesis of the 'click' derived 1,4-di(2-pyridyl)-1,2,3-triazole () chelator/ligand from 2-azidopyridine and 2-ethynylpyridine using Cu(i) and TBTA by microwave assisted synthesis is presented. The complexes of the subtly unsymmetric ligand with Cu(i), Pt(ii), Co(ii), and Ag(i) were structurally characterised by using conventional methods, as well as using single crystal and powder diffraction analysis. The results of the studies showed formation of discrete molecules displaying preferential binding of the d-metal cations through the pyridyl nitrogen N1 and the proximal triazolyl nitrogen N2 i.e. the 2-(1H-1,2,3-triazol-4-yl)pyridine or 'regular' chelate moiety despite the presence of a second potential binding pocket i.e. the 2-(1H-1,2,3-triazol-1-yl)pyridine chelate or 'inverse' moiety. This binding selectivity was corroborated through the study of the self-assembly of with Cu(i) and Ag(i) using (1)H NMR titration in CD3CN solution, as well as using UV-Vis absorption titrations; the former showing a broadening of the proton peaks associated with that chelate pocket.

Self-assembly formation of a healable lanthanide luminescent supramolecular metallogel from 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands.

The synthesis of five new 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands is described: the self-assembly behaviour of the tri-methyl ester, 1, with Eu(III) showed the formation of a luminescent 1:3 Eu : btp complex, Eu13, which was studied in solution and in the solid state; while the tri-carboxylic acid, 2, formed a hydrogel and its corresponding complex Eu23, gave rise to a strongly red luminescent healable metallogel.