Influence of the Reaction Sequence on the Complexation of an NS4-Macrocycle with CdII and CuI Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic CuI Complex

Abstract

In the construction of metallosupramolecules, the reaction sequence in a three-reactant system (one ligand plus two metal ions) could be one of the controlling factors influencing the outcome of the reaction. In this work, the formation of supramolecular isomers (1 and 2) and an endo/exocyclic Cu⁺ complex (4) of the NS₄-macrocycle (L) via different sequential metal addition protocols (routes I-III) is reported. In one-pot reactions of L with Cu(CH₃CN)₄PF₆ in the absence (route I) and presence (route II) of CdI₂, a cyclic dimer Cu^I complex, [Cu₂(L)₂](PF₆)₂ (1), and a one-dimensional coordination polymer, [Cu₂(L)₂]_n·n[CdI₄] (2), were obtained, respectively. Interestingly, the complex cations in 1 and 2 are supramolecular isomers formed via cyclization and polymerization upon complexation, respectively, probably due to different geometric and electronic complementarities, via the C-H···X^- hydrogen bonds, between L and the counterion. In the two-step reaction (route III), an endocyclic Cd²⁺ complex, [Cd(L)I₂] (3), obtained in the first step was utilized in the following reaction with Cu(CH₃CN)₄PF₆, giving rise to an endo/exocyclic tetranuclear Cu⁺ complex, [Cu₄(L)₂(CH₃CN)₆](PF₆)₄ (4), via Cd²⁺ → 2Cu⁺ substitution, which is not accessible by conventional procedures. Solution studies by comparative NMR and electrospray ionization mass spectroscopy also support metal substitution by showing the stronger binding affinity of Cu⁺ over Cd²⁺. These results demonstrate that the metal substitution protocol could be useful for reaching novel metallosupramolecules difficult to obtain by other methods.