Self-Assembly Reactions between the Cis-Protected Metal Corners (N−N)MII(N−N = Ethylenediamine, 4,4‘-Substituted 2,2‘-Bipyridine; M = Pd, Pt) and the Fluorinated Edge 1,4-Bis(4-pyridyl)tetrafluorobenzene

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Abstract

The self-assembly reactions between the fluorinated ditopic ligand 1,4-bis(4-pyridyl)tetrafluorobenzene (A) and different nitrogen-protected palladium(II) and platinum(II) complexes have been investigated. While dynamic equilibria between molecular triangles and squares were observed when the diimine compounds 4,4'-R2bipy (bipy = 2,2'-bipyridine; R = H, Me, t-Bu) were employed as ancillary ligands, only square species were obtained from ethylenediamine (en) derivatives. Characterization of the obtained metallomacrocycles was accomplished by 1H and 19F NMR spectroscopy in combination with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR). Molecular dynamics simulations (UFF) have been performed to interpret the influence of the fluorinated ring on the square/triangle relative stability. Density functional calculations using the GIAO method have been employed for the interpretation of the chemical shift assignments. The study of the ability of these compounds to act as hosts of electron-rich aromatic guests has shown that the palladium ethylenediamine square is capable of establishing this type of intermolecular interaction exclusively in aqueous media. The host-guest stoichiometry and association constants have been determinated by 1H NMR spectroscopy.

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