New insights into the factors that govern the square/triangle equilibria of Pd(II) and Pt(II) supramolecules. Unexpected participation of a mononuclear species in the equilibrium.

The new rigid fluorinated ligand 4,4'-bis(4-pyridyl)octafluorobiphenyl (L1) has been synthesized by a nucleophilic substitution reaction between the organolithium derivative of the 4-bromopyridine and the compound decafluorobiphenyl. The use of L1 as building block of supramolecular species containing diphosphane or ethylenediamine Pd(II) and Pt(II) fragments has been explored, and the results have been compared with those previously reported for the smaller ligand 1,4-bis(4-pyridyl)tetrafluorobenzene (L2). The observed differences (particularly, square/triangle ratio) are discussed in terms of different parameters such as the nature of the ancillary ligands, solvent, or reaction temperature. The synthesis of water-soluble palladium metallamacrocycles derived from L1 has been attempted using ethylenediamine (en) or tetramethylethylenediamine (tmen) as ancillary ligand. Interestingly, in the latter case, the resulting solutions of the compounds showed, together with the square/triangle equilibrium, the unexpected presence of an additional lower nuclearity species, whose nature has been determined by means of bidimensional (1)H NMR experiments.