Metal-directed self-assembly of constitutionally dynamic systems: control of the nuclearity of Pd(ii)/Pt(ii) metallacycles. Issue 1 (2nd December 2022)

• Record Type: Journal Article
• Authors: Neira, Iago; Domarco, Olaya; Rama, Tamara; Blanco, Victor; Peinador, Carlos; García, Marcos D.; Quintela, José M.
• Is Part Of: Dalton transactions. Volume 52:Issue 1(2022)
• Page Start: 90
• Page End: 96
• Publication Date: 2022-12-02
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt02955c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : 4, 4′-Bipyridinium-based ditopic ligands assemble with Pd(ii ) centers generating constitutionally dynamic systems in which concentration is a suitable stimulus to influence the speciation between mononuclear [PdL ] 5+ and dinuclear [Pd2 L 2 ] 10+ species. Abstract : Self-assembly with the square-planar Pd(ii ) or Pt(ii ) (en)M(ONO2 )2 (en = ethylenediamine) complexes of ditopic ligands incorporating both N, N ′-dialkyl-4, 4′-bipyridinium and N -monoalkyl-4, 4′-bipyridinium or N -monoalkyl-2, 7-diazapyrenium moieties leads to constitutionally dynamic systems responsive to the concentration of the components. At low concentrations, the metallamacrocyclic mononuclear [ML ] 5+ species is formed. In contrast, when the concentration is increased, a defined dinuclear [M2 L 2 ] 10+ structure appears as a second species in equilibrium, becoming the major one at high concentrations. Besides concentration changes, the addition of an aromatic guest also allows the control of the system speciation, shifting the outcome of the metal-directed self-assembly towards the mononuclear metallacycle. This dynamic behavior enables the control of the nuclearity of the metallacycles assembled by external stimuli.