Cu(II), Ag(I) and Pt(II) bipyridine oligomer metallomacrocycles that function as efficient host complexes for the encapsulation of alkali ion guests

Two open-chain bipyridine oligomers (1 and 2) were coordinated to Cu(II) (3 and 4) and Ag(I) (5 and 6) metal centers producing the corresponding closed-pocket monometallic macrocycles. The oligomers were also coordinated to two Pt(II) dichloride moieties (7 and 8) producing the bimetallic oligomeric complexes. The metallated complexes were more efficient alkali ion extractors than the free ligands and they displayed unique ion selectivities based on the nature of the metallomacrocycle that was formed. The largest monometallic Ag(I) system (6) displayed the highest extraction efficiency (EE) values for all ions (Na+, K+, and Cs+) with an ion selectivity order of Na+ > K+ > Cs+. The bimetallic Pt(II) systems (7 and 8) were less efficient overall than the monometallic complexes at extracting ions, but displayed greater ion selectivity. The ion selectivity order for these complexes was Cs+ > K+ > Na+. The uncomplexed host transition metal systems were characterized using H-1 NMR spectroscopy and MALDI-TOF mass spectrometry and the ion-encapsulated host-guest systems were characterized using ESI and MALDI-TOF mass spectrometry and UV-Vis spectroscopy. (C) 2011 Elsevier B. V. All rights reserved.