Phosphorescent Organometallic Knots of Gold(I)-Bis(acetylide) Strands Directed by Copper(I) π-Coordination
Abstract Through elaborate ligand design to create knotted structures with specific topologies is a major challenge for chemists. In this work, the self-assembly between U-shape 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H2L) and Au+ through gold(I)-bis(acetylide) linkages under π-bonded Cu+ template gives rise to complex 1 with two interlocked metallostrands as well as complexes 3 (n = 3) and 4 (n = 4) with [(AuL)n]n- metallostrands showing trefoil knot topology. Upon incorporating two [Au(dppb)Au]2+ (dppb = Ph2P(CH2)4PPh2) moieties through bis(Au-acetylide) coordination bonds, the interlocked structure (1) is fully closed to form a figure-eight knotted structure in complex 2. The folding and threading of metallocyclic strings are directed by Cu+, which are π-ligated to two or three acetylides to generate double-folding or triple-folding cross points. Complexes 1-4 show intense phosphorescence in both solutions and solid states at ambient temperature, originating from admixture of metal centered 3[d®p/s], 3IL (intraligand), and 3[p (L) ® s/p (Au/Cu)] 3LMCT triplet states.