Cu I /Cu II Complexes with Dipicolinoylbis( N , N ‐diethylthiourea): Structures, Magnetism, and Guest Ion Exchange

Potassium cations play a vital role in directing reactions of 2,6‐dipicolinoylbis( N , N ‐diethylthiourea) ( H 2 L ) with Cu(OAc) 2 . In the absence of K + , a redox reaction occurred, leading to the formation of a polymeric complex [Cu II Cu I 2 (L) 2 ] ∞ ( 1 ). On the other hand, adding a K + source (i.e KPF 6 ) directs the reaction to a self‐assembly process, forming the {2}‐metallacoronate [Cu II 2 K(L) 2 ](PF 6 ) ( 2 ) complexes. The polymeric structure of 1 is built by bridging neighboring [Cu II Cu I 2 (L) 2 ] units via Cu 2 S 2 linkages. The supramolecular structure of 2 is constructed by weak interactions between planar [Cu II 2 K(L) 2 ] + substructures. Cryomagnetic measurements reveal antiferromagnetic interactions between two Cu II centers in the same sub‐unit and ferromagnetic interactions between Cu II centers of the neighboring sub‐units. The guest K + cation exchange study for 2 suggests the formation of the [Cu II 2 M(L) 2 ](PF 6 ) series in CH 2 Cl 2 (M = Li, Na, K, Rb and Cs). The stability of the complexes decreases in the order [Cu II 2 K(L) 2 ] + > [Cu II 2 Na(L) 2 ] + > [Cu II 2 Rb(L) 2 ] + > [Cu II 2 Cs(L) 2 ] + > [Cu II 2 Li(L) 2 ] + .