Na/CuII/CuI Complexes of Compartmental Schiff Base Ligands Incorporating the [Cu(NCO)2]− Ion.

Two new NaI/CuI,II polynuclear compounds [(NaCu3((R,R)‐3‐MeOSalcy)2(NCO)2](1) and [(NaCu2(3‐MeOSalpn)(NCO)2] (2) have been synthesized using the Schiff base (SB) ligands, (R,R)‐3‐MeOSalcy=(R,R)–N,N′‐bis(3‐methoxysalicylidene)‐1,2‐diaminocyclohexane and 3‐MeOSalpn=N,N′‐bis(3‐methoxysalicylidene)‐1,3‐diaminopropane, respectively. Both complexes contain the rarely observed linear [Cu(NCO)2]− ion which links [{CuII(SB)}2Na]+ ions in 1 or [{CuII(SB)Na}2]2+ ions in 2 producing different linear chain topologies. The mixed valent CuI/IINa network in compound 1 allows for greater magnetic isolation of the paramagnetic ions as compared to compound 2, leading to differences in their EPR spectra. [ABSTRACT FROM AUTHOR]