Neutral and ionic complexes of C60with (ZnOEP)2·BPy coordination dimers

Coordination (ZnOEP)2·BPy dimers formed by zinc octaethylporphyrin and 4,4′-bipyridine co-crystallize with neutral C60 and the (TDAE˙+)·(C60˙–) ion-radical salt to form molecular and ionic multi-component complexes: {(ZnOEP)2·BPy}·(C60)2·(CHCl3)2 (1) and (TDAE˙+)2·{(ZnOEP)2·BPy}·(C60˙–)2·(C6H6)0.75·(C6H4Cl2)0.25 (2). The C60 molecules are arranged in layers in 1 with the interfullerene center-to-center distances of 10.04–10.17 A and in linear chains in 2 with the uniform interfullerene center-to-center distance of 10.61 A. EPR measurements show exchange interaction between C60˙– and TDAE˙+ ion-radicals in 2, which results in the appearance of one signal with g = 2.0027 and ΔHpp = 19.8 G at 295 K rather than two signals from individual ion-radicals. The EPR signal from 2 is split into two components below 30 K and its integral intensity decreases below 9.6 K, which is evidence of antiferromagnetic interactions of spins.