The positional isomers of <i>tert</i>-butylnitroxide
(NO) substituted 4,5,9,10-tetramethoxypyrene-based mono- and biradical
are synthesized. While the biradical 2,7-TMPNO in which two NO radical
moieties are attached at the nodal plane of pyrene adopts a semiquinoid
structure, the 1,6- and 1,8-isomers of the same exist in biradical
form. The tuning of the antiferromagnetic exchange interactions is
achieved by synthesizing the positional isomers of the biradical while
maintaining the same radical moiety as well as the π spacer