The principal C-13 chemical-shift values for the pi-[TCNE](2)(2-) dimer anion within an array of counterions have been measured to understand better the electronic structure of these atypical chemical species in several related TCNE-based structures. The structure of pi-[TCNE](2)(2-) is unusual as it contains two very long C-C bond lengths (ca. 2.9 angstrom) between the two monomeric units and has been found to exist as a singlet state, suggestive of a (1)A(1)g (b(2u)(2)b(1g)(0)) electronic configuration. A systematic study of several oxidation states of [TCNE](n) (n = 0, 1-, 2-) was conducted to determine how the NMR chemical-shift tensor values change as a function of electronic structure and to understand the interactions that lead to spin-pairing of the monomer units. The density functional theory (DFT) calculated nuclear shielding tensors are correlated with the experimentally determined principal chemical-shift values. Such theoretical methods provide information on the tensor magnitudes and orientations of their principal tensor components with respect to the molecular frame. Both theoretical and experimental ethylenic chemical-shielding tensors reveal high sensitivity in the component, delta(perpendicular to), lying in the monomer molecular plane and perpendicular to the pi-electron plane. This largest shift dependence on charge density is observed to be about -111 ppm/e(-) for delta(perpendicular to). The component in the molecular plane but parallel to the central C=C bond, delta\\, exhibits a sensitivity of approximately -43 ppm/ e(-). However, the out-of-plane component delta'(perpendicular to) shows a minimal dependence of -2.6 ppm/e(-) on the oxidation state (n) of [TCNE](n). These relative values support the claim that it is changes within the ethylenic pi- electrons and not the sigma-electrons that best account for the dramatic variations in bonding and shift tensors in this series of compounds. Concerning the intraion bonding, relatively weak Wiberg bond orders between the two monomeric components of the dimer correlate with the long bonds linking the two [TCNE center dot](-) monomers. The chemical-shift tensors for the cyano group, compared to the ethylene shifts, exhibit a reduced sensitivity on the TCNE oxidation state. The experimental principal chemical-shift components agree ( within typical errors) with the calculated quantum mechanical shieldings used to correlate the bonding. The embedded ion model (EIM) was used to investigate the typically large electrostatic lattice potential in these ionic materials. Chemical-shielding principal values calculated with the EIM model differ from experiment by +/- 3.82 ppm on average, whereas in the absence of an electrostatic field model, the experimental and theoretical results agree by +/- 4.42 ppm, which is only a modest increase in error considering the overall ionic magnitudes associated with the tensor variations. Apparently, the effects of the sizable long-range electrostatic fields cancel when the shifts are computed because of lattice symmetry.