The importance of the multiconfigurational description of the junction electronic structure is investigated in quantum transport through molecular devices. Using an accurate wavefunction-based description of the low-energy spectroscopy, transport through a 2-electron/2-molecular orbital prototype is evaluated, covering lowly - H-2-like - to highly - O-2-like - correlated regimes. The contributions arising from the presence of competing singlet and triplet states in magnetic systems are analyzed. It is shown that the electronic conductivity provides a signature of the full multiplet energy spectrum, as well as of the multideterminant structure of wavefunctions. (C) 2011 Elsevier B.V. All rights reserved.