Chirality has been a property of central importance in physics, chemistry and biology for more than a century. Recently, electrons were found to become spin polarized after transmitting through chiral molecules, crystals, and their hybrids. This phenomenon, called chirality-induced spin selectivity (CISS), presents broad application potentials and far-reaching fundamental implications involving intricate interplays among structural chirality, topological states, and electronic spin and orbitals. However, the microscopic picture of how chiral geometry influences electronic spin remains elusive, given the negligible spin-orbit coupling (SOC) in organic molecules. In this work, we address this issue via a direct comparison of magnetoconductance (MC) measurements on magnetic semiconductor-based chiral molecular spin valves with normal metal electrodes of contrasting SOC strengths. The experiment reveals that a heavy-metal electrode provides SOC to convert the orbital polarization induced by the chiral molecular structure to spin polarization. Our results illustrate the essential role of SOC in the metal electrode for the CISS spin valve effect. A tunneling model with a magnetochiral modulation of the potential barrier is shown to quantitatively account for the unusual transport behavior.
We report the synthesis, magnetic properties, and transport properties of paramagnetic metal complexes, [Co(DMF)4(TCNQ)2](TCNQ)2 (1), [La(DMF)8(TCNQ)](TCNQ)5 (2), and [Nd(DMF)7(TCNQ)](TCNQ)5 (3) (DMF = N,N-dimethylformamide, TCNQ = 7,7,8,8-tetracyanoquinodimethane). All three compounds contain fractionally charged TCNQδ- anions (0 < δ < 1) and mononuclear complex cations in which the coordination environment of a metal center includes several DMF molecules and one or two terminally coordinated TCNQδ- anions. The coordinated TCNQδ- anions participate in π-π stacking interactions with noncoordinated TCNQδ- anions, forming columnar substructures that provide efficient charge-transporting pathways. As a result, temperature-dependent conductivity measurements demonstrate that all three compounds exhibit semiconducting behavior.
