Orbital hybridization of donor and acceptor to enhance the conductivity of mixed-stack complexes.

Mixed-stack complexes which comprise columns of alternating donors and acceptors are organic conductors with typically poor electrical conductivity because they are either in a neutral or highly ionic state. This indicates that conductive carriers are insufficient or are mainly localized. In this study, mixed-stack complexes that uniquely exist at the neutral-ionic boundary were synthesized by combining donors (bis(3,4-ethylenedichalcogenothiophene)) and acceptors (fluorinated tetracyanoquinodimethanes) with similar energy levels and orbital symmetry between the highest occupied molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor. Surprisingly, the orbitals were highly hybridized in the single-crystal complexes, enhancing the room-temperature conductivity (10-4-0.1 S cm-1) of mixed-stack complexes. Specifically, the maximum conductivity was the highest reported for single-crystal mixed-stack complexes under ambient pressures. The unique electronic structures at the neutral-ionic boundary exhibited structural perturbations between their electron-itinerant and localized states, causing abrupt temperature-dependent changes in their electrical, optical, dielectric, and magnetic properties.

Single-crystalline oligomer-based conductors modeling the doped poly(3,4-ethylenedioxythiophene) family.

Conductive polymers with highly conjugated systems, such as the doped poly(3,4-ethylenedioxythiophene) (PEDOT) family, are commonly used in organic electronics. However, their structural inhomogeneity with various chain lengths makes it difficult to control their conductivities and structural details. On the other hand, low-molecular-weight materials have well-defined structures but relatively narrow conjugate areas with a limited range of Coulomb repulsion between carriers (Ueff), which hamper the flexible control of conductivities. To bridge this gap, we developed oligomer-based conductors, which are intermediate materials between polymers and low-molecular-weight materials. Using a library of single-crystal charge-transfer salts of oligo(3,4-ethylenedioxythiophene) (oligoEDOT) analogs that model the doped PEDOT family, we have investigated the structure-determining factors affecting their conductivities, such as counter anion variations, lengths of oligomer donor, and band fillings. Through the screening study, we developed oligoEDOT analogs with tunable room temperature conductivities by several orders of magnitude, including a metallic state above room temperature. In this study, we consistently evaluated the electronic structural insights by first-principles calculations and revealed that Ueff is the dominant factor that determines the relationship between the structures and conductivities. The unique features of oligoEDOT conductor systems with widely variable Ueff can differentiate these systems from strongly electron-correlated systems.

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family.

Modern organic conductors are typically low-molecular-weight or polymer-based materials. Low-molecular-weight materials can be characterized using crystallographic information, allowing structure-conductivity relationships to be established and conduction mechanisms to be understood. However, controlling their conductive properties through molecular structural modulation is often challenging because of their relatively narrow conjugate areas. In contrast, polymer-based materials have highly π-conjugated structures with wide molecular-weight distributions, and their structural inhomogeneity makes characterizing their structures difficult. Thus, we focused on the less-explored intermediate, i.e., single-molecular-weight oligomers that model doped poly(3,4-ethylenedioxythiophene) (PEDOT). The dimer and trimer models provided clear structures; however, the short oligomers led to much lower conductivities (<10-3 S cm-1) than that of doped PEDOT. Herein, we elongated the oligomer to a tetramer through geometrical tuning based on a mixed sequence. The "P-S-S-P" sequence (S: 3,4-ethylenedithiothiophene; P: 3,4-(2',2'-dimethypropylenedioxy)thiophene) with twisted S-S enhanced the solubility and chemical stability. The subsequent oxidation process planarized the oligomer and expanded the conjugate area. Interestingly, the sequence involving sterically bulky outer P units allowed the doped oligomer to form a pitched π-stack in the single-crystal form. This enabled the inclusion of excess counter anions, which modulated the band filling. The combined effects of conjugate area expansion and band-filling modulation significantly increased the room-temperature conductivity to 36 S cm-1. This is the highest value reported for a single-crystalline oligomer conductor. Furthermore, a metallic state was observed above room temperature in a single-crystalline oligoEDOT for the first time. This unique mixed-sequence strategy for oligomer-based conductors enabled the precise control of conductive properties.