Single‐Molecule Conductance of a π‐Hybridized Tripodal Anchor while Maintaining Electronic Communication

Abstract Direct hybridization between the π‐orbital of a conjugated molecule and metal electrodes is recognized as a new anchoring strategy to enhance the electrical conductance of single‐molecule junctions. The anchor is expected to maintain direct hybridization between the conjugated molecule and the metal electrodes, and control the orientation of the molecule against the metal electrodes. However, fulfilling both requirements is difficult because multipodal anchors aiming at a robust contact with the electrodes often break the π‐conjugation, thereby resulting in an inefficient carrier transport. Herein, a new tripodal anchor framework—a 7,7‐diphenyl‐7H‐benzo[6,7]indeno[1,2‐b]thiophene (PBIT) derivative—is developed. In this framework, π‐conjugation is maintained in the molecular junction, and the tripodal structure makes the molecule stand upright on the metal electrode. Molecular conductance is measured by the break junction technique. A vector‐based classification and first‐principles transport calculations determine the single‐molecule conductance of the tripodal‐anchoring structure. The conductance of the PBIT‐based molecule is higher than that of the tripodal anchor having sp³ carbon atoms in the carrier transport pathway. These results demonstrate that extending the π‐conjugation to the tripodal leg is an effective strategy for enhancing the conductivities of single‐molecule junctions.