Sulfur‐Bridged Annulene‐TCNQ Co‐Crystal: A Self‐Assembled ‘‘Molecular Level Heterojunction’’ with Air Stable Ambipolar Charge Transport Behavior

An alternatively stacked donor-acceptor complex from solution is obtained. As a self-assembled "molecular level heterojunction", this crystal displays stable ambipolar transport behaviors in ambient atmosphere. The balance hole and electron transport properties are rationalized through theoretical considerations from band structure calculation, theoretical analysis on super-exchange effects in the intermolecular electronic couplings as well as molecular reorganization energy. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.