Abstract
Mixed cocrystals derived from electron-rich donor (D) and electron-deficient acceptor (A) molecules showcase electronic, optical, and magnetic properties of interest for a wide range of applications. We explore the structural and electronic properties of a cocrystal synthesized from dithieno[3,2-a:2′,3′-c]phenazine (DTPhz) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), which has a mixed-stack packing arrangement of the (π-electronic) face-to-face stacks in a 2:1 D:A stoichiometry. Density functional theory investigations reveal that the primary electronic characteristics of the cocrystal are not determined by electronic interactions along the face-to-face stacks, but rather they are characterized by stronger electronic interactions orthogonal to these stacks that follow the edge-to-edge donor-donor or acceptor-acceptor contacts. These distinctive electronic characteristics portend semiconducting properties that are unusual for semiconducting mixed cocrystals and suggest further potential to design organic semiconductors with orthogonal transport characteristics for different charge carriers.
| Original language | English |
|---|---|
| Pages (from-to) | 4510-4515 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 8 |
| Issue number | 18 |
| DOIs | |
| State | Published - Sep 21 2017 |
Bibliographical note
Publisher Copyright:© 2017 American Chemical Society.
Funding
The work at the University of Kentucky was supported in part by the National Science Foundation (NSF DMR-1627428) and start-up funds provided by the University of Kentucky Vice President for Research. The work at New Mexico Highlands University was supported in part by the NSF via DMR-0934212, DMR-1523611 (PREM), and IIA-130134, with additional support from the Center for Emergent Materials, an NSF MRSEC under award number DMR-1420451, and New Mexico EPSCoR Infrastructure Seed Award. Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). We thank Dr. Sean Ryno for helpful discussions and Dr. Boris B. Averkiev for help with X-ray structural analysis. Y.A.G. thanks Professor Seth R. Marder for providing access to the electrochemical setup, synthetic facility, and reagents for the preparation of some of the TMS-BDDO starting material and Professor Yang Qin for providing access to synthetic and NMR facilities.
| Funders | Funder number |
|---|---|
| Center for Emergent Materials | |
| NSF MRSEC | DMR-1420451 |
| National Science Foundation (NSF) | 1301346, NSF DMR-1627428 |
| Office of Experimental Program to Stimulate Competitive Research | |
| University of Kentucky | |
| New Mexico State University | DMR-0934212, DMR-1523611, IIA-130134 |
| Office of the Vice President for Research, University of South Carolina |
ASJC Scopus subject areas
- General Materials Science
- Physical and Theoretical Chemistry