TY - JOUR
T1 - Electronic Properties of 1,5-Diaminonaphthalene:Tetrahalo-1,4-benzoquinone Donor-Acceptor Cocrystals
AU - Behera, Rakesh Kumar
AU - Goud, N. Rajesh
AU - Matzger, Adam J.
AU - Brédas, Jean Luc
AU - Coropceanu, Veaceslav
N1 - Funding Information:
This collaborative work is supported by the Army Research Office in the form of a Multidisciplinary University Research Initiative (MURI) (W911NF-13-1-0387). We acknowledge funding from NSF Grant No. CHE-0840456 for the Rigaku AFC10K Saturn 944+ CCD based X-ray diffractometer. We thank Dr. Jeff W. Kampf for single-crystal X-ray analysis and Dr. Alexandr Fonari for fruitful discussions.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/10/26
Y1 - 2017/10/26
N2 - We have investigated the electronic properties of four charge-transfer cocrystals involving 1,5-diaminonaphthalene (DAN) as donor and fluoranil (FA), chloranil (CA), bromanil (BA), and iodanil (IA) as acceptors. While DAN-FA, DAN-CA, and DAN-BA crystallized in a mixed-stack fashion, DAN-IA crystallized with segregated stacks. For the mixed-stack cocrystals, electronic-structure calculations using density functional theory predict large electron-hole couplings with small effective masses, which strongly suggests that these DAN-XA cocrystals are suitable for charge-transport applications. Among the four cocrystals, DAN-CA crystallized in a noncentrosymmetric space group; according to our computational analysis, it is predicted to be weakly ferroelectric with a second-order electrical susceptibility (χ(2)) similar to that of urea. The ionicities (ρ) of the cocrystals calculated using Mulliken population compare well with the experimental results. The couplings between donor and acceptor molecules in DAN-IA are very small, leading to a very small ρ. This is not typical for a system with a segregated-stack packing motif, indicating that hydrogen and halogen bondings can have a strong impact on the structure-property relations in cocrystals.
AB - We have investigated the electronic properties of four charge-transfer cocrystals involving 1,5-diaminonaphthalene (DAN) as donor and fluoranil (FA), chloranil (CA), bromanil (BA), and iodanil (IA) as acceptors. While DAN-FA, DAN-CA, and DAN-BA crystallized in a mixed-stack fashion, DAN-IA crystallized with segregated stacks. For the mixed-stack cocrystals, electronic-structure calculations using density functional theory predict large electron-hole couplings with small effective masses, which strongly suggests that these DAN-XA cocrystals are suitable for charge-transport applications. Among the four cocrystals, DAN-CA crystallized in a noncentrosymmetric space group; according to our computational analysis, it is predicted to be weakly ferroelectric with a second-order electrical susceptibility (χ(2)) similar to that of urea. The ionicities (ρ) of the cocrystals calculated using Mulliken population compare well with the experimental results. The couplings between donor and acceptor molecules in DAN-IA are very small, leading to a very small ρ. This is not typical for a system with a segregated-stack packing motif, indicating that hydrogen and halogen bondings can have a strong impact on the structure-property relations in cocrystals.
UR - http://www.scopus.com/inward/record.url?scp=85032642030&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85032642030&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.7b08360
DO - 10.1021/acs.jpcc.7b08360
M3 - Article
AN - SCOPUS:85032642030
VL - 121
SP - 23633
EP - 23641
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 42
ER -