TY - JOUR
T1 - Charge-Transport Properties of F6TNAP-Based Charge-Transfer Cocrystals
AU - Dasari, Raghunath R.
AU - Wang, Xu
AU - Wiscons, Ren A.
AU - Haneef, Hamna F.
AU - Ashokan, Ajith
AU - Zhang, Yadong
AU - Fonari, Marina S.
AU - Barlow, Stephen
AU - Coropceanu, Veaceslav
AU - Timofeeva, Tatiana V.
AU - Jurchescu, Oana D.
AU - Brédas, Jean Luc
AU - Matzger, Adam J.
AU - Marder, Seth R.
N1 - Funding Information: X.W., R.A.W., H.F.H., and A.A. contributed equally to this work. This material is based upon work supported by the U. S. Army Research Laboratory and the U. S. Army Research Office under contract/grant number W911NF-13-1-0387, and by the National Science Foundation under grants DMR-1627925, DMR-1708147, and DMR-1523611 (PREM program). The authors thank Cameron H. Feriante for acquiring the AFM data shown in Figure S11 in the Supporting Information. Publisher Copyright: © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/12/1
Y1 - 2019/12/1
N2 - The crystal structures of the charge-transfer (CT) cocrystals formed by the π-electron acceptor 1,3,4,5,7,8-hexafluoro-11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (F6TNAP) with the planar π-electron-donor molecules triphenylene (TP), benzo[b]benzo[4,5]thieno[2,3-d]thiophene (BTBT), benzo[1,2-b:4,5-b′]dithiophene (BDT), pyrene (PY), anthracene (ANT), and carbazole (CBZ) have been determined using single-crystal X-ray diffraction (SCXRD), along with those of two polymorphs of F6TNAP. All six cocrystals exhibit 1:1 donor/acceptor stoichiometry and adopt mixed-stacking motifs. Cocrystals based on BTBT and CBZ π-electron donor molecules exhibit brickwork packing, while the other four CT cocrystals show herringbone-type crystal packing. Infrared spectroscopy, molecular geometries determined by SCXRD, and electronic structure calculations indicate that the extent of ground-state CT in each cocrystal is small. Density functional theory calculations predict large conduction bandwidths and, consequently, low effective masses for electrons for all six CT cocrystals, while the TP-, BDT-, and PY-based cocrystals are also predicted to have large valence bandwidths and low effective masses for holes. Charge-carrier mobility values are obtained from space-charge limited current (SCLC) measurements and field-effect transistor measurements, with values exceeding 1 cm2 V−1 s1 being estimated from SCLC measurements for BTBT:F6TNAP and CBZ:F6TNAP cocrystals.
AB - The crystal structures of the charge-transfer (CT) cocrystals formed by the π-electron acceptor 1,3,4,5,7,8-hexafluoro-11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (F6TNAP) with the planar π-electron-donor molecules triphenylene (TP), benzo[b]benzo[4,5]thieno[2,3-d]thiophene (BTBT), benzo[1,2-b:4,5-b′]dithiophene (BDT), pyrene (PY), anthracene (ANT), and carbazole (CBZ) have been determined using single-crystal X-ray diffraction (SCXRD), along with those of two polymorphs of F6TNAP. All six cocrystals exhibit 1:1 donor/acceptor stoichiometry and adopt mixed-stacking motifs. Cocrystals based on BTBT and CBZ π-electron donor molecules exhibit brickwork packing, while the other four CT cocrystals show herringbone-type crystal packing. Infrared spectroscopy, molecular geometries determined by SCXRD, and electronic structure calculations indicate that the extent of ground-state CT in each cocrystal is small. Density functional theory calculations predict large conduction bandwidths and, consequently, low effective masses for electrons for all six CT cocrystals, while the TP-, BDT-, and PY-based cocrystals are also predicted to have large valence bandwidths and low effective masses for holes. Charge-carrier mobility values are obtained from space-charge limited current (SCLC) measurements and field-effect transistor measurements, with values exceeding 1 cm2 V−1 s1 being estimated from SCLC measurements for BTBT:F6TNAP and CBZ:F6TNAP cocrystals.
KW - charge transport
KW - crystal packing
KW - donor–acceptor cocrystals
KW - electronic couplings
KW - mobility values
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U2 - 10.1002/adfm.201904858
DO - 10.1002/adfm.201904858
M3 - Article
SN - 1616-301X
VL - 29
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 49
M1 - 1904858
ER -