ae9b01978_si_001.pdf (3.2 MB)
Harnessing Direct (Hetero)Arylation in Pursuit of a Saddle-Shaped Perylene Diimide Tetramer
journal contribution
posted on 2019-11-19, 17:04 authored by Josh D.
B. Koenig, Audrey Laventure, Gregory C. WelchThis contribution explores the direct (hetero)arylation
(DHA) cross-coupling
of a saddle-like, π-conjugated cyclooctatetrathiophene (Th4) core with the N-annulated perylene
diimide (PDI) chromophore. Replacing the bulky pivalic acid with acetic
acid enabled a facile cross-coupling, selectively forming a PDI tetramer
(Th4PDI4) in a 70% overall yield. The optoelectronic properties
of Th4PDI4 were characterized and density functional theory (DFT)
was used to calculate the optimized molecular geometry and molecular
orbitals (MOs). Energy levels of MOs determined by cyclic voltammetry
corresponded well with those
calculated using DFT. The molecular geometry calculated by DFT showed Th4PDI4 adopts two separate PDI–PDI conformations (propeller
and double-decker). Organic photovoltaic (OPV) devices were fabricated
using a blend of PTB7-Th/Th4PDI4, where an initial power conversion
efficiency (PCE) of 1.89% was improved by testing a series of solvent
additives and thermal annealing techniques. Through use of 3% (v/v)
1-chloronaphthalene additive, a combination of higher short circuit
current (Jsc = 10.2 mA/cm2)
and fill factor (FF = 42%) led to an overall increase in PCE to 4.26%.