Organic
donor–acceptor cocrystals can improve the light-harvesting
ability in visible or near-infrared regions, having a good photothermal
conversion efficiency in some cases. While the photothermal conversion
mechanism of organic cocrystals is still ambiguous. Here, the fluorescent
molecule pyrene with a wide energy gap is selected as a donor, and
the conjugated tetracyanide molecules are chosen as the acceptors.
Pyrene and tetracyanide molecules are readily self-assembled into
cocrystals (pyrene-tetracyanobenzene (PBC), pyrene-tetracyanoethylene
(PEC), and pyrene-tetracyanoquinodimethane (PQC)) through intermolecular
charge transfer. By changing the framework of acceptors, the optical
properties of these cocrystals are tuned from photoluminescence (PBC)
to photothermal conversion (PEC and PQC). PEC and PQC have an excellent
photothermal conversion efficiency under near-infrared laser (808
nm) irradiation, its values can reach 80.9 and 83.3%, respectively.
Based on the intermolecular interactions of cocrystals, femtosecond
transient absorption, and excited-state theoretical calculation studies,
the excellent photothermal conversion is attributed to the free rotation
of the −C(CN)2 group, which opens a tailormade
channel for the effective nonradiative decay of the excited charge-transfer
state. This study paves a way to design organic donor–acceptor
cocrystal materials with high photothermal conversion efficiency.