Shear- and UV-induced fluorescence switching in stilbenic pi-dimer crystals powered by reversible [2 + 2] cycloaddition.
We have designed and synthesized asymmetric cyano-stilbene derivatives containing trifluoromethyl (-CF(3)) substituents with the aim of producing tightly packed pi-dimer systems that as crystals exhibit reversible [2 + 2] cycloaddition with characteristic fluorescence modulation. (Z)-3-(3',5'-Bis(trifluoromethyl)biphenyl-4-yl)-2-(4'-(trifluoromethyl)biphenyl-4-yl)acrylonitrile (CN(L)-TrFMBE) and its derivatives were found to form antiparallel pi-dimer stacks in crystals due to their specific intermolecular interactions, including C-F...H and C-F...pi interactions. The CN(L)-TrFMBE pi-dimer crystals (and powder) are not at all fluorescent initially but switch to a highly fluorescent state (Phi(PL) = 24%) when an external shear-strain and/or prolonged UV (365 nm) irradiation is applied. Our experimental and theoretical investigations show that the fluorescence modulation in this particular system is due to the external and/or internal (in the case of UV irradiation) shear-induced lateral displacement of the pi-dimer molecular pair, which effectively turns the fluorescence emission on at the cost of frustrated [2 + 2] cycloaddition. Further, the fluorescence 'off' state can be restored by thermal annealing, which regenerates the tightly packed pi-dimer by reverse displacement together with the thermal dissociation of the [2 + 2] cycloaddition product. This system provides a very rare example of high-contrast reversible fluorescence switching that is driven by a change in the molecular packing mode in the solid state, which enables piezochromic and photochromic responses.
Chung
Jong Won
JW
Center for Supra molecular Optoelectronics Materials and Department of Materials Science and Engineering, ENG445, Seoul National University, San 56-1, Shilim-dong, Kwanak-ku, Seoul 151-744, Korea.
You
Youngmin
Y
Huh
Hyun Sue
HS
An
Byeong-Kwan
BK
Yoon
Seong-Jun
SJ
Kim
Se Hun
SH
Lee
Soon W
SW
Park
Soo Young
SY