Shear- and UV-Induced Fluorescence Switching in Stilbenic π-Dimer Crystals Powered by Reversible [2+2] Cycloaddition

被引:311
作者
Chung, Jong Won [1 ,2 ]
You, Youngmin [1 ,2 ]
Huh, Hyun Sue [3 ]
An, Byeong-Kwan [1 ,2 ]
Yoon, Seong-Jun [1 ,2 ]
Kim, Se Hun [1 ,2 ]
Lee, Soon W. [3 ]
Park, Soo Young [1 ,2 ]
机构
[1] Seoul Natl Univ, ENG445, Ctr Supra Mol Optoelect Mat, Seoul 151744, South Korea
[2] Seoul Natl Univ, ENG445, Dept Mat Sci & Engn, Seoul 151744, South Korea
[3] Sungkyunkwan Univ Nat Sci Campus, Dept Chem, Suwon 440746, South Korea
关键词
CYANO-SUBSTITUTED DIPHENYLBUTADIENES; SOLID-STATE PHOTODIMERIZATION; TRANS-CINNAMIC ACID; SINGLE-CRYSTAL; MOLECULAR PACKING; ORGANIC-CRYSTALS; SUPRAMOLECULAR CONTROL; COORDINATION POLYMER; LIQUID-CRYSTALLINE; EMISSION;
D O I
10.1021/ja900803d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have designed and synthesized asymmetric cyano-stilbene derivatives containing trifluoromethyl (-CF3) substituents with the aim of producing tightly packed pi-dimer systems that as crystals exhibit reversible [2 + 2] cycloaddition with characteristic fluorescence modulation. (2)-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 center dot center dot center dot H and C-F center dot center dot center dot 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.
引用
收藏
页码:8163 / 8172
页数:10
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