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. 2017 Feb 1;8(2):1163-1168.
doi: 10.1039/c6sc03177c. Epub 2016 Sep 2.

The HOF structures of nitrotetraphenylethene derivatives provide new insights into the nature of AIE and a way to design mechanoluminescent materials

Tao Yu  1 , Depei Ou  1 , Zhiyong Yang  1 , Qiuyi Huang  1 , Zhu Mao  1 , Junru Chen  1 , Yi Zhang  1 , Siwei Liu  1 , Jiarui Xu  1 , Martin R Bryce  2 , Zhenguo Chi  1
Affiliations

The HOF structures of nitrotetraphenylethene derivatives provide new insights into the nature of AIE and a way to design mechanoluminescent materials

Tao Yu et al. Chem Sci. .

Abstract

This study probes the effect of intramolecular rotations on aggregation-induced emission (AIE) and leads to a kind of supramolecular mechanoluminescent material. Two hydrogen-bonded organic frameworks (HOFs), namely HOFTPE3N and HOFTPE4N, have been constructed from nitro-substituted tetraphenylethene (TPE) building blocks, namely tris(4-nitrophenyl)phenylethene (TPE3N) and tetrakis(4-nitrophenyl)ethene (TPE4N). Using single-crystal X-ray diffraction analysis, two types of pores are observed in the HOFTPE4N supramolecular structure. The pore sizes are 5.855 Å × 5.855 Å (α pores) and 7.218 Å × 7.218 Å (β pores). Powder X-ray diffraction and differential scanning calorimetry studies further reveal that the α pores, which contain nitrophenyl rings, quench the emission of HOFTPE4N. This emission can be turned on by breaking the α pores in the HOFs by grinding the sample. Temperature-dependent emission studies demonstrate that the emission quenching of HOFTPE4N is attributed to the intramolecular rotations of nitro-substituted phenyl units within the space of the α pores. These results clearly reveal AIE by controlling the intramolecular rotations, which can serve as a basis for developing mechanoluminescent materials.

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Figures

Fig. 1
Fig. 1. Single crystal structures of TPE2N, HOFTPE3N and HOFTPE4N ; (a) single crystal structure of TPE2N; (b) single crystal structure of HOFTPE3N viewed down the b axis; (c) single crystal structure of HOFTPE4N viewed down the c axis (the nitro substituted phenyls in pore α are labeled in yellow); (d) single crystal structure of HOFTPE4N viewed down the b axis (the nitro substituted phenyls in pore α are labeled in yellow); (e) structure of pore α; (f) structure of pore β.
Fig. 2
Fig. 2. Mechanoluminescent properties of HOFTPE4N: (a) emission spectra of HOFTPE4N and ground HOFTPE4N, and (b) photographs of the mechanoluminescent properties of HOFTPE4N and the quenching processes.
Fig. 3
Fig. 3. pXRD spectra of TPE4N in different states: (a) crystal simulated, (b) HOF state, (c) ground HOF state, (d) amorphous state, (e) heated HOF state, (f) dichloromethane fumed amorphous state, and (g) heated amorphous state.
Fig. 4
Fig. 4. Temperature-emission spectra of HOFTPE4N. The inset shows photographs of the samples at 298 and 77 K.
See this image and copyright information in PMC

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