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Polymorph and anisotropic Raman spectroscopy of Phz-Hca cocrystals

Science China Materials 2021年第1期64卷 169-178页

作者： Weigang Zhu Yunli Wang Chengcheng Huang Lingyun Zhu Yonggang Zhen Huanli Dong Zhixiang Wei Dong Guo Wenping Hu Laboratory of Organic Solids Institute of ChemistryChinese Academy of SciencesBeijing100190China University of Chinese Academy of Sciences Beijing100049China Institute of Acoustics Chinese Academy of SciencesBeijing100190China School of Materials Science and Engineering Beihang UniversityBeijing100191China National Center for Nanoscience and Technology Beijing100190China Tianjin Key Laboratory of molecular Optoelectronic Sciences Department of ChemistrySchool of ScienceTianjin University&Collaborative Innovation Center of Chemical Science and Engineering(Tianjin)Tianjin300072China

The nucleation and growth mechanism and polymorph-property correlations in the molecular cocrystal field are widely sought but currently remain unclear. Herein, a new wire-like morphology of phenazine(Phz)-chloranilic acid(H2ca) cocrystal(PHC) is demonstrated for the first time, and the self-assembly of Phz and H2ca is controlled to selectively prepare kinetically stable wires and thermodynamically stable plates. Specifically, low precursor concentration is beneficial for one-dimensional(1D) self-assembly along the [010] crystallographic direction, while only supersaturation can trigger 2D self-assembly along the [100] and [010] directions, respectively. This is understandable in terms of the(020) face showing the largest attachment energy(Eatt) and the(002) face possessing the smallest surface energy(Esurf). Moreover, anisotropic Raman spectra related to the mode symmetry and atomic displacements in two types of PHCs are revealed, and the same Raman-active vibrational bands of PHC wire and plate show different polarization responses, which is intrinsically ascribed to their different molecular ***, this is the first case that morphologies of cocrystal are precisely tuned with comprehensive investigations of their anisotropic vibrational characteristics.

关键词： molecular cocrystal polymorph self-assembly Raman spectroscopy anisotropy

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