In Situ Imaging of On-Surface, Solvent-Free Molecular Single-Crystal Growth-山东大学晶体材料研究所

Guangfeng Liu^†,Jie Liu^†,Hao Sun^§,Xiaoxin Zheng^†,Yang Liu ^*^†,Xiaomin Li^‡,He Qi^‡,Xuedong Bai^‡,Kenneth A. Jackson^#, andXutang Tao ^*^†

^†State Key Laboratory of Crystal Materials,Shandong University, Jinan, Shandong 250100,P. R. China

^§Bruker (Beijing) Scientific Technology Co., Ltd., Beijing 100081,P. R. China

^‡Institute of Physics,Chinese Academy of Sciences, Beijing 100190,P. R. China

^#Department of Materials Science and Engineering,The University of Arizona, Tucson, Arizona 85721,United States

J. Am. Chem. Soc.,2015,137(15), pp 4972–4975

DOI:10.1021/jacs.5b02637

Publication Date (Web): April 7, 2015

*liuyangicm@sdu.edu.cn, *txt@sdu.edu.cn

AFM peak force error images from Movie S3 show the migration of [Ni(qt)2] NPs before crystallization. The trajectory of NPs’ migration is indicated by yellow arrows, and the remarkable changed regions on the film are highlighted by dashed circles. Film thickness, ∼30 nm; annealing temperature, 130 °C.

Abstract

The formation of crystalline materials has been studied for more than a century. Recent discoveries about the self-assembly of many inorganic materials, involving aggregation of nanoparticle (NP) precursors or pre-nucleation clusters, challenge the simple assumptions of classical crystallization theory. The situation for organic materials is even more of a terra incognita due to their high complexity. Using in situ high-temperature atomic force microscopy during the solvent-free crystallization of an organic compound [Ni(quinolone-8-thiolate)₂], we observe long-range migration of NPs on a silica substrate and their incorporation into larger crystals, suggesting a non-classical pathway in the growth of the molecular crystal.