Research Progress on Design and Preparation Methods of Organic Cocrystals

doi:10.16553/j.cnki.issn1000-985x.2025.0084

Abstract

Abstract: Organic cocrystals are a novel class of functional materials formed by the synergistic assembly of two or more organic molecules through non-covalent interactions. By strategically modulating the molecular composition and assembly patterns of donor （D） and acceptor （A） components， these materials transcend the performance limitations of single-component systems， exhibiting diverse stacking modes， abundant intermolecular interactions and versatile functional compositions. Their physicochemical properties can be tailored to meet specific requirements while demonstrating novel characteristics. With groundbreaking applications in optoelectronic materials and pharmaceutical formulations， the preparation methods of organic cocrystals have emerged as a central challenge in materials research. The key objective of cocrystal synthesis lies in the rational design and selection of D/A components to achieve desired morphologies， dimensions， and functionalities. This article summarizes the preparation methods for organic cocrystals， beginning with an introduction to their structural features and design principles， following by an overview of their unique properties. A detailed discussion of synthesis techniques is subsequently presented， concluding with perspectives on future development prospects in this field.

Key words: organic cocrystal; cocrystal engineering; self-assembly; solution method; vapor phase method; grinding method

CLC Number:

O782

WU Bingbing, ZHANG Xi, XIE Fang. Research Progress on Design and Preparation Methods of Organic Cocrystals[J]. Journal of Synthetic Crystals, 2025, 54(9): 1491-1500.

Figures/Tables 10

Fig.1 Schematic diagram of the structure of common donor （D） and acceptor （A）

Fig.2 Schematics diagram of intermolecular interactions

Fig.3 （a） A full color emissive organic cocrystal synthesized via CT interactions［14］；（b） chemical structures of CNDSB， HQ， and TFHQ， along with ASE of the CHQ cocrystal［19］；（c） azobenzene-dioxane cocrystal structure and its application schematic diagram in photolithography［21］；（d） strong CPL from a chiral polycyclic aromatic hydrocarbons and OFN co-assembly system［23］

Table 1 Principles， advantages and disadvantages of organic cocrystal preparation methods

制备方法	原理与优势	局限性
溶液法	基于溶解度差异诱导共晶析出，产物晶型完整度高	溶剂残留影响纯度，不适用于难溶体系
气相法	通过组分升华-共沉积实现原子级混合，产物纯度大于99%	设备成本高，仅适用于易升华小分子
研磨法	机械力驱动固-固相变，无需溶剂且反应时间短	易引入晶格缺陷，粒径分布宽

Fig.4 Schematic diagram of the preparation method for organic cocrystals by solution method

Fig.5 （a） Molecular structures of TMTES-P and DTTCNQ and their formed P1 and P2 phase cocrystals［25］；（b） NA［4］A and TCNB forming 1，2-NTC and 1，3-NTC cocrystals through temperature regulation［27］；（c） cocrystals of TCNB and naphthol derivatives［29］

Fig.6 Schematic diagram of physical vapor transport

Fig.7 （a） Schematics diagrams of micro-spacing air sublimation［35］；（b） schematic diagrams of the preparation of Pe-PeO and PeO-Pe heterojunctions［36］

Fig.8 （a） Schematic diagram of the grinding method；（b） co-crystallization of diphenylamine and benzophenone；（c） preparation of the cocrystal of IMBT and TCNB by grinding method［42］

Fig.9 Catalytic additive-assisted grinding method

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