Phosphorescent co-crystal assembled by 1,4-diiodotetrafluorobenzene with carbazole based on C-I•••π halogen bonding
Phosphorescent co-crystal assembled by 1,4-diiodotetrafluorobenzene with carbazole based on C-I•••π halogen bonding
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DOI：
10.1039/c2jm16257a
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发表时间：
2012-01-01
影响因子：
--
通讯作者：
Jin, Wei Jun
中科院分区：
文献类型：
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作者：
Gao, Hai Yue;Shen, Qian Jin;Jin, Wei Jun
1，4-二碘四氟苯（1，4-DITFB）是一种优良的卤素成键给体，可用于组装咔唑有机磷光共晶体，其中1，4-DITFB可作为功能合成子、通过卤素键连接咔唑分子的粘合剂和通过自旋轨道耦合增强咔唑磷光发光的重原子微扰剂。XRD分析表明，1，4-DITFB与咔唑的化学计量比为2：1。由C-I中心点中心点π卤素键和π中心点中心点π边对边堆积构成的无限长链在维持一维无限长链的稳定性方面具有重要意义。链间键合包括C-H中心点I氢键、H中心点F或F中心点F接触，以将无限长链延伸到3D结构。计算的卤素键合能为ca。23.0 kJ mol（-1），表明强卤素键合。该共晶还通过粉末XRD、FT-IR、拉曼和固体F-19 NMR光谱进行了良好表征。此外，通过将水滴入1，4-DITFB和咔唑的乙醇溶液中，可以非常容易地在水中组装作为悬浮微粒的共晶。1，4-DITFB与咔唑形成的C-I中心点π卤素键对一些纳米或微米磷光材料的开发具有指导意义。
1,4-diiodotetrafluorobenzene (1,4-DITFB) is an excellent halogen bonding donor and is used to assemble an organic phosphorescent co-crystal with carbazole in which 1,4-DITFB is expected to act as a functional synthon, the cement to link carbazole molecules by halogen bonding and heavy atom perturber to enhance phosphorescence of the emitter carbazole by spin-orbital coupling. The XRD reveals that the stoichiometry of (2 : 1) between 1,4-DITFB and carbazole occurs. An infinite chain is constructed by the C-I center dot center dot center dot pi halogen bonding and the pi center dot center dot center dot pi stacking of edge to edge between two 1,4-DITFB molecules is significant in maintaining stability of the 1D infinite chain. The inter-chain bonding includes C-H center dot center dot center dot I hydrogen bonding, H center dot center dot center dot F or F center dot center dot center dot F contacts to extend the infinite chain to 3D structure. The calculated halogen bonding energy is ca. 23.0 kJ mol(-1) based on the single crystal structure, indicating a strong halogen bonding. The co-crystal also is well characterized by powder XRD, FT-IR, Raman, and solid F-19 NMR spectroscopy. Moreover, the co-crystal as suspension microparticles can be very easily assembled in water by dropping water into an ethanol solution of 1,4-DITFB and carbazole. The C-I center dot center dot center dot pi halogen bonding of 1,4-DITFB with carbazole should be instructive to develop some phosphorescent nano-or micro-materials.