XRD reveals the single crystal of 9-bromophenanthrene (9-BrP) with an infinite herringbone chain structure constructed by itself based on C–H⋯π hydrogen bond and additional edge-to-edge type π–π interaction between phenanthrenes. While, 9-iodophenanthrene (9-IP) possesses an infinite zigzag chain assembled via C–I⋯π halogen bond (XB) and its structure is extended to 3D by typical π–π stacking between phenanthrenes. The interaction energies were estimated by theoretical calculation. The phosphorescence maximum emission wavelengths of two single crystal samples have a significant difference between each other with the 640 nm for 9-BrP and 590 nm for 9-IP, respectively. To understand the effect of interactions between 9-halophenanthrenes in crystals on their phosphorescence, two strategies were utilized to keep them monomers, including 9-halophenanthrenes within hydrophobic cavity of cyclodextrin (CD) with space-regulation of cyclohexane, and sandwiching them in NaDC aggregates. The phosphorescence spectra and decay curves from isolated 9-BrP/9-IP monomers were successfully obtained. All results indicate that the C–H⋯π hydrogen bond and C–I⋯π halogen bond should have smaller effect to their luminescent behaviors while different π–π interactions are the main reason to lead to the obvious different phosphorescent properties between 9-BrP and 9-IP crystals and the largely red-shifted emission bands by approximately 100 nm compared with that of isolated monomers in cyclodextrin/NaDC media or dilute solution of 9-BrP/9-IP. The microcrystal particles separated from suspensions of 9-halophenanthrenes have almost consistent phosphorescent properties compared with their single crystals. Powder XRD confirms the homogeneity of the single crystals and microcrystal particles separated from suspensions of 9-halophenanthrenes and their consistency in structures.

XRD揭示了9-溴菲（9-BrP）的单晶，其自身基于C–H⋯π氢键和菲之间的附加的边到边类型π–π相互作用而构建的无限的人字形链结构。而9-碘菲（9-IP）拥有通过C–I⋯π卤素键（XB）及其结构通过菲之间典型的π–π堆积扩展到3D。相互作用能通过理论计算来估计。两个单晶样品的最大磷光发射波长之间存在显着差异，分别对于9-BrP为640 nm，对于9-IP为590 nm。为了了解晶体中9-卤菲之间的相互作用对其磷光的影响，采用了两种策略将其保持在单体中，包括9-卤菲在环糊精（CD）的疏水腔中，并调节环己烷的空间，并将其夹在NaDC聚集体中。从分离出的9-BrP / 9-IP单体成功获得了磷光光谱和衰减曲线。所有结果表明，C–H⋯π氢键和C–I⋯π卤素键对它们的发光行为影响较小，而不同的π–π相互作用是导致9-BrP之间明显不同的磷光性质的主要原因。与9-IP晶体相比，与环糊精/ NaDC介质或9-BrP / 9-IP稀溶液中的分离单体相比，发射带明显偏红约100 nm。与9-卤菲悬浮液分离的微晶颗粒与其单晶相比具有几乎一致的磷光性质。粉末XRD证实了从9-卤菲悬浮液中分离出的单晶和微晶颗粒的均匀性及其结构一致性。