Cassingham Megan A, Lamahewage Sujeewa N S, Goh Yang G, Squires Alexander G, Ponnekanti Aamani, Karabadjakyan Sarah, Wapner Anna, Djurovich Peter I, Scanlon David O, Rossini Aaron J, Thompson Mark E, Melot Brent C
Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.
Ames National Laboratory, Division of Materials Science and Engineering, Ames, Iowa 50011, United States.
Chem Mater. 2025 Mar 25;37(7):2418-2426. doi: 10.1021/acs.chemmater.4c02364. eCollection 2025 Apr 8.
Hybrid metal halides are a remarkably dynamic family of materials that offer a flexible platform for exploring the novel crystal chemistry that emerges at the intersection of organic and inorganic solids. Herein, we report the discovery of a hybrid that contains two molecules effectively adopting isostructural geometry, (1-NA)PbI and (1-MQ)PbI, and our attempts to create solid solutions of the two beyond the 1:1 ratio. Single-crystal X-ray diffraction, combined with solid-state NMR measurements, clearly show that despite having nearly identical steric geometry, the only mixed phase attained was the composition (1-MQ)(1-NA)PbI, which exhibits a high degree of order between the two molecules. We propose that this ordering is primarily driven by local molecular dipoles, which ultimately creates a band structure in the blended phase that is highly characteristic of the end members, with little sign of rehybridization between the organic or inorganic components.
杂化金属卤化物是一类极具活力的材料家族，为探索有机和无机固体交界处出现的新型晶体化学提供了一个灵活的平台。在此，我们报告了一种杂化物的发现，该杂化物包含两个有效采用等结构几何形状的分子，即(1-NA)PbI和(1-MQ)PbI，以及我们尝试制备这两种分子比例超过1:1的固溶体的过程。单晶X射线衍射结合固态核磁共振测量清楚地表明，尽管这两个分子具有几乎相同的空间几何形状，但唯一获得的混合相是(1-MQ)(1-NA)PbI组成，其在两个分子之间表现出高度的有序性。我们认为这种有序性主要由局部分子偶极驱动，这最终在混合相中产生了一种带结构，该结构高度具有端元的特征，几乎没有有机或无机组分之间重新杂化的迹象。
