Wang Yu-Hang, Jiang De-Xuan, Liu De-Xuan, Li Fu-Ying, Zhao He, Pan Jie, Wei Qi, Wei Li, Yang Guo-Yu
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, P. R. China.
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China.
Inorg Chem. 2024 Oct 28;63(43):20774-20780. doi: 10.1021/acs.inorgchem.4c03500. Epub 2024 Oct 19.
Birefringent crystals, which can modulate and polarize light, play a vital role in the development of optical sensors and optoelectronic devices. Herein, we synthesized a new birefringent crystal [(CNH)(HIO)(HIO)(IO)] with large birefringence by integrating the large π-conjugated 4,4'-bipyridine group with two types of iodates anions ([IO] and [HIO]) characterized by high polarizability anisotropy and strong stereochemically active lone pairs (SCALP). The crystal exhibits a large measured birefringence of 0.171 at 550 nm, surpassing most organic-inorganic hybrid iodate birefringent materials reported in the literature. Theoretical analyses reveal that the optical properties of the crystal arise primarily from the synergistic interactions between the π-conjugated 4,4'-bipyridine group and I-O groups. This research presents an effective method for the strategic integration of large π-conjugated organic cations into iodates, facilitating the design of novel birefringent materials and encouraging further exploration of superior birefringent substances.
双折射晶体能够调制和偏振光，在光学传感器和光电器件的发展中起着至关重要的作用。在此，我们通过将大π共轭的4,4'-联吡啶基团与两种具有高极化率各向异性和强立体化学活性孤对电子（SCALP）的碘酸盐阴离子（[IO]和[HIO]）相结合，合成了一种具有大双折射的新型双折射晶体[(CNH)(HIO)(HIO)(IO)]。该晶体在550 nm处表现出0.171的大测量双折射，超过了文献中报道的大多数有机-无机杂化碘酸盐双折射材料。理论分析表明，该晶体的光学性质主要源于π共轭4,4'-联吡啶基团与I-O基团之间的协同相互作用。本研究提出了一种将大π共轭有机阳离子战略性地整合到碘酸盐中的有效方法，有助于新型双折射材料的设计，并鼓励进一步探索优异的双折射物质。
