（C7H10N）3Bi2I9·I2: π共轭阳离子与畸变[BiI6]八面体的协同作用，实现大红外双折射。

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-30 DOI:10.1021/acs.inorgchem.5c03848

Dingxuan Zhao,Shihui Ma,Jiajia Wang,Fei Liang,Dazhi Lu,Kui Wu,Ning Ye,Zhanggui Hu

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引用次数: 0

摘要

双折射晶体可以调制光的偏振，在红外光通信波段的光电和光子领域有着重要的应用。然而，现有的双折射晶体由于色散效应，在红外波段双折射明显降低（Δn≤0.26）。本文设计了一种具有层状π共轭阳离子的有机-无机杂化卤化物（C7H10N）3Bi2I9·I2。虽然该结构具有立体化学惰性孤对Bi3+，但该化合物表现出0.39@589 nm（钠d线）的大双折射，这与0.386@589 nm的理论计算一致。值得注意的是，第一性原理计算表明，它仍然保持0.42@1064 nm和0.32@1550 nm的大双折射。这可归因于π共轭1-乙基吡啶阳离子的高度畸变性质和BiI6八面体的显著畸变。这项工作强调了有机-无机杂化卤化物材料作为双折射晶体的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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(C7H10N)3Bi2I9·I2: Synergistic Cooperation of π-Conjugated Cations and Distorted [BiI6] Octahedra Enabling a Large Infrared Birefringence.

Birefringent crystals can modulate the polarization of light and have important applications in optoelectronic and photonic fields in the infrared optical communication band. However, existing birefringent crystals exhibit a significant decrease in birefringence (Δn ≤ 0.26) in the infrared waveband due to the dispersion effect. Herein, we designed a new organic-inorganic hybrid halide (C7H10N)3Bi2I9·I2, which possesses a layered structure with π-conjugation cations. Though the structure has a stereochemical inert lone pair Bi3+, the compound exhibits a large birefringence of 0.39@589 nm (sodium D-line), which is consistent with the theoretical calculations of 0.386@589 nm. Remarkably, first-principles calculations reveal that it still maintains a large birefringence of 0.42@1064 nm and 0.32@1550 nm. This can be attributed to the highly distorted nature of the π-conjugated 1-ethylpyridinium cation and the significant distortion of the BiI6 octahedra. This work highlights the persistently neglected potential of organic-inorganic hybrid halide materials as birefringent crystals.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.