β-CsHg2I5, a compound with rare [Hg2I5] dimers and large optical anisotropy†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Dalton Transactions Pub Date : 2024-06-27 DOI:10.1039/D4DT01536C
Yingying Kong, Hongshan Wang, Wang Zhao, Qi Sun, Junjie Li and Shilie Pan
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Abstract

Hg-based compounds show abundant structural diversity and distinguished properties. Herein, a new phase transition compound CsHg2I5 was reported. The high-temperature phase β-CsHg2I5 with rare [Hg2I5] dimers was synthesized by the flux method at 573 K, and it shows a reversible phase transition at a low temperature of ∼100 K to form the low-temperature phase α-CsHg2I5. The two phases crystallize in the same P21/c space group, with different crystal structures. β-CsHg2I5 is composed of rare [Hg2I5] dimers and [CsI11] polyhedral units, while α-CsHg2I5 is composed of [Hg4I11] and [CsI10] units. The experimental band gap of β-CsHg2I5 was found to be 2.58 eV. Owing to the presence of [Hg2I5] pseudo-layers, β-CsHg2I5 exhibits large optical anisotropy with a calculated birefringence of 0.132@1064 nm. Meanwhile, β-CsHg2I5 is a congruent compound and the congruent point is ∼481 K. Theoretical calculations indicate that the rare [Hg2I5] dimer is a nonlinear active unit, which can be used as a new fundamental building block for the design of advanced nonlinear optical materials. Moreover, a CsI–HgI2 pseudo-binary diagram was drawn. The results enrich the structural diversity of Hg-based halides and give some insights into the development of new functional materials based on rare [Hg2I5] dimers.

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β-CsHg2I5,一种具有稀有[Hg2I5]二聚体和较大光学各向异性的化合物
汞基化合物具有丰富的结构多样性和独特的性质。本文报告了一种新的相变化合物 CsHg2I5。在 573 K 温度下,通过通量法合成了具有稀有[Hg2I5]二聚体的高温相 β-CsHg2I5,并在约 100 K 的低温下发生可逆相变,形成低温相 α-CsHg2I5。这两种相在相同的 P21/c 空间群中结晶,具有不同的晶体结构。β-CsHg2I5由罕见的[Hg2I5]二聚体和[CsI11]多面体单元组成,而α-CsHg2I5则由[Hg4I11]、[CsI10]单元组成。据测量,β-CsHg2I5 的实验带隙为 2.58 eV。由于[Hg2I5]∞伪层的存在,β-CsHg2I5 表现出很大的光学各向异性,计算得出的双折射为 0.132@1064 nm。理论计算表明,稀有的[Hg2I5]二聚体是一种非线性活性单元,可作为设计先进非线性光学材料的新基础构件。此外,还绘制了 CsI-HgI2 伪二元图。这些结果丰富了汞基卤化物的结构多样性,并为基于稀有[Hg2I5]二聚体的新型功能材料的开发提供了一些启示。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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