Structural Diversity and Giant Birefringence in Cyanates BaCNOX (X = Cl, Br, I, and CNO) Containing Linear π-Conjugated Units: A Combined Experimental and Theoretical Study,Crystal Growth & Design

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Structural Diversity and Giant Birefringence in Cyanates BaCNOX (X = Cl, Br, I, and CNO) Containing Linear π-Conjugated Units: A Combined Experimental and Theoretical Study
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-01-08 , DOI: 10.1021/acs.cgd.9b01504
Jian Tang _{1,

2} , Xianghe Meng _{3,

4} , Fei Liang _{3,

4} , Kaijin Kang _{1,

2} , Tixian Zeng ₂ , Mingjun Xia _{3,

4} , Wenlong Yin _{1,

5} , Zheshuai Lin ₃ , Bin Kang _{1,

5}

Affiliation

Four novel cyanates BaCNOX (X = Cl, Br, I, and CNO) containing linear π-conjugated anions were obtained by solid-state metathesis reactions for the first time. BaCNOCl crystallizes in a monoclinic space group P2₁/m with a = 5.5757(15) Å, b = 4.4925(10) Å, c = 7.850(2) Å, β = 102.38(3)°, Z = 2, whereas the remaining three compounds belong to the same orthorhombic space group Pnma with a = 8.227–8.713 Å, b = 4.290–4.552 Å, c = 10.986–11.803 Å, Z = 4. The crystal structures of these four compounds are divergent, exhibiting rich structural diversity ranging from simple to complex when X changes from Cl to Br and I, and then to CNO. Their thermal, vibrational, and optical properties were characterized in detail. Besides, the first-principles calculations reveal that all four compounds show giant optical anisotropy of Δn > 0.20 at 800 nm owing to the superior arrangement of linear (CNO)⁻ π-conjugated groups. Successful synthesis of these cyanates not only further explains the influence of microscopic ions on the structures, but also enriches the structure chemistry of cyanates and provides enlightenment for the study of birefringence in CNO-based compounds.

中文翻译：

包含线性π共轭单元的氰酸盐BaCNOX（X = Cl，Br，I和CNO）的结构多样性和超双折射：组合的实验和理论研究

首次通过固态复分解反应获得了四种含线性π-共轭阴离子的新型氰酸盐BaCNOX（X = Cl，Br，I和CNO）。BaCNOCl结晶在单斜晶系空间群P 2 ₁ /米与一个= 5.5757（15）埃，b = 4.4925（10）埃，c ^ = 7.850（2），β= 102.38（3）°，Ž = 2，而其余三个化合物属于相同的正交空间群Pnma，其a = 8.227–8.713Å，b = 4.290–4.552Å，c = 10.986–11.803Å，Z＝ 4。这四种化合物的晶体结构是发散的，当X从Cl变成Br和I，然后变成CNO时，表现出从简单到复杂的丰富的结构多样性。详细描述了它们的热，振动和光学性能。此外，第一原理计算显示，所有四种化合物显示Δ巨光学各向异性Ñ >由于线性的优越布置0.20在800nm处（CNO）^- π共轭基团。这些氰酸盐的成功合成，不仅进一步说明了微观离子对结构的影响，而且丰富了氰酸盐的结构化学，并为研究CNO基化合物的双折射提供了启示。

更新日期：2020-01-09

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