[C3H7N6]3[B3O5(OH)2] 和 [C3H8N6]4[B12O19(OH)6]：两种具有大双折射的三聚氰胺硼酸盐。

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-12-02 Epub Date: 2024-11-18 DOI:10.1021/acs.inorgchem.4c04170

Ya-Lan Deng, Chun-Li Hu, Jiang-Gao Mao

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引用次数: 0

摘要

π-共轭[C3H6+xN6]x+（x = 0-3）阳离子是一种良好的官能团，因其具有较高的超极化性和光学各向异性，被广泛应用于制备非线性光学（NLO）和双折射材料。本文在 H3BO3:C3H6N6 = 1:1 的摩尔比条件下，采用硼酸熔融法合成了第一种羟基硼酸三聚氰胺[C3H7N6]3[B3O5(OH)2]（MelBO-I）。MelBO-I（P21/c）呈现出二维（2D）{[C3H7N6]3[B3O5(OH)2]}∞层，由通过氢键相互连接的[C3H7N6]+阳离子和[B3O5(OH)2]3阴离子组成。MelBO-I 具有明显的双折射（Δn = 0.286@546 纳米）。在 H3BO3/C3H6N6 = 3:1 的摩尔比条件下，分离出 [C3H8N6]4[B12O19(OH)6]（MelBO-II）。在 MelBO-II （P21）中，高度聚合的[B12O19(OH)6]8-基团通过氢键形成三维网络，其特点是由[C3H8N6]2+阳离子填充的 8 元环和 16 元环组成的一维隧道。MelBO-II 是第一种非中心对称（NCS）双官能团三聚氰胺硼酸盐，具有适度的 SHG 响应（0.4 × KDP）和较大的双折射（Δn = 0.285@546 nm）。结果表明，在硼酸盐中加入 [C3H6+xN6]x+ （x = 0-3）阳离子可以有效地诱导双折射。高浓度的硼酸可促进大硼酸簇阴离子的形成，并有助于从 CS 结构转变为 NCS 结构。

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[C₃H₇N₆]₃[B₃O₅(OH)₂] and [C₃H₈N₆]₄[B₁₂O₁₉(OH)₆]: Two Melamine Borates with Large Birefringence.

The π-conjugated [C₃H_6+xN₆]^x+ (x = 0-3) cations are good functional groups, which are widely employed in the preparations of nonlinear optical (NLO) and birefringent materials due to their high hyperpolarizability and optical anisotropy. In this paper, the first melamine hydroxyborate [C₃H₇N₆]₃[B₃O₅(OH)₂] (MelBO-I) was synthesized by the boric acid melting method under the molar ratio of H₃BO₃:C₃H₆N₆ = 1:1. MelBO-I (P2₁/c) exhibits a two-dimensional (2D) {[C₃H₇N₆]₃[B₃O₅(OH)₂]}_∞ layer composed of [C₃H₇N₆]⁺ cations and [B₃O₅(OH)₂]^3- anions interconnected via hydrogen bonds. MelBO-I exhibits significant birefringence (Δn = 0.286@546 nm). Under the molar ratio of H₃BO₃/C₃H₆N₆ = 3:1, [C₃H₈N₆]₄[B₁₂O₁₉(OH)₆] (MelBO-II) was isolated. In MelBO-II (P2₁), highly polymerized [B₁₂O₁₉(OH)₆]^8- groups form a 3D network through hydrogen bonding, featuring 1D tunnels of 8-membered and 16-membered rings filled by [C₃H₈N₆]²⁺ cations. MelBO-II is the first noncentrosymmetric (NCS) bifunctional melamine borate with a moderate SHG response (0.4 × KDP) and large birefringence (Δn = 0.285@546 nm). The results indicate that incorporating [C₃H_6+xN₆]^x+ (x = 0-3) cations into borate can effectively induce birefringence. A high concentration of boric acid promotes the formation of large boric acid cluster anions and facilitates the transformation from the CS to NCS structure.

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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.