Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex
Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex
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DOI：
10.1039/d0tc04280c
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发表时间：
2020-11
影响因子：
6.4
通讯作者：
So Yokomori;Shun Dekura;Tomoko Fujino;M. Kawamura;T. Ozaki;H. Mori
中科院分区：
文献类型：
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作者：
So Yokomori;Shun Dekura;Tomoko Fujino;M. Kawamura;T. Ozaki;H. Mori
氢键（H-键合）长期以来一直用于结构调节。最近，已经报道了一些基于通过H键直接调制电子状态来切换导电性和磁性的例子。如果将这一策略应用于包括光学性质在内的广泛功能，将极大地拓展功能分子材料的设计标准。在这里，我们报告了一种新的锌二硫纶配合物晶体，它表现出一种新的气相变色诱导电子转移通过H-键。这种晶体表现出可见光吸收和光致发光特性的变化，由甲醇或水蒸气吸收引起的单晶到单晶（SCSC）的转变。单晶结构分析表明，锌二硫纶配合物形成的蒸汽分子的H-键。重要的是，基于周期性晶体结构的第一性原理计算表明，该晶体中的蒸发变色仅由氢键形成引起，而不是由结构变化引起。晶体轨道的能量和形状的详细调查，以及Mulliken人口分析表明，通过H-键的电子转移引起该晶体中的蒸发光致变色。研究结果提供了重要的见解到新型的vapochromic材料的材料设计，以及其他刺激响应材料考虑在固态的分子间氢键。
Hydrogen bonding (H-bonding) has long been used for structural regulations. Recently, some examples have been reported where electrical conductivity and magnetism were switched based on direct modulation of electronic states through H-bond. If the application of this strategy is realized to a wide range of functionalities, including optical properties, it will greatly expand the design criteria of functional molecular materials. Here, we report a novel zinc dithiolene complex crystal, which exhibits a new vapochromism induced by electron transfer through H-bonds. This crystal exhibits changes in both visible-light absorption and photoluminescence properties with single-crystal-to-single-crystal (SCSC) transformations caused by methanol or water vapor absorption. Single-crystal structural analysis revealed that the zinc dithiolene complex formed H-bonds with the vapor molecules. Importantly, first-principles calculations based on the periodic crystal structures indicated that the vapochromism in this crystal was solely induced by H-bond formation, not by structural changes. Detailed investigations of the energies and shapes of the crystal orbitals as well as Mulliken population analysis revealed that electron transfer through the H-bonds caused vapochromism in this crystal. The findings provide important insights into the material designs of novel vapochromic materials as well as other stimuli-responsive materials considering the intermolecular H-bonds in the solid-state.