A-Site Cation Template-Induced N–H···O Hydrogen-Bond Orientations for Constructing Three-Dimensional Cesium-Based Energetic Molecular Perovskites

IF 7.1 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-21 DOI:10.1021/acs.chemmater.6c01921

Zhenghang Luo, Ruibing Lv, Qi Zhang

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Abstract

Energetic molecular perovskites (EMPs) are a high-energy subclass of molecular perovskites that integrate oxidizers and fuels within a single framework. However, the structures of reported EMPs remain rather limited, and the structural contribution and governing role of their component ions remain elusive. Herein, we develop an A-site cation-templated strategy to direct the spatial orientation of N–H···O hydrogen bonds, enabling the rational engineering of two Cs-based EMPs with distinct 3D frameworks: trigonal DCP-1 and tetragonal TCP-1. The inductive effect of the A-site cation in framework construction is elucidated. Unlike H₂hmta²⁺, H₂dabco²⁺ features a unique parallel N–H vector field, which drives the connection of [Cs(ClO₄)₆] octahedra through a rare alternating face-sharing and corner-sharing mode. This assembly results in the first EMP crystallizing in the R3̅c space group. Such structural divergence, governed by the spatial orientation of hydrogen bonds, leads to a significant differentiation in physicochemical properties. This work not only introduces cesium into EMPs for the first time but also expands the structural diversity of EMPs by introducing an unusual trigonal framework. The universal principle of tailoring crystal structures and energetic properties by A-site hydrogen-bond vectors is revealed, providing insights into next-generation high-performance energetic materials.

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构建三维铯基高能分子钙钛矿的a位阳离子模板诱导N-H···O氢键取向

高能分子钙钛矿（EMPs）是一种高能分子钙钛矿亚类，它将氧化剂和燃料整合在一个单一的框架内。然而，已报道的电磁脉冲的结构仍然相当有限，其组成离子的结构贡献和控制作用仍然难以捉摸。在此，我们开发了一种a位阳离子模板策略来指导N-H···O氢键的空间取向，从而实现了具有不同3D框架的两种基于cs的emp的合理工程：三角形DCP-1和四边形TCP-1。阐明了a位阳离子在框架结构中的诱导作用。与H2hmta2+不同，H2dabco2+具有独特的平行N-H向量场，通过一种罕见的面共享和角共享交替模式驱动[Cs(ClO4)6]八面体的连接。这种组合导致了第一个EMP在R3 _ c空间群中结晶。这种由氢键的空间取向控制的结构差异导致了物理化学性质的显著差异。这项工作不仅首次将铯引入到emp中，而且通过引入一个不寻常的三角形框架扩展了emp的结构多样性。揭示了利用a位氢键载体裁剪晶体结构和能量特性的普遍原理，为下一代高性能能材料的研究提供了新的思路。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.