Kronawitter Silva M, Kieslich Gregor
Department of Chemistry, TUM School of Natural Sciences, Technical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany.
Chem Commun (Camb). 2024 Oct 10;60(82):11673-11684. doi: 10.1039/d4cc03833a.
The substitution of atoms with molecular building blocks to form hybrid organic-inorganic networks has been an important research theme for several decades. ABX molecular perovskites (MolPs) are a subclass of hybrid networks, adopting the perovskite structure with cationic and anionic molecules on the A-site and X-site. MolPs such as ((CH)NH)Zn(HCOO) or ((-CH)N)Mn(CN) show a range of fascinating structure-chemical properties, including temperature-driven phase transitions that include a change of polarity as interesting for ferroelectrics, pressure-driven order-disorder phase transitions as interesting for barocaloric solid-state refrigeration, and most recently, melting-behaviour before decomposition with subsequent glass formation after cooling. In this feature article, we take a more personal perspective, overviewing the field's current state and outlining future directions. We start by comparing the MolPs' structural chemistry with their inorganic parents, a comparison that helps us identify opportunities for material design. After discussing the MolPs' potential as barocalorics, ferroelectrics, and in the area of glasses, we outline some challenges that lie ahead. Beyond their relevance as a hybrid analogue of inorganic perovskites, we find that MolPs' chemical parameter space provides exciting opportunities for systematically developing design guidelines for functional materials.
用分子构建块取代原子以形成有机-无机杂化网络，几十年来一直是一个重要的研究主题。ABX分子钙钛矿（MolPs）是杂化网络的一个子类，在A位和X位采用具有阳离子和阴离子分子的钙钛矿结构。诸如((CH)NH)Zn(HCOO) 或 ((-CH)N)Mn(CN) 等MolPs表现出一系列迷人的结构化学性质，包括温度驱动的相变，其中包括对铁电体来说有趣的极性变化、对气压热固态制冷来说有趣的压力驱动的有序-无序相变，以及最近发现的在分解前的熔化行为以及冷却后随后形成玻璃的现象。在这篇专题文章中，我们从更个人的角度进行阐述，概述该领域的当前状况并概述未来方向。我们首先将MolPs的结构化学与其无机母体进行比较，这种比较有助于我们确定材料设计的机会。在讨论了MolPs作为气压热材料、铁电体以及在玻璃领域的潜力之后，我们概述了一些未来面临的挑战。除了它们作为无机钙钛矿的杂化类似物的相关性之外，我们发现MolPs的化学参数空间为系统地制定功能材料的设计指南提供了令人兴奋的机会。
