In recent years, there has been significant attention drawn towards metal halide perovskites, aclass of semiconducting materials distinguished by their remarkable optoelectronic properties.
In the halide perovskite structure, the metal halide octahedron ([BX6]n-, B = metal cation, X =
halide anion) is the fundamental building block and functional unit. This dissertation aims to
present a novel perspective by proposing a supramolecular approach to manipulate the metal
halide octahedral building blocks. The new supramolecular building block is constructed from
the ionic halide perovskite octahedral unit and crown ether supramolecular cations, resulting in
the formation of a novel (crown-ether@A)2BX6 (A = alkali metal cation) dumbbell structural
unit. The chemistry, properties, and application of this supramolecular approach constitute the
main topics of this dissertation.
Chapter 1 provides an overview of halide perovskite materials, encompassing their structure,
synthesis, properties, and applications. The concept of dimensionality in halide perovskites and
the significance of the metal halide octahedral [BX6]n- building blocks are introduced, laying
the foundation for the subsequent discussion on the supramolecular assembly approach. In
Chapter 2, we delve into the details of the supramolecular assembly approach, highlighting its
structural and compositional adaptability, along with its immense potential in various
optoelectronic applications. Chapter 3 delves into the synthesis and characterization of two new
blue and green emitters with near-unity photoluminescence quantum yield (PLQY), (18-
Crown-6@K)2HfBr6 and (18-Crown-6@K)2ZrCl4Br2, derived from the supramolecular
assembly approach. Comprehensive optical studies of these materials are presented, along with
demonstrations of their applications in display and 3D-printing technologies. Lastly, chapter 4
provides a summary of the research findings and offers insights into the future directions for
the supramolecular assembly approach, establishing a solid foundation for the future
development and application of halide perovskites.