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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Connectivity-Driven Electronic Structure and Charge Separation in Morpholinium-Based Bi³⁺/Sb³⁺ Halides.

Tamara J Bednarchuk¹, Magdalena N Rowińska¹, Oleksandr Korolevych¹

¹Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław, Poland.

Inorganic Chemistry

|July 2, 2026

Summary

Morpholinium-based halides exhibit diverse structures and electronic properties. Cation choice and halide composition influence crystal architecture and charge transport, impacting potential applications in optoelectronics.

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Published on: February 7, 2017

Area of Science:

Materials Science
Solid-State Chemistry
Crystallography

Background:

Organic-inorganic metal-halide double perovskites (A₂MM'X₆) exhibit diverse structures and electronic properties influenced by A-site cations and M-site metals.
The connectivity of M'X₆ octahedra and electronic characteristics are crucial for material functionality.

Purpose of the Study:

To synthesize and characterize novel morpholinium (MOR)-based halides.
To investigate the structure-property relationships in these materials, focusing on crystal architecture, charge transport, and optoelectronic behavior.

Main Methods:

Single-crystal X-ray diffraction for structural determination.
Density Functional Theory (DFT) calculations for electronic structure and effective mass analysis.
Photoluminescence spectroscopy to probe electronic transitions and recombination mechanisms.

Main Results:

Four morpholinium-based halides, (MOR)₂CsBiCl₆ (1), (MOR)₂CsSbCl₆ (2), (MOR)₂KBiCl₆ (3), and (MOR)₂RbSbI₆ (4), were synthesized and structurally characterized.
Compounds 1 and 2 display anisotropic charge transport with higher electron mobility, while compound 1 shows spatial separation of charge densities, indicative of a Z-scheme heterojunction.
Compound 3 exhibits suppressed charge mobility due to large Cl···Cl separations, and photoluminescence studies reveal distinct recombination mechanisms in compound 1.

Conclusions:

The study highlights the critical roles of cation size, lone-pair activity, and halide polarizability in directing the structure and electronic properties of organic-inorganic metal-halide materials.
These findings provide insights into designing novel materials with tailored optoelectronic characteristics.