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Volume 31
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10.3390/molecules31122012
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Article

Design and Control of Supramolecular Structure in Crown Ether–Manganese Thiocyanate Complexes Tuned by Aliphatic Diamine Alkyl Chains: Parity-Dependent Modulation of Dielectric and Electrochemical Properties

by
Tong Zhang
1,2,
Hongzhi Hu
1,2,*,
Adila Abuduheni
1,2,
Yang Liu
1,2,3,* and
Zunqi Liu
1,2,3,*
1
Chemistry and Chemical Engineering College, Xinjiang Agricultural University, Urumqi 830052, China
2
Xinjiang Key Laboratory for High Value Utilization of Agricultural and Livestock By-Products, Urumqi 830052, China
3
Xinjiang Sub-Center National Engineering Research Center of Novel Equipment for Polymer Processing, Urumqi 830052, China
*
Authors to whom correspondence should be addressed.
Molecules 2026, 31(12), 2012; https://doi.org/10.3390/molecules31122012
Submission received: 20 March 2026 / Revised: 3 June 2026 / Accepted: 4 June 2026 / Published: 9 June 2026
(This article belongs to the Special Issue Opportunities and Challenges in Organic Optoelectronic Materials)
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Abstract

Aliphatic diamines possess two amino functional groups and exhibit diverse chemical properties and tunable molecular structures. By selecting the guest [(C2H2n+4N2), n = 2–6] and host 18-crown-6, and controlling the design and assembly processes via modulation by thiocyanate and a manganese salt, a series of dumbbell-shaped crown ether complexes, (C2H2n+6N2)2+(18-crown-6)2[Mn(NCS)4]2−·(δn,2C2H3N), n = 2–6, (1)–(5), was synthesized and analyzed by single-crystal X-ray diffraction (SCXRD) at 100 K and 293 K. Variable-temperature infrared and XRD analyses confirmed that compounds 3 and 5 underwent a phase transition. As the length of the carbon chain increases and alternates between odd and even, the interplanar dihedral angle of the crown ether exhibits a distinct pattern: Even-number chains arrange in parallel, whereas odd-number chains form a pronounced angle. This structural pattern influences macroscopic deformation of the crystal and induces corresponding periodic variations in the dielectric and electrochemical properties. The wide-bandgap insulators and magnetic properties are primarily governed by the inorganic components of the system and are less influenced by the organic portion. This study reveals principles for regulating supramolecular conformation and functional properties through the parity of the organic chain lengths, providing a strategy for the molecular-level design of supramolecular crystal materials with ordered structures and tunable properties.
Keywords: alkyl chain of aliphatic diamine; 18-crown-6; dielectric properties; molecular-level design; crystal materials alkyl chain of aliphatic diamine; 18-crown-6; dielectric properties; molecular-level design; crystal materials
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MDPI and ACS Style

Zhang, T.; Hu, H.; Abuduheni, A.; Liu, Y.; Liu, Z. Design and Control of Supramolecular Structure in Crown Ether–Manganese Thiocyanate Complexes Tuned by Aliphatic Diamine Alkyl Chains: Parity-Dependent Modulation of Dielectric and Electrochemical Properties. Molecules 2026, 31, 2012. https://doi.org/10.3390/molecules31122012

AMA Style

Zhang T, Hu H, Abuduheni A, Liu Y, Liu Z. Design and Control of Supramolecular Structure in Crown Ether–Manganese Thiocyanate Complexes Tuned by Aliphatic Diamine Alkyl Chains: Parity-Dependent Modulation of Dielectric and Electrochemical Properties. Molecules. 2026; 31(12):2012. https://doi.org/10.3390/molecules31122012

Chicago/Turabian Style

Zhang, Tong, Hongzhi Hu, Adila Abuduheni, Yang Liu, and Zunqi Liu. 2026. "Design and Control of Supramolecular Structure in Crown Ether–Manganese Thiocyanate Complexes Tuned by Aliphatic Diamine Alkyl Chains: Parity-Dependent Modulation of Dielectric and Electrochemical Properties" Molecules 31, no. 12: 2012. https://doi.org/10.3390/molecules31122012

APA Style

Zhang, T., Hu, H., Abuduheni, A., Liu, Y., & Liu, Z. (2026). Design and Control of Supramolecular Structure in Crown Ether–Manganese Thiocyanate Complexes Tuned by Aliphatic Diamine Alkyl Chains: Parity-Dependent Modulation of Dielectric and Electrochemical Properties. Molecules, 31(12), 2012. https://doi.org/10.3390/molecules31122012

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