LnIII(Ln = La, Gd, and Dy) Benzimidazolium Tricarboxylate Coordination Polymers with Hydrogen Bonding Modulated Magnetic Relaxation

Ramakant, GA and Ahmed, N and Tarannum, I and Mehta, S and Nandeshwar, M and Mondal, A and Singh, SK and Prabusankar, G (2022) LnIII(Ln = La, Gd, and Dy) Benzimidazolium Tricarboxylate Coordination Polymers with Hydrogen Bonding Modulated Magnetic Relaxation. In: Crystal Growth and Design .

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Abstract

The novel LnIII {Ln = Dy (1-Dy), Gd (2-Gd), and La (3-La)} benzimidazolium tricarboxylate coordination polymers have been synthesized, and their magnetic properties have been investigated. Single-crystal X-ray analysis revealed that 1-Dy, 2-Gd, and 3-La are one-dimensional coordination polymers with general molecular formulas of {[Ln(L)2(H2O)4]·(6Br)}∞ [L = 3,3′,3′′-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(1-(carboxymethyl)-benzimidazolium)], which crystallized in the monoclinic, P21/c space group. The solid-state packing of these coordination polymers shows the spiral propagation in a one-dimensional direction. The direct current (dc) magnetic data (susceptibility and magnetization) were collected for 1-Dy and 2-Gd. The alternating current (ac) magnetic measurement for 1-Dy at zero field shows the characteristic signature of single-molecule magnets (SMMs) at low temperatures but without clear maxima. Further, to rationalize the experimentally observed magnetic behavior and to understand the factors affecting the dynamic magnetic behavior of 1-Dy, we performed detailed completed active space self-consistent field (CASSCF) based calculations on 1-Dy. Our detailed theoretical analysis suggests that the hydrogen bonding interaction between the coordinated water molecule and the Br– counteranion increases the equatorial electron density, eradicating the slow relaxation in 1-Dy.

Item Type:	Journal Article
Publication:	Crystal Growth and Design
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Electric impedance measurement; Hydrogen; Magnetic susceptibility; Magnetism; Molecules; Single crystals, C-space; Carboxymethyl; Coordination Polymers; Coordination-polymers; Molecular formulae; Monoclinics; One-dimensional coordination polymer; Single crystal X-ray analysis; Synthesised; Trimethylbenzene, Hydrogen bonds
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	05 Oct 2022 06:19
Last Modified:	05 Oct 2022 06:19
URI:	https://eprints.iisc.ac.in/id/eprint/77042

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