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

Ramakant, Girbide Amitkumar and Ahmed, Naushad and Tarannum, Ibtesham and Mehta, Sakshi and Nandeshwar, Muneshwar and Mondal, Abhishake and Singh, Saurabh Kumar and Prabusankar, Ganesan (2022) LnIII (Ln = La, Gd, and Dy) Benzimidazolium Tricarboxylate Coordination Polymers with Hydrogen Bonding Modulated Magnetic Relaxation. Crystal Growth & Design. pp. 1-10. ISSN 1528-7483

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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]center dot(6Br)}infinity [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.

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IITH Creators:
IITH CreatorsORCiD
Prabusankar, GanesanUNSPECIFIED
Singh, Saurabh KumarUNSPECIFIED
Item Type: Article
Additional Information: G.P. gratefully acknowledges the CSIR (01 (2884) /17/EMR-II) and DST-SERB (EMR/2017/001211) for financial support. A.G. thanks CSIR-JRF for the JRF fellowship. M.N. thanks CSIR-SRF and IITH for providing a fellowship and research facilities. N.A. thanks the Department of Science and Technology DST-SERB (File No. PDF/2020/000074) for the national postdoctoral fellowship and research grants and IIT Hyderabad for the research facilities. S.K.S. acknowledges the DST-SERB (SRG/2020/001323) and IIT Hyderabad for the start-up research grant. S.K.S. acknowledges the NSM-PARAM Shivay supercomputing facility IIT-BHU. A.M. thanks the Solid State and Structural Chemistry Unit (SSCU) and the Indian Institute of Science (IISc) Bangalore, India, for extending support for the use of the SQUID Magnetometer facility.
Subjects: Chemistry
Divisions: Department of Chemistry
Depositing User: . LibTrainee 2021
Date Deposited: 30 Sep 2022 04:44
Last Modified: 30 Sep 2022 04:44
URI: http://raiith.iith.ac.in/id/eprint/10741
Publisher URL: http://doi.org/10.1021/acs.cgd.2c00674
OA policy: https://v2.sherpa.ac.uk/id/publication/7772
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