Citation: Ying-Qian Zhou, Chan-Ying Yao, Ze-Yu Ruan, Bang-Heng Lyu, Shan-Nan Du, Si-Guo Wu, Yan-Cong Chen, Wei Deng, Jun-Liang Liu, Ming-Liang Tong. Proton control of Raman relaxation in bis-hydrazone single-molecule magnets[J]. Chinese Chemical Letters, ;2026, 37(8): 111179. doi: 10.1016/j.cclet.2025.111179 shu

Proton control of Raman relaxation in bis-hydrazone single-molecule magnets

Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, Sun Yat-sen University, Guangzhou 510006, China

dengw55@mail.sysu.edu.cn

liujliang5@mail.sysu.edu.cn

Received Date: 17 February 2025
Revised Date: 28 March 2025
Accepted Date: 3 April 2025
Available Online: 3 April 2025

Figures(4)

The under-barrier Raman relaxation process has long presented a formidable challenge in advancing the performance of single-molecule magnets (SMMs). Exploring the nuanced differences in Raman relaxation processes between two structurally analogous systems remains relatively uncharted territory. Herein, two Dy(Ⅲ)-based single-ion magnets (SIMs) with pentagonal bipyramidal geometry were reported, and their Raman relaxation behaviors were regulated by precisely adjusting the protonation level of the bis-hydrazone moiety. Intriguingly, under the optimal magnetic field, the degree of protonation shows no impact on the Raman exponent n but causes a distinct variation in the Raman relaxation coefficient C. The effects of deprotonation on the molecular geometry and charge distribution were elucidated through ab initio and electrostatic potential (ESP) calculations. Deprotonation results in an asymmetric charge distribution within the equatorial plane, causing the coefficient C to increase substantially by 3.5 times, aligning closely with the theoretical calculation value of approximately 2.8 times. This study provides concise and effective molecular archetypes for investigating the Raman relaxation process.
- Single-molecule magnets,
- Pentagonal bipyramid,
- Raman magnetic relaxation,
- Protonation,
- Bis-hydrazone ligands
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