Theoretical Study of Pentacoordinated Lanthanide Single-Ion Magnets via Ab Initio Electronic Structure Calculation

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

Wang et al reported the theoretical studies of 16 pentacoordinated Dy complexes, which exhibit single ion magnet (SIM) properties. To my knowledge, the theoretical studies for obtaining the quantum tunneling of magnetization (QTM) time (τ_QTM), and effective energy barrier (U_eff) are essential for directing others to design high-performance Dy-based SIMs. Additionally, the work was written well. Therefore, I recommend the work to be published in magnetochemistry after the authors answer the following queries.

(1) I understand that, for most complexes, the blocking temperature could not be reported. In page 4, authors stated the temperature of the peaks in the out-of-phase (χ'') ac susceptibilities (T_AC) was used to quantify T_B. As we know, many complexes with high T_AC could not exhibit magnetic hysteresis loops even at 2.0 K. Can you provide some references to verify it?

(2) Authors stated that the contribution from the equatorial coordinating atoms might be even more important than that from the axial coordinating atoms. Could you explain it by some sentences?

(3) Additionally, authors stated that the axial O-Dy-O angle might be a probable way to improve the SMM performance of pentacoordinated Ln-SIMs. Can you explain it by some sentences? Moreover, in this work, authors investigated Dy complexes. I think the word “Ln-SIMs” might be not reasonable. please check it.

(4) I think some Dy-based SIMs with Dy in other coordination geometries and Dy-based SMMs could be cited in the introduction part, for example, CrystEngComm, 2021, 23, 3175–3184; Inorg. Chem. 2021, 60, 18739−18752.

Author Response

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Author Response File: Author Response.pdf

Reviewer 2 Report

Comments and Suggestions for Authors

The manuscript by wang et al. is an interesting theoretical investigation that deserves to be published in Magnetochemistry. Only minor points should be addressed.

-Further details on 'the difficulty to get accurate Chi_anis' should be provided. What do you mean that nuclear contributions should have an effect?

-What is the physical meaning of Trep? Is there any relationship with the blocking temperature?

-The point charge model can provide a rough estimate of the CF but several discrepancies are expected due to significant covalent contributions. See for instance  Chem. Sci., 2019,10, 7233-7245 and Chem. Sci., 2024,15, 113-123. These papers should be properly discussed.

-In the second above-cited paper, a non-negligible role of the 8th rank term of the CF is observed, which should not be present in the pure electrostatic picture. Do you observe the same in your case?

Author Response

Please see the attachment

Author Response File: Author Response.pdf