Chalcogen Bonds, Halogen Bonds and Halogen···Halogen Contacts in Di- and Tri-iododiorganyltellurium(IV) Derivatives

Round 1

Reviewer 1 Report

Interesting paper deserving revision after a minor revision.

The Authors investigated theoretically the occurrence of chalcogen bonds, halogen bonds and halogen…halogen contacts in different iodo organyl tellurium (IV) compounds in the solid state. For this purpose, they carried out DFT calculations using extended atomic basis sets, dispersion interactions being taken into account empirically. The studied species have been well chosen. The different possible noncovalent interactions have been carefully characterized using several descriptors. The paper is well written, illustrated, documented and pleasant to read.

To my opinion, only few points deserve more explanation before publication.

Regarding the method of calculation, it is not clear for me how the use of the empirical dispersion D3 acts on the different noncovalent interactions and on the computed interaction energies. High-level post-HF calculations that include dispersion rigorously seem more appropriate for such studies. Please, comment.

In the EDA analysis, is the Basis Set Superposition Error (BSSE) taken into account?

In all figures, although it is generally obvious, please indicate the colors of the atoms.

Author Response

First, we would like to thank this reviewer for his/her careful reading of the manuscript, corrections and suggestions. Our "point-by-point" responses are detailed below:

The Authors investigated theoretically the occurrence of chalcogen bonds, halogen bonds and halogen…halogen contacts in different iodo organyl tellurium (IV) compounds in the solid state. For this purpose, they carried out DFT calculations using extended atomic basis sets, dispersion interactions being taken into account empirically. The studied species have been well chosen. The different possible noncovalent interactions have been carefully characterized using several descriptors. The paper is well written, illustrated, documented and pleasant to read.

General reply: Thank you for your positive opinion and recommendation.

To my opinion, only few points deserve more explanation before publication.

Regarding the method of calculation, it is not clear for me how the use of the empirical dispersion D3 acts on the different noncovalent interactions and on the computed interaction energies. High-level post-HF calculations that include dispersion rigorously seem more appropriate for such studies. Please, comment.

Reply: We agree with the reviewer that post-HF methods would be recommended. However, it has been demonstrated that the PBE0-D3 method gives comparable results to CCSD(T) with lower computational cost. See ref [113]. Some sentences have been added in the computational methods

In the EDA analysis, is the Basis Set Superposition Error (BSSE) taken into account?

Reply: It is not taken into account. However the BSSE is very small when using DFT calculations. This has been also commented in the theoretical methods

In all figures, although it is generally obvious, please indicate the colors of the atoms.

Reply: Done

Reviewer 2 Report

The manuscript by A. Frontera et al. presents the results of the CSD survey aimed at finding various types of interactions present in crystal structures containing both iodine and tellurium atoms. This comprises halogen (type II halogen-halogen contacts) and chalcogen bonds and also type I halogen-halogen contacts. To analyse these interactions the Authors use the following methods: QTAIM, NCI plot and Kitaura-Morokuma energy decomposition scheme. I think that the manuscript should be published in Inorganics after the minor revision. The following remarks should are addressed:

1) In the “Materials and Methods” section there is no information whether the structural parameters of studied systems were optimized or not. I assume that they were not but it should be clearly stated.

2) The choice of the DFT functional for the study should be somehow justified. Was the PBE0 functional with the D3 dispersion correction used in previous studies of systems containing iodine or tellurium atoms? Or it performs well in studies of halogen and chalcogen bonding?

Minor technical issues:

1) Lines 37-38: The citations in this sentence should be rather “Chalcogen bonding (ChB) is a sub-class of σ-hole interaction that has been recently 37 defined by the IUPAC [2] similarly to that of halogen bond [1].” (according to the references numbering from the manuscript)

2) Line 49: “Torubayev” instead of “Turubaev”.

3) Line 350: There is no section entitled “computational methods” and due to this the parentheses can be misleading.

4) Figure 13: The Figure together with its captions can be misleading due to different ordering of the terms in the figure and its caption. Also the order of type of interaction and the structure refcode is different for the two first systems.

5) Cartesian coordinates taken from the crystal structures for further QM computations should be given in Supplementary Materials (such file is not available or I missed something).

Author Response

First, we would like to thank this reviewer for his/her careful reading of the manuscript, corrections and suggestions. Our "point-by-point" responses are detailed below:

The manuscript by A. Frontera et al. presents the results of the CSD survey aimed at finding various types of interactions present in crystal structures containing both iodine and tellurium atoms. This comprises halogen (type II halogen-halogen contacts) and chalcogen bonds and also type I halogen-halogen contacts. To analyse these interactions the Authors use the following methods: QTAIM, NCI plot and Kitaura-Morokuma energy decomposition scheme. I think that the manuscript should be published in Inorganics after the minor revision. The following remarks should are addressed:

General reply: thank you for your positive opinion and recommendation.

1) In the “Materials and Methods” section there is no information whether the structural parameters of studied systems were optimized or not. I assume that they were not but it should be clearly stated.

Reply: Thank you. This has been clarified in the theoretical methods.

2) The choice of the DFT functional for the study should be somehow justified. Was the PBE0 functional with the D3 dispersion correction used in previous studies of systems containing iodine or tellurium atoms? Or it performs well in studies of halogen and chalcogen bonding?

Reply: Thank you. This has been justified in the theoretical methods.

Minor technical issues:

1) Lines 37-38: The citations in this sentence should be rather “Chalcogen bonding (ChB) is a sub-class of σ-hole interaction that has been recently 37 defined by the IUPAC [2] similarly to that of halogen bond [1].” (according to the references numbering from the manuscript)

Reply: Fixed!

2) Line 49: “Torubayev” instead of “Turubaev”.

Reply: in reference 50 the name is written Turubaev, see https://doi.org/10.3390/molecules26061583!

3) Line 350: There is no section entitled “computational methods” and due to this the parentheses can be misleading.

Reply: Fixed!

4) Figure 13: The Figure together with its captions can be misleading due to different ordering of the terms in the figure and its caption. Also the order of type of interaction and the structure refcode is different for the two first systems.

Reply: Figure 13 has been modified accordingly.

5) Cartesian coordinates taken from the crystal structures for further QM computations should be given in Supplementary Materials (such file is not available or I missed something).

Reply: Done. The ESI has been created with the coordinates.