Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers
, Dmitry I. Pavlov, Alexey A. Ryadun, Vladimir P. Fedin * and Andrei S. Potapov *Round 1
Reviewer 1 Report
Key issues:
1. The abstract fails to highlight the strengths of the study, the introduction should be concise to highlight the key points; in the foreword, the introduction about the background is not clear enough, and some confusion in logic needs to reorganized the ideas;
2. Some parts of Zn-MOF are bolded and some parts are not bolded, which needs to be standardized;
3. The drawings need to be beautified (Figure 1, Figure 4(a), Figure 5). The relevant information should be added as much as possible.
Other issues:
1. The layout of the images is not standardized, as well as the alignment of the figure notes below is not standardized, and the format needs to be standardized.
2. Please check the subscripts in the full text, some ionic forms do not have subscripts for numbers, such as [Fe(H2O)] in 3.5 part, and there are also references that do not have subscripts for numbers.
3. Is it necessary to indent the first line of the image label? For example, figure5 and figure 6 are not consistent.
4. In page 2, check the grammar. In the sentence "However, their widespread application for detection of Fe3+ is", a "the" should be added after "for ".
5. In the text, the representation of Figure is not uniform, such as (Figure 2c) and (Figure 5,a), is there a comma between the number and the letter?
Key issues:
1. The abstract fails to highlight the strengths of the study, the introduction should be concise to highlight the key points; in the foreword, the introduction about the background is not clear enough, and some confusion in logic needs to reorganized the ideas;
2. Some parts of Zn-MOF are bolded and some parts are not bolded, which needs to be standardized;
3. The drawings need to be beautified (Figure 1, Figure 4(a), Figure 5). The relevant information should be added as much as possible.
Other issues:
1. The layout of the images is not standardized, as well as the alignment of the figure notes below is not standardized, and the format needs to be standardized.
2. Please check the subscripts in the full text, some ionic forms do not have subscripts for numbers, such as [Fe(H2O)] in 3.5 part, and there are also references that do not have subscripts for numbers.
3. Is it necessary to indent the first line of the image label? For example, figure5 and figure 6 are not consistent.
4. In page 2, check the grammar. In the sentence "However, their widespread application for detection of Fe3+ is", a "the" should be added after "for ".
5. In the text, the representation of Figure is not uniform, such as (Figure 2c) and (Figure 5,a), is there a comma between the number and the letter?
Author Response
- The abstract fails to highlight the strengths of the study, the introduction should be concise to highlight the key points; in the foreword, the introduction about the background is not clear enough, and some confusion in logic needs to reorganized the ideas;
The abstract was significantly reworked and expanded with special emphasis on logical development of ideas discussed.
- Some parts of Zn-MOF are bolded and some parts are not bolded, which needs to be standardized;
Zn-MOF is now bold everywhere in the manuscript.
- The drawings need to be beautified (Figure 1, Figure 4(a), Figure 5). The relevant information should be added as much as possible.
These figures were updated and the resolution was ensured for effective reproduction.
Other issues:
- The layout of the images is not standardized, as well as the alignment of the figure notes below is not standardized, and the format needs to be standardized.
The formatting was made in accordance with Inorganics template.
- Please check the subscripts in the full text, some ionic forms do not have subscripts for numbers, such as [Fe(H2O)] in 3.5 part, and there are also references that do not have subscripts for numbers.
Typos corrected.
- Is it necessary to indent the first line of the image label? For example, figure5 and figure 6 are not consistent.
Figure notations were corrected.
- In page 2, check the grammar. In the sentence "However, their widespread application for detection of Fe3+ is", a "the" should be added after "for ".
A thorough check was done on the grammar and spelling, several corrections, including for the mentioned one, were introduced.
- In the text, the representation of Figure is not uniform, such as (Figure 2c) and (Figure 5,a), is there a comma between the number and the letter?
Representation was made uniform.
Reviewer 2 Report
The manuscript titled “Synthesis, crystal structure and luminescent sensing properties of a supramolecular 3D zinc(II) metal-organic framework with terephthalate and bis(imidazol-1-yl)methane linkers” of the authors V. V. Matveevskaya, D. I. Pavlov, A. A. Ryadun, Vladimir P. Fedin, and A. S. Potapov is well-organized and well-written. My first opinion was that this manuscript presents valuable results adequately, but I have found many serious disagreements between the submitted checkcif and the one obtained by running the checkcif of the submitted cif file. I send the checkcif file in the attachment. Please address these issues.
Some minor remarks are:
· For the IR spectra, it should be mentioned if the ATR or KBr technique was used.
· Some letters should be italics (for example lines 14 and 97 P42/n, Lines 109, 111, 113, and Table 1 names of the axis)
· In Table 1, the angle values should be omitted, it is clear they are 90 degrees.
· Line 174: There is a typo in hexaaquairon(III).
Comments for author File: 
Comments.pdf
Author Response
My first opinion was that this manuscript presents valuable results adequately, but I have found many serious disagreements between the submitted checkcif and the one obtained by running the checkcif of the submitted cif file. I send the checkcif file in the attachment. Please address these issues.
The CIF file uploaded as a supplementary material was not finalized and did not correspond to the file deposited with CCDC. We are sorry for this oversight and now provide the CIF file identical to the deposited one, which does not have critical alerts in the CheckCIF report.
Some minor remarks are:
For the IR spectra, it should be mentioned if the ATR or KBr technique was used.
The IR spectra were recorded in KBr pellets (it is now indicated in line 277)
Some letters should be italics (for example lines 14 and 97 P42/n, Lines 109, 111, 113, and Table 1 names of the axis)
Corrected.
In Table 1, the angle values should be omitted, it is clear they are 90 degrees.
Table 1 was corrected, the angles were omitted.
Line 174: There is a typo in hexaaquairon(III).
Corrected.
Reviewer 3 Report
Authors synthesized Zn-MOF and characterized the structure by X-ray crystallography. They described that Zn-MOF is a layer interpenetrated 3D network. They also reported the luminescent sensing property.
The article is well organized, but they should revise description of the structure of Zn-MOF. The article is recommended for publication on Inorganic after major revision.
Revision points:
(1) In the text, they mentioned that “Separations between the asymmetric and symmetric stretching frequencies are 284 and 248 cm-1”, but it does not show in Fig. S2. They measured IR down to 500 cm-1.
(2) The space group P42n should be P42n.
(3) They mentioned that “The coordination environment of each Zn2+ ion is distorted square pyramidal.”, but it doesn’t like square pyramidal, and doesn’t like the apical position as N(1). The coordination environment should be tetrahedral with chelating bonding and two N and one O.
(4) They said that the free volume is 28%. Is this void volume of Zn-MOF without solvent? How did they calculate the free volume? It is different from the value calculated by PLATON.
(5) If they used PLATON SQUEEZE to remove data for solvents, they should put the condition of SQUEEZE in cif.
Author Response
(1) In the text, they mentioned that “Separations between the asymmetric and symmetric stretching frequencies are 284 and 248 cm-1”, but it does not show in Fig. S2. They measured IR down to 500 cm-1.
284 and 248 cm-1 are not meant to represent exact band positions, but rather the difference value (D) between them. The notation was added to line 162 to avoid misunderstanding.
(2) The space group P42n should be P42n.
Corrected.
(3) They mentioned that “The coordination environment of each Zn2+ ion is distorted square pyramidal.”, but it doesn’t like square pyramidal, and doesn’t like the apical position as N(1). The coordination environment should be tetrahedral with chelating bonding and two N and one O.
Figure 2a was adjusted to better represent the coordination polyhedral of Zn in this case. We agree that square pyramidal environment for Zn2+ ion is rare, however, according to the calculated t5 value, it should be denoted as square pyramidal.
(4) They said that the free volume is 28%. Is this void volume of Zn-MOF without solvent? How did they calculate the free volume? It is different from the value calculated by PLATON.
An updated CIF file was resubmitted, the free volume calculated by PLATON is 29%.
(5) If they used PLATON SQUEEZE to remove data for solvents, they should put the condition of SQUEEZE in cif.
An updated CIF was resubmitted and now it includes the SQUEEZE details.
Round 2
Reviewer 2 Report
The manuscript titled “Synthesis, crystal structure and luminescent sensing properties of a supramolecular 3D zinc(II) metal-organic framework with terephthalate and bis(imidazol-1-yl)methane linkers” of the authors V. V. Matveevskaya, D. I. Pavlov, A. A. Ryadun, Vladimir P. Fedin, and A. S. Potapov has been improved and the all mentioned issues were resolved. I have only one remaining remark – the disorder in the structure should be described in the manuscript.
Author Response
Disorder of one bim ligand in the structure of Zn-MOF is now mentioned in lines 166-168 of the revised manuscript and is shown in Figure S3 of the Supplementary materials.
