Thiazole- and Thiadiazole-Based Metal–Organic Frameworks and Coordination Polymers for Luminescent Applications
Round 1
Reviewer 1 Report
The Ms submitted by Dr. A. Rossin is a mini review that describes and review the recent literature work (2015-2019) on the thiazole- and thiadiazole derivatives of MOFs and CPs and their potential applications luminescent sensors. The main approach of the review depends on introducing simultaneously bridging of metal ions to S- and N-donor atoms via the thiazol and thiadiazole based ligands and poly carboxylic ligands with different degrees of linking capabilities. These of course leads to the construction of MOFs with variable pores (cavities) and CPs with different dimensionality. Overall, this review is useful for researchers working in this area and for coordination chemists in general. The Ms should be accepted after minor changes, which I can summarize as follows:
1) In fact N-donor ligands cannot be considered as hard Lewis bases as it was indicated on p-3 but instead, it is classified at the border line of HSAB concept. Please check and see Polyhedron 2012, 31, 601 and J. Mol. Struct. 2011, 1006, 570.
2) Please insert as space for all references cited after line 66, ………. [XX] …….
3) There should be a space for paragraphs between lines 66-99.
4) Line 116: Dpe was proved …. (not proves)
5) Line 164: …., in the presence and absence of Hg(II) ions ….. (not both alone and in the presence of Hg(II) ions).
Author Response
1. In fact N-donor ligands cannot be considered as hard Lewis bases as it was indicated on p-3 but instead, it is classified at the border line of HSAB concept.
The reviewer is right, but in this case we were referring to nitrogen (as an element) as hard Lewis base in comparison with sulphur that is undoubtedly softer than nitrogen.
2. Line 116: Dpe was proved …. (not proves); Line 164: …, in the presence and absence of Hg(II) ions …(not both alone and in the presence of Hg(II) ions).
All these sentences have been checked and corrected.
Reviewer 2 Report
The subject of the review has a particular importance in the recently advances in MOFs and CPs. The content appears to be comprehensive of the synthetic approaching of new MOFs and CPs including their luminescent applications. The range of considered luminescent applications is also quite exhaustive of the most investigated materials in this field in the recent years. As a conclusion, the review appears to be appealing for the scientific community.
Author Response
Thanks for reviewer's positive review report. There is no more response.
Reviewer 3 Report
This mini-review submitted by Rossin and coworkers represents a solid work that summarizes in a detailed but brief way the works conducted during the last five years in which thiazole- and thiadiazole-containing metal-organic frameworks (MOFs) and coordination polymers (CPs) possessing luminescent sensing performance are described. Overall, the work is interesting and it should be accepted for the journal after some minor revisions.
1) In the introduction of the review, authors have omitted some important references related to the luminescence of metal ions with d10 electronic configuration (see for instance Chem. Commun., 2008, 2185 and CrystEngComm 2016, 18, 8556). These works should be cited along with reference no. 10.
2) In the next sentence, authors state “Metal-centered luminescence (mainly phosphorescence) is seen primarily in MOFs containing f-elements as nodes.” Although this sentence is true, some relevant works published during the last years have shown that phosphorescence may also happen for MOFs containing metal ions with d10 electronic configuration (see the following micro-review: Eur. J. Inorg. Chem. 2018, 2155 and references therein).
3) In page 4, authors mention some common pyridyl-like ligands that have been extensively employed in coordination polymers such as 1,2-bis(4-pyridyl)ethylene and 1,2-bis(4-pyridyl)ethane. These ligands are shortened in the manuscript as dpe and bpe, although, as far as I am aware, they are more commonly referred to as bpe and bpa, respectively. I encourage authors to use these other more common acronyms.
4) In the first paragraph of section 2, the examples given talk about the luminescence properties of compounds containing pyridyl-like molecules as co-ligands. Which is the paper of thiazole-containing ligands in these compounds? I mention this because the review focuses on them and not on other co-ligands.
5) Please, correct the following typo error in the sentence: “The group of Arici et al. (Eskiseir, TK) prepared three novel Co(II) coordination polymers…”. In any case, is this cobalt-based compound luminescent as to be included in this review? I do not see the connection with this work.
6) Please, give molecular formulae of MOFs in a proper way: for instance highlighting their polymeric nature such as in the case of “formula {[Zr6O4(OH)4(BTDB)6] 8H2O 6DMF}n”.
7) Related with the previous comment, please give the correct molecular formulae (in a unified way) for all MOFs reported in this work. Any reader should know the formula of the material that is being discussed in each paragraph.
8) I would retype the sentence on line 325 as follows: “In 2019, the same MOF has also been exploited by Eddaoudi and co-workers…”
Provided that authors accomplish and correctly address the previous comments I believe that the work could become publishable.
Author Response
1. In the introduction of the review, authors have omitted some important references related to the luminescence of metal ions with d10 electronic configuration (see for instance Chem. Commun.,2008, 2185 and CrystEngComm 2016, 18, 8556). These works should be cited along with reference no. 10.
The quoted references have been added as new references [11] and [12], as requested.
2. In the next sentence, authors state “Metal-centered luminescence (mainly phosphorescence) is seen primarily in MOFs containing f-elements as nodes.” Although this sentence is true, some relevant works published during the last years have shown that phosphorescence may also happen for MOFs containing metal ions with d10 electronic configuration (see the following micro-review: Eur. J. Inorg. Chem. 2018, 2155 and references therein).
The reviewer is right. We have modified the sentence accordingly, and added the quoted microreview to the text (new reference [14]).
3. Please, correct the following typo error in the sentence: “The group of Arici et al. (Eskiseir, TK) prepared three novel Co(II) coordination polymers…”. In any case, is this cobalt-based compound luminescent as to be included in this review? I do not see the connection with this work.
The typo has been corrected. The connection with this work in this case is simply limited to the presentation of the adsorption spectra of ligands and polymers. No emission or application is described. We are aware of the fact that this has little to do with the review subject, but we wanted to be exhaustive in the collection of the literature data, in order to have a survey as complete as possible.
4. Please give the correct molecular formulae (in a unified way) for all MOFs reported in this work. Any reader should know the formula of the material that is being discussed in each paragraph.
We believe that we have already provided such an information as requested by the reviewer.
