Lanthanide(III) Complexes with Thiodiacetato Ligand: Chemical Speciation, Synthesis, Crystal Structure, and Solid-State Luminescence
Round 1
Reviewer 1 Report
The manuscript reports on the synthesis, structural characterization and solid state luminescence of two Ln-based thiodiacetate (tda) complexes. In this work it has been also revisited the solution chemistry of the H2tda + Ln3+ systems by potentiometry. The work was carried out at a high experimental level. The manuscript is well written. As a comment, I would like to note that the introduction contains an erroneous statement «no reports can be found containing bis-chelated fragments in mononuclear compounds, and these structures always contain a coligand». Work [32] in References just contains the first example of bis-chelated [Co(tda)2]2- anionic complex. Also the common name «thiodiacetate» should be used instead «thiodiacetato». I recommend the manuscript for publication in Crystals after minor corrections.
Author Response
We appreciate very much the comments of Reviewer #1.
There was an error in the Introduction section as stated by the reviewer, which was corrected.
We have used the IUPAC nomenclature, i.e. «thiodiacetate» for the anion, and «thiodiacetato» for the ligand along the manuscript. We checked it and changed if necessary.
Reviewer 2 Report
The manuscript reported that three new coordination polymer and its luminescence emission of both complexes in the solid state. Although I appreciated the idea, there are quite a few problems before it can be recommended for publication. The main problems are listed as follows: 1. In Fig. 2, all the atoms are labeled superscript for i, ii, iii 2. Please provide the TGA data 3.” with general formula [Ln2(tda)3(H2O)5].3H2O (Ln = Sm, Eu; tda = thiodiacetato)” changed to with general formula [Ln2(tda)3(H2O)5].3H2O (Ln = Sm for 1, Eu for 2; tda = thiodiacetato)4.In addition, they have great potential as functional solid materials such as luminescent materials, magnetic devices, chemical sensors, etc. There some popular application, such as biomedical, and gas adsorption, such as Inorganics, 10(2022) 202; Journal of Materials Chemistry B, 2021, 9, 4459 – 4474; J. Mater. Chem. B., 2022, 10, 5105 – 5128 and Micropor. Mesopor. Mat, 341(2022) 112098.
5. The ref 66, 67 should be updated
6. The fig 3 should be redraw, the guest water should be involved the hydrogen-bonded interaction.
Author Response
We appreciate the comments of Reviewer #2.
- Superscripts were added in Figure 2.
- TGA were added as well as a brief discussion of them.
- We checked it and changed if necessary.
- We have seen the proposed references, buy they are not related with this work or future applications of the materials presented in the manuscript. In this sense, we prefer not to add more references.
- These references are the last ones recommended by IUCr
https://journals.iucr.org/m/services/stdswrefs.html
- Figure 3 contains packing and disposition of the polyhedral. If H-bons are added, it will be very confusing. A new figure (S5) has been added, showing intermolecular H-bonds.
Reviewer 3 Report
In this manuscript, Torres et al. describe two new Ln3+ complexes with anion of thiodiglycolic acid. It is very surprizing that the authors managed to isolate new phases in these systems because other similar Ln3+ complexes with lower number of H2O molecules are known. So, alone this fact justifies publication in Crystals. The text is well written; characterization of the samples is performed in due order so overall there are not too many recommendations:
1) It would be nice to add TGA data to see the rate and tempreature of water elimination. This is not obligatory, but is would improve the work.
2) References. There are several works on Ln3+ complexes with this ligand which are yet not mentioned:
a) 10.1021/acs.cgd.0c00294
b) 10.1016/S1387-7003(01)00330-6
c) 10.1016/j.ica.2016.01.005
d) 10.1107/S1600536811002923
e) 10.1071/CH98051
Also, there are several recent works on Ln3+ carboxylates which are, in my opinion, work being mentioned in Intro (not obligatory, but it could be useful):
a) 10.1007/s11172-022-3498-y
b) 10.1134/S1070328422030058
с) 10.1134/S1070363220120439
d) 10.1134/S1070328422090056
e) 10.1134/S1070328422080073
f) 10.1134/S002247662203009X
g) 10.1134/S0022476621100152
Author Response
We appreciate very much the comments of Reviewer #3.
TGA were added as well as a brief discussion of them. We have incorporated the missing references of Ln complexes with tda. We also thank general references noted by the reviewer which will very useful for our future work.
