Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and General Characterization of Square Pyramidal Clusters
2.2. Crystal Structure of Compounds
2.3. Physicochemical Properties
2.4. UV-Vis-NIR Absorption
3. Materials and Methods
3.1. Chemicals and Materials
3.2. Syntheses
3.2.1. [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)t5]Br pzH·H2O (Denoted as [1red]Br)
3.2.2. [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)t5]Br2 2H2O (Denoted as [1ox]Br2)
3.2.3. [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)bs4Bra]Br (Denoted as [2]Br)
3.2.4. [{Mo5(μ3-S)i4(μ4-S)i(μ-4-Br-pz)i4}(pzH)t5]Br2 (Denoted as [3]Br2)
3.2.5. [{Mo5(μ3-S)i4(μ4-S)i(μ-4-Br-pz)i4}(pzH)bs4Bra]Br (Denoted as [4]Br)
3.3. Physical Methods
3.4. Single-Crystal X-ray Diffraction Analysis (XRD)
3.5. Cyclic Voltammetry
3.6. EPR
3.7. Magnetic Susceptibility
3.8. DFT Calculations
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Compound | Mobs–Mobs (Average) | Mobs–Moa (Average) | Mo–μ3-S (Average) | Mo–μ4-S (Average) |
---|---|---|---|---|
[1red]Br | 2.7980(3)–2.8010(4) (2.8000) | 2.6384(4)–2.6459(4) (2.6422) | 2.3982(8)–2.4395(8) (2.4187) | 2.4235(6)–2.4318(6) (2.4277) |
[1ox][Mo6I14] | 2.8136(6)–2.8249(6) (2.8193) | 2.6288(6)–2.6322(6) (2.6305) | 2.3781(14)–2.4523(12) (2.4168) | 2.4296(12)–2.4390(12) (2.4343) |
[2]Br·2.5H2O·0.5DMF | 2.7951(17)–2.8217(17) (2.8080) | 2.6285(18)–2.6345(18) (2.6310) | 2.368(4)–2.479(4) (2.423) | 2.443(4)–2.447(4) (2.446) |
[3]Br2·CH3CN·Et2O | 2.8073(10)–2.8244(10) (2.8168) | 2.6185(10)–2.6341(10) (2.6269) | 2.363(2)–2.465(2) (2.402) | 2.436(2)–2.449(2) (2.441) |
[4]Br·1.25H2O·2DMSO | 2.7816(9)–2.7985(17) (2.790) | 2.6468(11)–2.6526(10) (2.6497) | 2.387(2)–2.441(3) (2.411) | 2.432(2)–2.436(2) (2.434) |
Mo5Se5red | 2.8398(2) | 2.6823(3) | 2.5572(2) | 2.5329(3) |
Mo5Se5ox | 2.865(1) | 2.660(1)–2.674(1) (2.667) | 2.499(1)–2.5712(8) (2.5326) | 2.547(1)–2.550(1) (2.548) |
Mo–Nμ-pz (average) | Mobs–NpzH (average) | Moa–NpzH (average) | Moa–Br (average) | |
[1red]Br | 2.183(3)–2.194(2) (2.186) | 2.207(3)–2.210(3) (2.209) | 2.199(4) | – |
[1ox][Mo6I14] | 2.155(4)–2.177(4) (2.165) | 2.189(4)–2.198(4) (2.194) | 2.197(6) | – |
[2]Br·2.5H2O·0.5DMF | 2.145(14)–2.180(15) (2.167) | 2.212(12)–2.225(13) (2.216) | – | 2.632(3)–2.640(3) (2.636) |
[3]Br2·CH3CN·Et2O | 2.149(7)–2.188(7) (2.175) | 2.190(7)–2.209(7) (2.200) | 2.236(8) | – |
[4]Br·1.25H2O·2DMSO | 2.223(7) | 2.189(6)–2.193(6) (2.191) | – | 2.6327(15) |
Mo5Se5red (a) | 2.184(2)–2.194(2) (2.189) | 2.217(2) | 2.239(4) | – |
Mo5Se5ox (a) | 2.164(8)–2.209(7) (2.179) | 2.214(7)–2.230(7) (2.222) | 2.25(1) | – |
Compound | Solvent | Process [a] | Ea | Ec | E1/2 | Ref. |
---|---|---|---|---|---|---|
Mo5Se5red | ACN | 15 VEC to 16 VEC, qrev | –0.54 | –0.60 | –0.57 | [24] |
15 VEC to 14 VEC, rev | 0.14 | 0.07 | 0.11 | |||
[1ox]Br2 | ACN | 14 VEC to 15 VEC, rev | 0.17 | 0.10 | 0.14 | This work |
15 VEC to 16 VEC, qrev | –0.53 | –0.61 | –0.57 | |||
DCM | 14 VEC to 15 VEC, rev | 0.22 | 0.14 | 0.18 | ||
15 VEC to 16 VEC, qrev | –0.46 | –0.57 | –0.52 | |||
[2]Br | DCM | 14 VEC to 15 VEC, rev | –0.03 | –0.12 | –0.08 | |
15 VEC to 16 VEC, irrev | – | –0.80 | – | |||
[3]Br2 | DCM | 14 VEC to 15 VEC, rev | 0.38 | 0.29 | 0.33 | |
15 VEC to 16 VEC, qrev | –0.34 | –0.42 | –0.38 | |||
[4]Br | DCM | 14 VEC to 15 VEC, rev | 0.17 | 0.09 | 0.13 | |
15 VEC to 16 VEC, qrev | –0.51 | –0.60 | –0.56 |
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Savina, I.V.; Ivanov, A.A.; Eltsov, I.V.; Yanshole, V.V.; Kuratieva, N.V.; Komarovskikh, A.Y.; Syrokvashin, M.M.; Shestopalov, M.A. Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties. Int. J. Mol. Sci. 2023, 24, 13879. https://doi.org/10.3390/ijms241813879
Savina IV, Ivanov AA, Eltsov IV, Yanshole VV, Kuratieva NV, Komarovskikh AY, Syrokvashin MM, Shestopalov MA. Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties. International Journal of Molecular Sciences. 2023; 24(18):13879. https://doi.org/10.3390/ijms241813879
Chicago/Turabian StyleSavina, Iulia V., Anton A. Ivanov, Ilia V. Eltsov, Vadim V. Yanshole, Natalia V. Kuratieva, Andrey Y. Komarovskikh, Mikhail M. Syrokvashin, and Michael A. Shestopalov. 2023. "Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties" International Journal of Molecular Sciences 24, no. 18: 13879. https://doi.org/10.3390/ijms241813879