Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and X-ray Crystal Structures
2.2. Optimized Geometries
2.3. Magnetic Properties
2.4. Effect of the Substituents and QTAIM Analysis
3. Materials and Methods
3.1. General
3.2. Synthesis of [Fe4(μ3-O)2(μ-LNO2)4] (1)
3.3. Synthesis of [Fe4(μ3-O)2(μ-LCl)4] (2)
3.4. Synthesis of [Fe4(μ3-O)2(μ-LOMe)4] (3)
3.5. Crystal Structure Determination
3.6. Theoretical Calculations
3.7. Magnetic Measurements
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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1·1.5iPr2O 3 | 2·2iPr2O | 3 | |
---|---|---|---|
Fe1–O17 | 1.784(5), 1.783(5) | 1.7994(11) | – |
1.818 | 1.825 | 1.829 | |
Fe4–O18 | 1.797(5), 1.789(5) | 1.8040(11) | – |
1.818 | 1.825 | 1.829 | |
Fe2–O17 | 1.948(5), 1.979(5) | 1.9380(12) | – |
1.951 | 1.947 | 1.944 | |
Fe2–O18 | 1.967(5), 1.964(5) | 1.9461(11) | – |
1.951 | 1.946 | 1.944 | |
Fe3–O17 | 1.970(5), 1.948(5) | 1.9567(11) | – |
1.951 | 1.946 | 1.944 | |
Fe3–O18 | 1.939(5), 1.967(5) | 1.9389(12) | – |
1.951 | 1.947 | 1.944 | |
Fe1–O1 | 1.865(5), 1.865(5) | 1.9021(13) | – |
1.892 | 1.891 | 1.891 | |
Fe1–O5 | 1.925(5), 1.925(5) | 1.8662(12) | – |
1.892 | 1.889 | 1.891 | |
Fe1–N1 | 2.160(6), 2.165(7) | 2.1636(11) | – |
2.170 | 2.158 | 2.150 | |
Fe1–N4 | 2.193(6), 2.171(6) | 2.1930(15) | – |
2.170 | 2.157 | 2.150 | |
Fe2–O4 | 1.964(5), 1.924(5) | 1.9698(13) | – |
1.956 | 1.960 | 1.967 | |
Fe2–O13 | 1.954(5), 1.915(6) | 1.9319(11) | – |
1.956 | 1.959 | 1.967 | |
Fe2–N3 | 2.211(6), 2.198(7) | 2.2609(12) | – |
2.225 | 2.224 | 2.211 | |
Fe2–N10 | 2.207(7), 2.233(6) | 2.2729(13) | – |
2.224 | 2.224 | 2.211 | |
Fe1···Fe2 | 3.426(2), 3.427(2) | 3.4241(4) | – |
3.419 | 3.424 | 3.427 | |
Fe1···Fe3 | 3.402(2), 3.406(2) | 3.3738(5) | – |
3.419 | 3.426 | 3.427 | |
Fe4···Fe2 | 3.413(2), 3.415(2) | 3.4210(5) | – |
3.419 | 3.426 | 3.427 | |
Fe4···Fe3 | 3.420(2), 3.428(2) | 3.3736(4) | – |
3.419 | 3.424 | 3.427 | |
Fe1···Fe4 | 6.168(2), 6.172(2) | 6.1128(7) | – |
6.155 | 6.174 | 6.183 | |
Fe2···Fe3 | 2.929(2), 2.937(2) | 2.9683(4) | – |
2.980 | 2.965 | 2.957 |
1 (NO2) | 2 (Cl) 1 | 3 (OMe) | |
---|---|---|---|
Jbb (cm–1) | –0.94 ± 0.06 | –41.7 ± 0.2 | –14.0 ± 0.3 |
Jwb (cm–1) | –1.20 ± 0.02 | –25.2 ± 0.1 | –8.2 ± 0.1 |
Jbb/Jwb | 0.79 ± 0.05 | 1.66 ± 0.01 | 1.71 ± 0.04 |
Ground state | |5,5,0〉 | |3,5,2〉 | |3,5,2〉 |
1 (NO2) | 2 (Cl) | 3 (OMe) | |
---|---|---|---|
Feb | 1.899 | 1.898 | 1.897 |
Few | 1.836 | 1.838 | 1.839 |
μ3-O | –1.204 | –1.207 | –1.208 |
Σ{Fe4(μ3-O)2} | 5.062 | 5.058 | 5.056 |
ρBCP (e Å–3) | ∇2ρBCP (e Å–5) | GBCP (Hartree Å–3) | VBCP (Hartree Å–3) | HBCP (Hartree Å–3) | |
---|---|---|---|---|---|
Compound 1 | |||||
Feb–O | 0.628 | 11.7 | 0.132 | –0.143 | –0.011 |
Few–O | 0.889 | 16.9 | 0.210 | –0.245 | –0.035 |
Compound 2 | |||||
Feb–O | 0.636 | 11.9 | 0.134 | –0.146 | –0.012 |
Few–O | 0.870 | 16.6 | 0.205 | –0.237 | –0.032 |
Compound 3 | |||||
Feb–O | 0.640 | 12.0 | 0.135 | –0.147 | –0.012 |
Few–O | 0.863 | 16.5 | 0.202 | –0.234 | –0.032 |
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Marchi, L.; Carlino, S.; Castellano, C.; Demartin, F.; Forni, A.; Ferretti, A.M.; Ponti, A.; Pasini, A.; Rigamonti, L. Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core. Int. J. Mol. Sci. 2023, 24, 5808. https://doi.org/10.3390/ijms24065808
Marchi L, Carlino S, Castellano C, Demartin F, Forni A, Ferretti AM, Ponti A, Pasini A, Rigamonti L. Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core. International Journal of Molecular Sciences. 2023; 24(6):5808. https://doi.org/10.3390/ijms24065808
Chicago/Turabian StyleMarchi, Lorenzo, Stefano Carlino, Carlo Castellano, Francesco Demartin, Alessandra Forni, Anna M. Ferretti, Alessandro Ponti, Alessandro Pasini, and Luca Rigamonti. 2023. "Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core" International Journal of Molecular Sciences 24, no. 6: 5808. https://doi.org/10.3390/ijms24065808