Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis
2.1.1. Synthesis of the Ligand L
2.1.2. Synthesis of the Complex [Fe(L)2](BF4)2
2.2. X-ray Crystallography
2.3. NMR Spectroscopy
2.3.1. Evans Method
2.3.2. Temperature-Dependence of Chemical Shifts
2.3.3. Analysis of Theoretical Chemical Shifts
2.4. Quantum Chemistry
3. Results and Discussion
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Parameter | [Fe(L)2](BF4)2·2CH3CN (red) | [Fe(L)2](BF4)2·0.5H2O (red) | [Fe(L)2](BF4)2·2CH3CN (Yellow) | |
---|---|---|---|---|
Formula unit | 2(C62H58Cl8FeN10), 4(BF4), 4(C2H3N) | 2C62H58Cl8FeN10, 4BF4, H2O | C62H58Cl8FeN10, 2BF4, 2C2H3N | C62H58Cl8FeN10, 2BF4, 2C2H3N |
Formula weight | 3088.73 | 2930.52 | 1538.36 | 1539.37 |
T, K | 120 | 120 | 120 | 293 |
Crystal system | Orthorhombic | Monoclinic | Orthorhombic | Orthorhombic |
Space group | Pcbn | P21/n | Fdd2 | Fdd2 |
Z | 4 | 2 | 8 | 8 |
a, Å | 45.272(7) | 16.9032(12) | 42.2980(16) | 43.047(14) |
b, Å | 13.335(2) | 21.2547(15) | 14.6224(6) | 14.742(6) |
c, Å | 24.665(4) | 17.4043(12) | 22.9540(9) | 23.161(6) |
β, ° | 90 | 91.033(2) | 90 | 90 |
V, Å3 | 14,890(4) | 6251.9(8) | 14,197.0(10) | 14,699(8) |
Dcalc (g cm−1) | 1.378 | 1.557 | 1.439 | 1.390 |
Linear absorption, μ (cm−1) | 5.58 | 6.59 | 5.85 | 5.65 |
F(000) | 6328 | 2996 | 6304 | 6304 |
2θmax, ° | 52 | 54 | 54 | 54 |
Reflections measured | 93,601 | 66,188 | 37,118 | 36,822 |
Independent reflections | 14,645 | 13,643 | 7759 | 8029 |
Observed reflections [I > 2σ(I)] | 6631 | 7932 | 6893 | 3666 |
Parameters | 938 | 841 | 509 | 474 |
R1 | 0.1504 | 0.0521 | 0.0341 | 0.0656 |
wR2 | 0.4839 | 0.1237 | 0.0776 | 0.1776 |
GOF | 1.067 | 0.993 | 1.024 | 0.939 |
Δρmax/Δρmin (e Å−3) | 1.398/−0.664 | 0.753/−0.644 | 0.538/−0.332 | 0.847/−0.544 |
Parameter | [Fe(L)2](BF4)2·2CH3CN (red) | [Fe(L)2] (BF4)2·0.5H2O (red) | [Fe(L)2](BF4)2·2CH3CN (Yellow) | |
---|---|---|---|---|
120 K | 293 K | |||
Fe-NPy, Å | 1.901(12)–1.912(13) | 1.910(3)–1.916(3) | 2.044(5)–2.046(5) | 2.056(9)–2.067(12) |
Fe-NPz, Å | 2.025(12)–2.050(9) | 2.023(3)–2.032(3) | 2.196(3)–2.187(3) | 2.202(6)–2.205(7) |
θ,° | 89.61(11) | 89.545(1) | 88.882(1) | 90.53(9) |
φ,° | 179.4(4) | 179.30(12) | 180 | 180.00(4) |
γ,° | 89.7(5)–90.0 (7) av. 89.85 | 86.42(13)–89.49(13) av. 88.05 | 89.94(14)–89.04(13) av. 89.49 | 88.3(4)–89.0(4) av. 88.65 |
S(OC-6) | 2.599 | 2.299 | 3.786 | 3.819 |
S(ebcT-6) | 13.151 | 13.485 | 11.286 | 11.206 |
Parameter | [Fe(L)2](BF4)2 |
---|---|
T1/2, K | 175 |
∆H, kJ/mol | 15.2 |
∆S, J/mol | 86.9 |
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Melnikova, E.K.; Aleshin, D.Y.; Nikovskiy, I.A.; Denisov, G.L.; Nelyubina, Y.V. Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy. Crystals 2020, 10, 793. https://doi.org/10.3390/cryst10090793
Melnikova EK, Aleshin DY, Nikovskiy IA, Denisov GL, Nelyubina YV. Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy. Crystals. 2020; 10(9):793. https://doi.org/10.3390/cryst10090793
Chicago/Turabian StyleMelnikova, Elizaveta K., Dmitry Yu. Aleshin, Igor A. Nikovskiy, Gleb L. Denisov, and Yulia V. Nelyubina. 2020. "Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy" Crystals 10, no. 9: 793. https://doi.org/10.3390/cryst10090793