Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States
Abstract
:1. Introduction
2. Polyoxovanadoborates: Vanadate and Borate Fragments
2.1. Vanadate Fragments
2.2. Borate Fragments
3. Structural Description of the [V12B18O60] Core
4. [V12B18O60] Cores with Protonated Amines as Counterbalancing Ions
Compound | Formula | VIV/VV Ratio | Ref. |
---|---|---|---|
1 | (enH2)5{(VO)12O6[B3O6(OH)]6} H2O | 10/2 | [42] |
2 | (1,3-diapH2)5{(VO)12O6[B3O6(OH)]6} 6H2O | 10/2 | [42] |
3 | (H2dap)2H6{(VO)12O6[B3O6(OH)]6(H2O)} 13H2O | 10/2 | [49] |
4 | [H3teta]3[V12B18O54(OH)6(H2O)] (H3O) 5H2O | 10/2 | [34] |
5 | (NH4)8(1,3-diapH2)[V12B18O60H6] 5H2O | 10/2 | [57] |
5. [V12B18O60] Cores with Transition Metal Ions and Coordination Compounds as Counterbalancing Cations
Compound | Formula | VIV/VV Ratio | Ref. |
---|---|---|---|
6 | [Zn(en)2]6[(VO)12O6B18O39(OH)3] 13H2O | 9/3 | [43] |
7 | H3{[Cu(en)2]5[(VO)12O6B18O42]}[B(OH)3]2 16H2O | 7/5 † | [44] |
8 | [Ni(en)2]6H2[(VO)12O6B18O42] 15H2O | 8/4 | [45] |
9 | [Zn(teta)]6[(VO)12O6B18O36(OH)6](H2O) 8H2O | 12/0 | [48] |
10 | {[Zn(dien)]2[Zn(dien)(H2O)]4(VO)12O6[B3O6(OH)]6(H2O)}2 15H2O | 12/0 | [49] |
11 | {[Cu(dien)(H2O)]3V12B18O54(OH)6(H2O)} 4H3O 5.5H2O | 10/2 | [55] |
12 | {[Cd(H2O)2]3V12B18O54(OH)6(H2O)} 4H3O 9.5H2O | 10/2 | [55] |
13 | [Zn(H2teta)2V12B18O54(OH)6] 4H3O | 10/2 | [63] |
6. [V12B18O60] Cores with Alkaline Ions as Counterbalancing Cations
Compound | Formula | VIV/VV Ratio | Ref. |
---|---|---|---|
14 | (Na)10[(H2O)V12B18O60H6] 18H2O | 10/2 | [51] |
15 | {Na2B18V12O54(OH)6(H2O)[Na8(H2O)16]} 2H2O | 10/2 | [54] |
16 | {K2V12B18O54(OH)6(H2O)[K8(H2O)16]} 3H2O | 10/2 | [67] |
17 | {K10V12B18O54(OH)6(H2O)} 14H2O | 10/2 | [67] |
18 | K8(NH4)2[V12B18O60H6] 18H2O | 10/2 | [57] |
19 | K10[V12B18O60H6] 10H2O | 10/2 | [57] |
20 | K8Cs2[V12B18O60H6] 10H2O | 10/2 | [57] |
21 | Li8(NH4)2[V12B18O60H6] 8.02H2O | 10/2 | [58] |
7. [V12B18O60] Cores with Organic Ammonium, Alkaline, and/or Transition Metal Ions as Counterbalancing Cations: The Mixed Family
Compound | Formula | VIV/VV Ratio | Ref. |
---|---|---|---|
22 | (enH2)4Na4H3[(V12O6B18O42] 8H2O | 9/3 | [46] |
23 | K3Na5(H2NCH2CH2NH3)2{(VO)12O6[B3O6(OH)]6}(H2O) 12H2O | 10/2 | [47] |
24 | Na8[Cu(en)2]2[V12B18O60H6](NO3)2 14.7H2O | 8/4 | [51] |
25 | Na7[Cu(en)2]2[V12B18O60H6](NO3) 15.5H2O | 8/4 | [51] |
26 | [Na(H2O)]2[Na(H2O)2]2[Cu(en)2][V12B18O54(OH)6] (H3O)2 (H2O)18 | 8/4 | [50] |
27 | {[Na(H2O)4]3[V12B18O54(OH)6(H2O)]2}(H4tren)4 (H3O) 41H2O | 10/2 | [53] |
28 | Na8(H3O){[Ni(H2O)5][V12B18O60H6]} 12.5H2O | 11/1 | [52] |
29 | Na5(H3O)4{[Ni(H2O)3(en)][V12B18O60H6]} 9H2O | 11/1 | [52] |
30 | Na9(H3O){Zn0.5[V12B18O60H6]} 11H2O | 11/1 | [52] |
31 | [Hen][H2en]{[Zn(en)2]3[V12B18O60H6]} 3H2O | 9/3 | [52] |
32 | {[Na(H2O)3]4Na2V12B18O56(OH)4(H2O)}(H3dien)2 | 10/2 | [55] |
33 | {V12B18O54(OH)6(H2O)[K6(H2O)12]} 2(H2dien) 3H2O | 10/2 | [67] |
34 | K6(CH3NH3)4[V12B18O54(OH)6(H2O)] 2en 12H2O | 10/2 | [68] |
35 | K(H3O)(enH2)4[V12B18O60H6] 9.60H2O | 10/2 | [58] |
36 | K5(H3O)2(1,3-diapH2)2[V12B18O60H6] 10.8H2O | 11/1 | [59] |
37 | K2(H3O)7(enH2)[V12B18O60H6] 9.0H2O | 11/1 | [59] |
38 | [Zn(H3tepa)V12B18O54(OH)6][H2en]2 H3O 3H2O | 10/2 | [63] |
39 | [V12B18Zn3O63H12] 3(C4N3H16) 10NH4 5H2O | - | [56] |
40 | [V12B18Mn3O63H12] 3(C4N3H16) 10NH4 5H2O | - | [56] |
41 | [V12B18Ni3O63H12] 3(C4N3H16) 10NH4 5H2O | - | [56] |
8. Coordination Geometry Analysis of the Counterbalancing Alkaline and Secondary Transition Metal Ions
Cation | Geometry | Geometry Symbol |
---|---|---|
Li | Square Pyramid | (SPY-5) |
Na | Vacant Octahedron | (vOC-5) |
Trigonal Bipyramid | (TBPY-5) | |
Square Pyramid | (SPY-5) | |
Pentagonal Pyramid | (PPY-6) | |
Octahedron | (OC-6) | |
Trigonal Prism | (TPR-6) | |
K | Pentagonal Pyramid | (PPY-6) |
Octahedron | (OC-6) | |
Trigonal Prism | (TPR-6) | |
Capped Octahedron | (COC-7) | |
Capped Trigonal Prism | (CTPR-7) | |
Square Antiprism | (SAPR-8) | |
Triangular Dodecahedron | (TDD-8) | |
Tricaped Trigonal Prism | (TCTPR-9) | |
Cs | Hexagonal Bipyramid | (HBPY-8) |
Mn | Trigonal Prism | (TPR-6) |
Ni | Octahedron | (OC-6) |
Cu | Square | (SP-4) |
Octahedron | (OC-6) | |
Zn | Tetrahedron | (T-4) |
Square Pyramid | (SPY-5) | |
Vacant Octahedron | (vOC-5) | |
Octahedron | (OC-6) |
9. Spectroscopic Properties
10. Magnetic Properties
Compound | Auxiliary cations | VIV/VV Ratio | χT (emu K mol−1) (300 K) | χT (emu K mol−1) (2 K) | Ref. |
---|---|---|---|---|---|
5 | NH4+, (1,3-diapH2)2+ | 10/2 | 3.34 | 0.33 | [57] |
11 | [Cu(dien)(H2O)]2+ | 10/2 | 4.81 (3.68) * | 0.56 | [55] |
12 | Cd(H2O)22+ | 10/2 | 3.60 | 0.10 | [55] |
15 | Na+ | 10/2 | 3.53 | 0.23 | [54] |
18 | K+, NH4+ | 10/2 | 3.57 | 0.40 | [57] |
19 | K+ | 10/2 | 3.58 | 0.38 | [57] |
27 | [Na(H2O)4]+, (H4tren)4+ | 10/2 | 3.83 | 0.15 | [53] |
38 | Zn(H3tepa)2+, (enH2)2+ | 10/2 | 1.54 | 0.11 | [63] |
11. Final Remarks
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Hermosilla-Ibáñez, P.; Muñoz-Becerra, K.; Paredes-García, V.; Fur, E.L.; Spodine, E.; Venegas-Yazigi, D. Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States. Inorganics 2015, 3, 309-331. https://doi.org/10.3390/inorganics3030309
Hermosilla-Ibáñez P, Muñoz-Becerra K, Paredes-García V, Fur EL, Spodine E, Venegas-Yazigi D. Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States. Inorganics. 2015; 3(3):309-331. https://doi.org/10.3390/inorganics3030309
Chicago/Turabian StyleHermosilla-Ibáñez, Patricio, Karina Muñoz-Becerra, Verónica Paredes-García, Eric Le Fur, Evgenia Spodine, and Diego Venegas-Yazigi. 2015. "Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States" Inorganics 3, no. 3: 309-331. https://doi.org/10.3390/inorganics3030309