Solid-State Coordination Chemistry: Structural Influences of Copper−Phenanthroline Subunits on Oxovanadium Organophosphonate Phases. Hydrothermal Synthesis and Structural Characterization of the Two-Dimensional Materials [Cu(phen)(VO)(O<sub>3</sub>PCH<sub>2</sub>PO<sub>3</sub>)(H<sub>2</sub>O)], [{Cu(phen)}<sub>2</sub>(V<sub>2</sub>O<sub>5</sub>)(O<sub>3</sub>PCH<sub>2</sub>CH<sub>2</sub>PO<sub>3</sub>)], and [{Cu(phen)}<sub>2</sub>(V<sub>3</sub>O<sub>5</sub>)(O<sub>3</sub>PCH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>PO<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)] and of the Three-Dimensional Phase [{Cu(phen)}<sub>2</sub>(V<sub>3</sub>O<sub>5</sub>)(O<sub>3</sub>PCH<sub>2</sub>PO<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)]
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Bibliographic record
Abstract
The hydrothermal reactions of CuCl2*2H2O, Na3VO4, 1,10-phenanthroline, and the appropriate organodiphosphonate ligand yield [Cu(phen)(VO)(O3PCH2PO3)(H2O)] (1), [[Cu(phen)]2(V2O5)(O3PCH2CH2PO3)] (2), [[Cu(phen)]2(V3O5)(O3PCH2CH2CH2PO3)2 (H2O)] (3), and [[Cu(phen)]2(V3O5)(O3PCH2PO3)2(H2O)] (4). Compounds 1-3 exhibit two-dimensional structures. The structures exhibit distinct vanadium building blocks: square pyramidal, mononuclear V(IV) sites in 1, a binuclear unit of corner-sharing V(V) tetrahedra in 2, and a trinuclear unit of corner-sharing V(V) square pyramids and a V(IV) octahedron in 3. The network structures of 1 and 2 are constructed from one-dimensional oxovanadium-diphosphonate chains linked by Cu(II) square pyramids into two-dimensional layers. In contrast, compound 3 exhibits a two-dimensional oxovanadium-organodiphosphonate network, with Cu(II) sites decorating the surfaces. Compound 4 is unique in exhibiting a framework structure, which may be described as a three-dimensional oxovanadium-organodiphosphonate substructure with [Cu(phen)]2+ subunits covalently attached to the surface of channels running parallel to the a-axis. The magnetic properties of 1-4 are also correlated to the structural characteristics. The magnetic behavior of 2 is thus dominated by antiferromagnetic interactions. The magnetic behavior of 1 and 4 is consistent with the presence of two distinct paramagnetic metal ions, Cu(II) and V(IV). In contrast, 3 does not exhibit ferrimagnetic behavior, but rather weak antiferromagnetic coupling. Crystal data: 1, C13H10N2CuP2VO8, monoclinic P2(1)/c, a = 9.0656(5) A, b = 8.6584(5) A, c = 20.934(1) A, beta = 97.306(1) degrees, Z = 4; 2, C26H20N4Cu2P2V2O11, triclinic P1, a = 10.6096(5) A, b = 11.6951(5) A, c = 13.1796(6) A, alpha = 71.369(1) degrees, beta = 70.790(1) degrees, gamma = 80.738(1) degrees, Z = 2; 3, C30H28N4Cu2P4V3O18, triclinic P1, a = 9.4356(6) A, b = 10.6556(6) A, c = 11.0354(7) A, alpha = 118.187(1) degrees, beta = 91.416(1) degrees, gamma = 107.821(1) degrees, Z = 1; 4, C26H20N4Cu2P4V3O18, monoclinic, P2(1)/c a = 8.3947(3) A, b = 16.8401(7) A, c = 11.9144(5) A, beta = 93.903(1) degrees, Z = 2.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.028 | 0.016 |
| Meta-epidemiology (narrow) | 0.055 | 0.061 |
| Meta-epidemiology (broad) | 0.047 | 0.025 |
| Bibliometrics | 0.018 | 0.045 |
| Science and technology studies | 0.026 | 0.036 |
| Scholarly communication | 0.016 | 0.031 |
| Open science | 0.035 | 0.028 |
| Research integrity | 0.034 | 0.041 |
| Insufficient payload (model declined to judge) | 0.001 | 0.009 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it