Preparation, X-ray Structures, Spectroscopic, and Redox Properties of Di- and Trinuclear Iron–Zirconium and Iron–Hafnium Porphyrinoclathrochelates
Bibliographic record
Abstract
The first hybrid di- and trinuclear iron(II)–zirconium(IV) and iron(II)–hafnium(IV) macrobicyclic complexes with one or two apical 5,10,15,20-tetraphenylporphyrin fragments were obtained using transmetalation reaction between n -butylboron-triethylantimony-capped or bis(triethylantimony)-capped iron(II) clathrochelate precursors and dichlorozirconium(IV)- or dichlorohafnium(IV)-5,10,15,20-tetraphenylporphyrins under mild conditions. New di- and trinuclear porphyrinoclathrochelates of general formula FeNx 3 ((B n -Bu)(MTPP)) and FeNx 3 (MTPP) 2 [M = Zr, Hf; TPP = 5,10,15,20-tetraporphyrinato(2-); Nx = nioximo(2-)] were characterized by one-dimensional ( 1 H and 13 C{ 1 H}) and two-dimensional (COSY and HSQC) NMR, high-resolution electrospray ionization mass spectrometry, UV–visible, and magnetic circular dichroism spectra, single-crystal X-ray diffraction experiments, as well as elemental analyses. Redox properties of all complexes were probed using electrochemical and spectroelectrochemical approaches. Electrochemical and spectroelectrochemical data suggestive of a very weak, if any, long-range electronic coupling between two porphyrin π-systems in FeNx 3 (MTPP) 2 complexes. Density functional theory and time-dependent density functional theory calculations were used to correlate spectroscopic signatures and redox properties of new compounds with their electronic structures.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".