Tuning of intramolecular charge transfer properties and charge distributions in ferrocene-appended catechol derivatives by chemical substitution
Bibliographic record
Abstract
In this study, we report intramolecular charge transfer (ICT) properties and charge distributions in a series of FcC derivatives (FcC = 4-ferrocenylcatecholate where Fc = ferrocene and C = catecholate). This series consists of a previously reported complex FcV (4-ferrocenylveratrole) and newly synthesized complexes FcA (4-ferrocenylcatechol bis(acetate) and Pt((t)Bu2bpy)(FcC) ((t)Bu2bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl). An electrochemical analysis of Pt((t)Bu2bpy)(FcC) using cyclic voltammetry revealed two well-defined, reversible waves which were assigned to the sequential oxidation of the Pt((t)Bu2bpy)(C) and Fc moieties. The potential splitting between the waves (524 mV) indicated that there was an electronic interaction between both moieties. ICT property and charge distribution of [Pt((t)Bu2bpy)(FcC)]˙(+) were rationalized by comparison with the [FcV]˙(+) and [FcA]˙(+) (4-ferrocenylcatechol bis(acetate)). DFT calculations and UV-vis-NIR spectroscopy revealed that [Pt((t)Bu2bpy)(FcC)]˙(+), [FcV]˙(+), and [FcA]˙(+) were ferrocenium (Fc(+))-centered rather than semiquinone ligand-centered and that these complexes exhibited ICT transition bands from the catechol-derivatized framework to the Fc(+) moiety in the near infrared (NIR) region. Both the electronic coupling parameter (HAB) and delocalization parameter (α) increased in value as the electron-donating strength of the substituent groups in the catechol-derivatized framework increased (OCOCH3 ([FcA]˙(+)) < OCH3 ([FcV]˙(+)) < O(-) ([Pt((t)Bu2bpy)(FcC)]˙(+))). The electronic interactions between the organometallic center and the non-innocent framework were tuned by changing the substituents. The potential energy surfaces of the Fc(+) derivatives, obtained using two-state Marcus-Hush theory, can be modulated by changing the energy level of the molecular orbitals of the appended catechol-derivatized moieties.
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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".