On the Viability of Cyclometalated Ru(II) Complexes for Light-Harvesting Applications
Bibliographic record
Abstract
The effects of replacing a single polypyridyl ligand with an analogous anionic cyclometalating ligand were investigated for a set of three structurally related series of Ru(II) compounds formulated as [Ru(bpy)(2)(L)](z), [Ru(tpy)(L)](z), and [Ru(tpy)(L)Cl](z), where z = 0, +1, or +2, and L = polypyridyl (e.g., bpy = 2,2'-bipyridine, tpy = 2,2':6',2''-terpyridine) or cyclometalating ligand (e.g., deprotonated forms of 2-phenylpyridine or 3-(2-pyridinyl)-benzoic acid). Each of the complexes were synthesized and characterized by (1)H NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and/or elemental analyses (EA). Cyclic voltammetry reveals that cyclometalation causes a shift of the first oxidation and reduction potentials by -0.5 to -0.8 V and -0.2 to -0.4 V, respectively, relative to their polypyridyl congeners. These disparate shifts have the effect of inducing a bathochromic shift of the lowest-energy absorption bands by as much as 90 nm. With the aid of time-dependent density functional theory (DFT), the lowest-energy bands (lambda(max) = 500-575 nm) were assigned as predominantly metal-to-ligand charge-transfer (MLCT) transitions from Ru to the polypyridyl ligands, while Ru-->C(wedge)NN (or C(wedge)N(wedge)N or N(wedge)C(wedge)N) transitions are found within the absorption bands centered at ca. 400 nm. The properties of a series of compounds furnished with carboxylic acid anchoring groups at various positions are also examined for applications involving the sensitization of metal-oxide semiconductors. It is determined that the thermodynamic potentials of many of these compounds are appropriate for conventional photoelectrochemical cells (e.g., dye-sensitized solar cells) that utilize a titania electrode and iodide-based electrolyte.
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".