Synthesis and Coordination Chemistry of a Benzannulated Bipyridine: 6,6′-Biphenanthridine
Bibliographic record
Abstract
The synthesis, characterization, and coordination chemistry of a doubly π-extended bipyridine analogue, 6,6′-biphenanthridine (biphe), is presented. The structure of the molecule has been determined in the solid state by X-ray diffraction, showing an angle of 72.6° between the phenanthridine planes. The free, uncoordinated organic molecule displays blue fluorescence in solution. It can be singly protonated with strong acids, and the protonated form displays more intense yellow emission. The effect of acid on the excited states is interpreted with the aid of TDDFT calculations. Two Ru(II) coordination complexes, tris(6,6′-biphenanthridine)ruthenium(II) dichloride, [Ru(biphe)3]Cl2, and bis(2,2′-bipyridine)(6,6′-biphenanthridine)ruthenium(II) tetraphenylborate, [Ru(bpy)2(biphe)](BPh4)2, are also reported and their structures determined in the solid state by X-ray diffraction. Both complexes display emission at 77 K that is strongly bathochromically shifted by almost 200 nm compared to that of the archetypal 3MLCT emitter [Ru(bpy)3]2+. Such a red shift is consistent with the more extended conjugation and lower-energy π* orbitals associated with the biphe ligand, lowering the energy of the 3MLCT excited state, as revealed by TDDFT calculations. The efficient non-radiative decay that is typical of such low-energy emitters renders the phosphorescence extremely weak and short-lived at ambient temperature, and rapid ligand photodissociation also competes with radiative decay, especially in the heteroleptic complex. Electrochemical analysis illustrates the effect of biphe’s stabilized vacant π* manifold, with multiple reversible reductions evident at much less negative potentials than those observed for [Ru(bpy)3]2+.
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 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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.004 | 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 teacher head, 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".