Syntheses, Characterization, and Photophysical Properties of Conjugated Organometallic Pt-Acetylide/Zn(II) Porphyrin-Containing Oligomers
Bibliographic record
Abstract
Two conjugated organometallic oligomers of the type (-C[triple bond]CPt(L)(2)C[triple bond]C(ZnP)-)(n) and model compounds [PhC[triple bond]CPt(L)(2)C[triple bond]C(ZnP)C[triple bond]CPt(L)(2)C[triple bond]CPh] with L = tri(n-butyl)-phosphine and ZnP = zinc(II)(10,20-bis(Ar)porphyrine) (Ar = mesityl (Mes; P1 and M1) or 3,4,5-trihexadecyloxyphenyl (P2 and M2)) were synthesized and characterized ((1)H and (31)P NMR, HRMS, elemental analysis, IR, GPC, and TGA). GPC indicates that P1 and P2 exhibit respectively approximately 6 and approximately 3 units with a polydispersity of 1.4. M1 was also characterized by X-ray crystallography. The Pt...Pt separation in M1 is 1.61 nm, which makes P1 approximately 9.6 nm long. The spectral measurements show that the absorption and photoluminescence spectra of M1, M2, P1, and P2 are remarkably red-shifted. For example, the low energy Q-band is observed at 677 +/- 1 nm in comparison with their precursors HC[triple bond]C(ZnP)C[triple bond]CH, L1 and L2 (Ar = mesityl (Mes; L1) or 3,4,5-trihexadecyloxyphenyl (L2)), both at 298 and 77 K, for which the Q-band is observed at 622 nm. The photophysical parameters, fluorescence lifetimes (tau(F)), and quantum yields (Phi(F)) show a slight decrease by a factor of approximately 2 (at most 3) following the trend L1 approximately L2 > M1 approximately M2 > P1 approximately P2, a trend explained by a combination of the heavy atom effect and an increase in internal conversion rate due to the increase in oligomer dimension. This small variation of the photophysical data for materials of a few nm in dimension contrasts with the larger change in tau(P), phosphorescence lifetimes of the Pt-containing unit in the (-C(6)H(4)C[triple bond]CPt(L)(2)C[triple bond]C-CC(6)H(4)(ZnP)-)(n) oligomers with n = 3, 6, and 9 reported earlier (Liu, L.; Fortin, D.; Harvey, P. D. Inorg. Chem. 2009, 48, 5891-5900). In this later case, tau(P) decreased by steps of an order of magnitude as n increased from 3 to 6 to 9. This decrease was explained by a T(1) energy transfer from the Pt unit (donor) to MP (acceptor) in combination with an excitonic process (energy delocalization). Because of the full conjugation in P1 and P2, these oligomers behave as distinct molecules, and no energy transfer occurs. These properties make these materials suitable candidates for photocell applications.
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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 | 0.000 |
| 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) | 0.003 | 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".