Preparation and Characterization of {[M(dmb)<sub>2</sub>]TCNQ·<i>x</i>TCNQ°}<i><sub>n</sub></i> Polymers (M = Cu,Ag; dmb = 1,8-Diisocyano-<i>p</i>-menthane; <i>x</i> = 0, 0.5, 1.0, 1.5; TCNQ = 7,7,8,8-Tetracyano-<i>p</i>-quinodimethane) and Design of New Semi- and Photoconducting Organometallic Materials
Bibliographic record
Abstract
New thermoplastic organometallic materials of the type [[M(dmb)2]TCNQ.xTCNQo.y solvent], (M = Cu(I), Ag(I); dmb = 1,8-diisocyano-p-menthane; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, x = 0, 0.5, 1.0, 1.5; solvent = none, THF or toluene) have been prepared and characterized from X-ray powder diffraction patterns, X-ray crystallography (for some Ag polymers), DSC, and conductivity measurements. While the [[M(dmb)2]TCNQ.xTCNQo]n polymers (M = Cu,Ag; x = 0, 0.5) are insulating, the others (x = 1.0 and 1.5) are semiconducting, and the relative conductivity is found to be a function of the molecular weight and crystallinity. The [[Cu(dmb)2]TCNQ.1.5TCNQ]n material is also photoconducting, while the Ag analogue is not. Photochemical and luminescence quenching experiments in the solid-state established that the Cu+ center and TCNQo act as electron donor and acceptor, respectively, in this photoprocess. Finally photocells of the type glass/SnO2/[Cu(dmb)2]TCNQ.TCNQo]n + 0.5 acceptor/Al (acceptor = TCNQo, C60 and TCNN (13,13,14,14-tetracyano-5,12-naphthacenequinodimethane)) have been designed and characterized. The quantum yields (number of photoproduced electrons/number of photons) are as follows: TCNQ, 1.6 x 10(-4), C60, 5 x 10(-5), TCNN, 3.0 x 10(-4) at lambdaexc = 330 nm. X-ray data for [[Ag(dmb)2]TCNQ.2THF]n: space group P2(1/c), monoclinic, a = 13.5501(10), b = 9.9045(10), c = 32.564(2) A, beta = 91.130(10) degrees, Z = 4. X-ray data for [[Ag(dmb)2]TCNQ.0.5TCNQo.0.5 toluene]n: space group P2(1/c), monoclinic, a = 14.3669(19), b = 9.1659(3), c = 34.012(3) A, beta = 92.140(8) degrees, Z = 4. X-ray data for [[Ag(dmb)2]TCNQ.1.5TCNQo]n: space group C2/c, monoclinic, a = 25.830(11), b = 9.680(2), c = 42.183(19) A, beta = 104.87(4) degrees, Z = 8. X-ray data for [[Ag(dmb)2]DCTC]n: space group P2(1/a), monoclinic, a = 26.273(3), b = 9.730(3), c = 31.526(3) A, beta = 112.12(2)degrees, Z = 4.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 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 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".