Hapticity-Dependent Charge Transport through Carbodithioate-Terminated [5,15-Bis(phenylethynyl)porphinato]zinc(II) Complexes in Metal–Molecule–Metal Junctions
Bibliographic record
Abstract
Single molecule break junction experiments and nonequilibrium Green's function calculations using density functional theory (NEGF-DFT) of carbodithioate- and thiol-terminated [5,15-bis(phenylethynyl)-10,20-diarylporphinato]zinc(II) complexes reveal the impact of the electrode-linker coordination mode on charge transport at the single-molecule level. Replacement of thiolate (-S(-)) by the carbodithioate (-CS2(-)) anchoring motif leads to an order of magnitude increase of single molecule conductance. In contrast to thiolate-terminated structures, metal-molecule-metal junctions that exploit the carbodithioate linker manifest three distinct conductance values. We hypothesize that the magnitudes of these conductances depend upon carbodithoate linker hapticity with measured conductances across Au-[5,15-bis(4'-(dithiocarboxylate)phenylethynyl)-10,20-diarylporphinato]zinc(II)-Au junctions the greatest when both anchoring groups attach to the metal surface in a bidentate fashion. We support this hypothesis with NEGF-DFT calculations, which consider the electron transport properties for specific binding geometries. These results provide new insights into the origin of molecule-to-molecule conductance heterogeneity in molecular charge transport measurements and the factors that optimize electrode-molecule-electrode electronic coupling and maximize the conductance for charge transport.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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".