Reactivity of CuI and CuBr toward Et<sub>2</sub>S: a Reinvestigation on the Self-Assembly of Luminescent Copper(I) Coordination Polymers
Bibliographic record
Abstract
CuI reacts with SEt(2) in hexane to afford the known strongly luminescent 1D coordination polymer [(Et(2)S)(3){Cu(4)(mu(3)-I)(4)}](n) (1). Its X-ray structure has been redetermined at 115, 235, and 275 K in order to address the behavior of the cluster-centered emission and is built upon Cu(4)(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging SEt(2) ligands. However, we could not reproduce the preparation of a coordination polymer with composition [(Et(2)S)(3){Cu(4)(mu(3)-Br)(4)}](n) as reported in Inorg. Chem. 1975, 14, 1667. In contrast, the autoassembly reaction of SEt(2) with CuBr results in the formation of a novel 1D coordination polymer of composition [(Cu(3)Br(3))(SEt(2))(3)](n) (2). The crystal structure of 2 has been solved at 115, 173, 195, and 235 K. The framework of the luminescent compound 2 consists of a corrugated array with alternating Cu(mu(2)-Br)(2)Cu rhomboids, which are connected through two bridging SEt(2) ligands to a tetranuclear open-cubane Cu(4)Br(4) SBU, ligated on two external Cu atoms with one terminal SEt(2). The solid-state luminescence spectra of 1 and 2 exhibit intense halide-to-metal charge-transfer emissions centered at 565 and 550 nm, respectively, at 298 K. A correlation was also noted between the change in the full width at half-maximum of the emission band between 298 and 77 K and the relative flexibility of the bridging ligand. The emission properties of these materials are also rationalized by means of density functional theory (DFT) and time-dependent DFT calculations performed on 1.
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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 | 0.001 |
| 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 | 0.001 |
| 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".