Structure and Emissive Properties of Heterobimetallic Ln–Au Coordination Polymers: Role of Tb and Eu in Non-aurophilic [<sup>n</sup>Bu<sub>4</sub>N]<sub>2</sub>[Ln(NO<sub>3</sub>)<sub>4</sub>Au(CN)<sub>2</sub>] versus Aurophilic Ln[Au(CN)<sub>2</sub>]<sub>3</sub>·3H<sub>2</sub>O/3D<sub>2</sub>O Chains
Bibliographic record
Abstract
This investigation is focused on comparing photophysical properties between two series of lanthanide-dicyanoaurate coordination polymers that contain and lack aurophilic interactions, respectively. Luminescence and crystallographic studies have been carried out on five different coordination polymer chain frameworks: the non-aurophilic [(n)Bu4N]2[LnxGd1-x(NO3)4Au(CN)2] (Ln = Eu, Tb; x = 0.01, 0.02, 0.04, 0.08) and[(n)Bu4N]2[EuxTb1-x(NO3)4Au(CN)2] (x = 0.25, 0.5, 0.75), as well as the analogous solid-solutions of aurophilic LnxGd1-x[Au(CN)2]3·3H2O and EuxTb1-x[Au(CN)2]3·3H2O. The single-crystal structures of M[Au(CN)2]3 ·3H2O (M = Eu, Gd) are also reported for comparison. In the aurophilic frameworks the close proximity of gold(I) centers on neighboring chains allows for Au-Au interactions to take place that facilitate energy transfer between lanthanides. Terbium- and europium-doped aurophilic frameworks show energy transfer between one of the lanthanide ions and dicyanoaurate centers as observed via luminescence measurements. In the non-aurophilic frameworks the [(n)Bu4N] cations separate the Au-Au chains, thereby preventing interaction between them, and preventing energy transfer. By preparing the aurophilic EuxTb1-x[Au(CN)2]3·3D2O frameworks, it was shown that the O-H vibrational energy in the hydrated (aurophilic) samples can partially quench the Ln signal.
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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 | 0.004 | 0.003 |
| Meta-epidemiology (narrow) | 0.008 | 0.008 |
| Meta-epidemiology (broad) | 0.008 | 0.003 |
| Bibliometrics | 0.003 | 0.006 |
| Science and technology studies | 0.003 | 0.005 |
| Scholarly communication | 0.002 | 0.005 |
| Open science | 0.005 | 0.003 |
| Research integrity | 0.005 | 0.005 |
| Insufficient payload (model declined to judge) | 0.000 | 0.001 |
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; both teacher heads agree on what is shown here.
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".