Controllable synthesis of Zn/Cd(<scp>ii</scp>) coordination polymers: dual-emissive luminescent properties, and tailoring emission tendency under varying excitation energies
Bibliographic record
Abstract
Based on a new asymmetric semi-rigid V-shaped tricarboxylate ligand 3-(2',3'-dicarboxylphenoxy)benzoic acid (H3dpob), a series of zinc/cadmium(ii) coordination polymers, {[Cd(Hdpob)(H2O)3]·H2O}n (1), [Cd(Hdpob)(bib)]n (2), [Zn(Hdpob)(bib)0.5]n (3), {[Cd1.5(dpob)(2,2'-bipy)]·0.5H2O}2n (4) and {[Cd3(dpob)2(4,4'-bipy)2]·3H2O}n (5) [bib = 1,4-bis(1-imidazolyl)benzene; 2,2'-bipy = 2,2'-bipyridine; 4,4'-bipy = 4,4'-bipyridine], have been successfully synthesized via hydro(solvo)thermal reactions. 1 forms a three dimensional (3D) supramolecular structure linked by two types of intermolecular hydrogen bonds based on zig-zag 1D chains, whereas 2 and 3 are obtained with a similar 2D layer structure by the same ligands and further connected into a 3D structure through hydrogen bonds. 4 displays a homochiral 2D structure though two achiral ligands 2,2'-bipy and H3dpob, which contains right-handed helical infinite chains. 5 is a 3D structure containing 2D metal-pyridine layer motifs, which are further pillared by beaded dpob(3-) ligands to complete the structure and form a 6-connected pcu (primitive cubic) net. In DMSO solvent, 1-5 illustrate dual-emission properties but have different low-energy emission (LE) intensities relatively. Extraordinarily, the difference resulting from central metals between 2 and 3 makes the intensity of LE dramatically enhanced and quenched. In this regard, the luminescence of 2 and 3 can be tuned between blue and green regions by varying the excitation light, and the tuning tendency can be tailored with inverse directions. Comparing their tunable-sensitivity to energy quantitatively, the theoretical calculation displays that 3 (4.29%) is little higher than 2 (3.59%) in a relative lower excitation wavelength zone. Meanwhile, five coordination polymers show distinct luminescence thermochromism in the solid state. When the temperature decreases from 298 K to 77 K, the red-shift from blue/green to the pure yellow light region is highlighted. The fantastic and unique luminescence phenomenon not only brings an insight into the synthesis of dual-emissive materials, but helps us to understand the luminescence behavior deeply as well.
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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 | 0.001 | 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) | 0.000 | 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".