Bibliographic record
Abstract
Spacial control within solid state materials is a method for controlling their properties. This thesis demonstrates the structural and functional control of oligothiophenes within coordination polymers and cyclic trinuclear complexes. Solvothermal and room temperature reaction conditions were used to synthesize oligothiophene metal-organic frameworks (71–85, 92–98). Appendage of phenyl and n-hexyl groups to the β-position of oligothiophene linkers induces structural changes in both the local and extended structures of the coordination polymers. Frameworks are sensitive to the linker functionality: phenyl groups promote the formation of 1D and 2D coordination polymers (74, 77, 80, 85, 92, 98) while aggregation of n-hexyl groups directs the local and extended structure of 2D and 3D materials (75, 78, 81, 94). Manganese(II) terthienyl coordination polymers (96 and 97) exist as isomers that form under solvothermal and post-solvothermal conditions, respectively. The photoluminescent properties of the coordination polymers generally matches those of the proligand. A bathochromic shift in oligothiophene-based emission occurs in 83 while compounds 75 and 81 undergo hypsochromic shifts. Quenching of oligothiophene emission in compound 81 occurs via incomplete energy transfer. The magnetic susceptibility of manganese(II) compounds reflects the local structure, and a spin-canting transition is present the acentric compound 96. Collapse of the framework of 94 prohibits a spin-canting transition. Gold(I) thienyl pyrazolate cyclic trinuclear complexes form dimeric or polymeric species in the solid state. Metal-perturbed ligand-based phosphorescence with lifetimes on the order of 5 ms are found in gold(I) monothienyl pyrazolates (126, 127, 130, 131). Bithienyl complexes (128, 129, 132, 133) do not exhibit phosphorescence at 77 K. Density functional theory confirms the contributions of gold(I) ions to the electronic structure of the S1 and T1 states. Oxidative polymerization of monothienyl (130) and bithienyl (132 and 133) complexes with n-hexyl derivatives generates conductive thin films.
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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 | 0.000 | 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) | 0.002 | 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".