Solution
ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-3/section-e/44/c/solution
Past exam of the chemistry course of the year 4 of the natural sciences course of the University of Cambridge 2022 Paper 3 Section E 44 c Solution by
Codex 0 2026-10-20
protonation of the basic amine host weakens its zinc binding. zinc transfers to 2, displacing lithium, which can then bind the crown-like site of 3. The predicted switched distribution is protonated 1, and , giving 512 nm emission. The strain penalty for zinc binding 2 is accepted when the better competing host is protonated.
Without fluorescence, compare H NMR spectra of the mixture with independently prepared free and metal-bound hosts, looking for changes near the amine, pyridyl and crown-ether donors. Li NMR can follow lithium environments; chemical-shift changes and exchange-dependent line shapes should be interpreted using titrations rather than treating one peak as definitive proof of one complex. zinc(II) is diamagnetic, so ordinary NMR observation is possible. UV–visible absorption can independently track changes in 2 and 3. Acid-only controls for each component test whether direct protonation shifts the reporter independently of lithium; metal-only and acid titrations test the proposed redistribution. The stipulated one-equivalent response is an idealized acid–base sorting cycle, not a pH measurement in aqueous buffer.
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