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Title: Sensitized terbium (III) macrocyclic-phthalimide complexes as luminescent pH switches
Author(s): Bligh, Annie Sim Wan 
Author(s): Chen, G.
Wardle, N. J.
Sarris, J.
Chatterton, N. P.
Issue Date: 2013
Publisher: Royal Society of Chemistry
Journal: Dalton Transactions 
Volume: 42
Issue: 39
Start page: 14115
End page: 14124
Four new macrocyclic-phthalimide ligands were synthesised via the coupling of N-(3-bromopropyl)phthalimide either to cyclen (1,4,7,10-tetraazacyclododecane) itself or its carboxylate-functionalized analogues, and photophysical studies were carried out on their corresponding Tb(III) complexes in aqueous media as a function of pH. Luminescence intensities of Tb·L1a1a–Tb·L3a3a were in ‘switched off’ mode under acidic conditions (pH < 4), and were activated on progression to basic conditions as the phthalimido functions therein were hydrolysed to their corresponding phthalamates Tb·L1b1b1b–Tb·L3b3b3b. Emission of phthalamate-based macrocyclic Tb(III) complexes Tb·L1b1b1b–Tb·L3b3b3b was in ‘switched on’ mode between pH 4 and 11, exhibiting high quantum yields (Φ) and long lifetimes (τ) of the order of milliseconds at pH ∼ 6. Tb(III) emissions were found to decline with increasing number of chromophores. The values of Φ and τ were 46% and 2.4 ms respectively for Tb·L1b1b at pH ∼ 6 when activated. This is the best pH-dependent sensor based on a Tb(III) complex reported to date, benefiting from the macrocyclic architecture of the ligand.
DOI: 10.1039/c3dt51236c
CIHE Affiliated Publication: No
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