Journal
DALTON TRANSACTIONS
Volume 44, Issue 14, Pages 6581-6592Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4dt03424d
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Funding
- Department of Science and Technology (DST), Govt. of India [SR/S1/IC-48/2009]
- Council of Scientific and Industrial Research (CSIR) [01/2551/12/EMR-II]
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On reaction of 2,2'-bipyridine with iridium(III), an aggregation induced phosphorescence (AIP) active rollover complex, [Ir(PPh3)(2)(bipy-H)(Cl)(H)] (bipy-H = kappa(2)-N, C-2,2'-bipyridine) or [Ir(bipy-H)], is obtained. The emission colour changes from bluish-green to yellowish-orange and vice versa after repeated protonation and deprotonation of [Ir(bipy-H)], respectively, which unequivocally supports its reversible nature. [Ir(bipy-H)] is sensitive to acids with different pK(a) values. Tuning of the emission properties can be achieved in the presence of acids with different pK(a)s. This behaviour allows the complex, [Ir(bipy-H)], to function as a phosphorescent acid sensor in both solution and the solid state, as well as a chemosensor for detecting acidic and basic organic vapours. The protonated form, [Ir(bipy-H)H+], which is generated after protonation of [Ir(bipy-H)] can be used as a solvatochromic probe for oxygen containing solvents, and also shows vapochromic properties. The emission, absorption and H-1 NMR spectra of [Ir(bipy-H)] under acidic and basic conditions demonstrate its reversible nature. DFT based calculations suggest that changes in the electron affinity of the pyridinyl rings are responsible for all these processes.
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