TY - JOUR
T1 - Phosphorescent Iridium(III) Complexes with Acyclic Diaminocarbene Ligands as Chemosensors for Mercury
AU - Eremina, Anzhelika A.
AU - Kinzhalov, Mikhail A.
AU - Katlenok, Evgene A.
AU - Smirnov, Andrey S.
AU - Andrusenko, Elena V.
AU - Pidko, Evgeny A.
AU - Suslonov, Vitalii V.
AU - Luzyanin, Konstantin V.
PY - 2020
Y1 - 2020
N2 - A new application for bis(cyclometalated) iridium(III) species containing ancillary acyclic diaminocarbene ligands, viz. for sensing of mercury(II) ions, is disclosed. A family of bis(cyclometalated) iridium(III) species supported by both parent isocyanide and acyclic diaminocarbene ligands was prepared, and their electrochemical and photophysical properties were evaluated, revealing efficient blue-green phosphorescence in solution with quantum yields of up to 55%. We uncovered that the photophysical properties of these complexes are dramatically altered by the presence of metal ions and that the complex [Ir(ppy)2(CN){C(NH2)(NHC6H4-4-X)}] with an ADC ligand reacts selectively with Hg2+ ions, enabling its use for sensing of mercury(II) ions in solution. The limit of detection was as low as 2.63 × 10-7 M, and additional mechanistic studies indicated the formation of an unusual dinuclear iridium(III) cyclometalated intermediate, bridged by a mercury dicyano fragment as a driving force of mercury sensing.
AB - A new application for bis(cyclometalated) iridium(III) species containing ancillary acyclic diaminocarbene ligands, viz. for sensing of mercury(II) ions, is disclosed. A family of bis(cyclometalated) iridium(III) species supported by both parent isocyanide and acyclic diaminocarbene ligands was prepared, and their electrochemical and photophysical properties were evaluated, revealing efficient blue-green phosphorescence in solution with quantum yields of up to 55%. We uncovered that the photophysical properties of these complexes are dramatically altered by the presence of metal ions and that the complex [Ir(ppy)2(CN){C(NH2)(NHC6H4-4-X)}] with an ADC ligand reacts selectively with Hg2+ ions, enabling its use for sensing of mercury(II) ions in solution. The limit of detection was as low as 2.63 × 10-7 M, and additional mechanistic studies indicated the formation of an unusual dinuclear iridium(III) cyclometalated intermediate, bridged by a mercury dicyano fragment as a driving force of mercury sensing.
UR - http://www.scopus.com/inward/record.url?scp=85079563632&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b02833
DO - 10.1021/acs.inorgchem.9b02833
M3 - Article
C2 - 32011868
SN - 0020-1669
VL - 59
SP - 2209
EP - 2222
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -