Phosphorescent Iridium(III) Complexes with Acyclic Diaminocarbene Ligands as Chemosensors for Mercury

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Phosphorescent Iridium(III) Complexes with Acyclic Diaminocarbene Ligands as Chemosensors for Mercury. / Eremina, Anzhelika A.; Kinzhalov, Mikhail A.; Katlenok, Evgene A.; Smirnov, Andrey S.; Andrusenko, Elena V.; Pidko, Evgeny A.; Suslonov, Vitalii V.; Luzyanin, Konstantin V.

In: Inorganic Chemistry, Vol. 59, No. 4, 17.02.2020, p. 2209-2222.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{3a19797caba041a2bad96b8cd189d724,

title = "Phosphorescent Iridium(III) Complexes with Acyclic Diaminocarbene Ligands as Chemosensors for Mercury",

abstract = "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.",

keywords = "CYCLOMETALATED IR(III) COMPLEXES, EXCITED-STATE PROPERTIES, BLUE PHOSPHORESCENCE, HG2+, SENSOR, CHEMODOSIMETER, CARBENE, DESIGN, COORDINATION, PHOTOPHYSICS",

author = "Eremina, {Anzhelika A.} and Kinzhalov, {Mikhail A.} and Katlenok, {Evgene A.} and Smirnov, {Andrey S.} and Andrusenko, {Elena V.} and Pidko, {Evgeny A.} and Suslonov, {Vitalii V.} and Luzyanin, {Konstantin V.}",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = feb,

day = "17",

doi = "10.1021/acs.inorgchem.9b02833",

language = "English",

volume = "59",

pages = "2209--2222",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

RIS

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 - 2020/2/17

Y1 - 2020/2/17

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.

KW - CYCLOMETALATED IR(III) COMPLEXES

KW - EXCITED-STATE PROPERTIES

KW - BLUE PHOSPHORESCENCE

KW - HG2+

KW - SENSOR

KW - CHEMODOSIMETER

KW - CARBENE

KW - DESIGN

KW - COORDINATION

KW - PHOTOPHYSICS

UR - http://www.scopus.com/inward/record.url?scp=85079563632&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/62b5bfd8-ecd8-3dd4-82ee-e62121bb7b90/

U2 - 10.1021/acs.inorgchem.9b02833

DO - 10.1021/acs.inorgchem.9b02833

M3 - Article

C2 - 32011868

AN - SCOPUS:85079563632

VL - 59

SP - 2209

EP - 2222

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -

ID: 51872008