Enhanced emission and analyte sensing by cinchonine iridium(III) cyclometalated complexes bearing bent diphosphine chelators

S X Luo; L Wei; X H Zhang; M H Lim; K X V Lin; M H V Yeo; W H Zhang; Z P Liu; David James Young; T S A Hor

doi:10.1021/om400028n

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Enhanced emission and analyte sensing by cinchonine iridium(III) cyclometalated complexes bearing bent diphosphine chelators

Journal article

Peer reviewed

Enhanced emission and analyte sensing by cinchonine iridium(III) cyclometalated complexes bearing bent diphosphine chelators

S X Luo, L Wei, X H Zhang, M H Lim, K X V Lin, M H V Yeo, W H Zhang, Z P Liu, David James Young and T S A Hor

Organometallics, Vol.32(10), pp.2908-2917

2013

DOI: https://doi.org/10.1021/om400028n

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Abstract

1 ,2bis(diphenylphosphino)benzene

cyclometalated complexes

cyclometalating ligand

diphosphine ligand

electron-deficient

nonradiative energy transfer

solid-state structures

Ir(III) complexes of cyclometalating ligands derived from the natural product cinchonine and bent (4,6-bis(diphenylphosphino)phenoxazine (Nixantphos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos)) and planar diphosphine ligands (1,2-bis(diphenylphosphino)benzene (dppb)) exhibit good luminescence with quantum efficiencies higher than those of their parent congeners. Steric hindrance by both the bulky cinchonine-derived ligand and bent diphosphine could limit nonradiative energy transfer. The cinchonine-derived and parent complexes cover a broad emission range from 472 to 569 nm with quantum efficiencies up to 0.38 and lifetimes from 0.01 to 0.46 μs in degassed CH2Cl2 solution at room temperature. DFT calculations on selected examples are in good agreement with solid-state structures determined crystallographically and accurately predict wavelengths of emission by excited electron decay from a quinoline-centered orbital to an Ir 5d-phenyl molecular orbital. The complex [(pcn)2Ir(Nixantphos)] [PF6] (2; pcn = 2â€²-phenyl-9-O-benzyl-10,11-dihydrocinchonine- C2,N) exhibits the highest quantum yield and could detect electron-deficient aromatic species at ppm levels. © 2013 American Chemical Society.

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Title: Enhanced emission and analyte sensing by cinchonine iridium(III) cyclometalated complexes bearing bent diphosphine chelators
Authors: S X Luo (Author) - Institute of Materials Research and Engineering, Singapore
L Wei (Author) - Institute of Materials Research and Engineering, Singapore
X H Zhang (Author) - Institute of Materials Research and Engineering, Singapore
M H Lim (Author) - National University of Singapore, Singapore
K X V Lin (Author) - Institute of Materials Research and Engineering, Singapore
M H V Yeo (Author) - Institute of Materials Research and Engineering, Singapore
W H Zhang (Author) - Institute of Materials Research and Engineering, Singapore
Z P Liu (Author) - Fudan University, China
David James Young (Author) - Institute of Materials Research and Engineering, Singapore
T S A Hor (Author) - Institute of Materials Research and Engineering, Singapore
Publication details: Organometallics, Vol.32(10), pp.2908-2917
Publisher: American Chemical Society
Date published: 2013
DOI: 10.1021/om400028n
ISSN: 0276-7333
Organisation Unit: University of the Sunshine Coast, Queensland
Language: English
Record Identifier: 99449166402621
Output Type: Journal article

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