Aurophilicity in Action: Fine-tuning the Gold(I)–Gold(I) Distance in the Excited State to Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)–NHC complexes

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Abstract

The solution state emission profiles of a series of dinuclear Au(I) complexes 4 – 6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1–3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and, in the case of 5, which is non-emissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, while the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au–Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a d
Original languageEnglish
Pages (from-to)4720–4732
JournalInorganic Chemistry
Volume55
DOIs
Publication statusPublished - 2016

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Bromides
Excited states
Gold
Tuning
tuning
gold
bromides
excitation
Cations
Luminescence
red shift
Wavelength
Molecules
manipulators
luminescence
cations
profiles
wavelengths
molecules
energy

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@article{2b355c2f481c4357bcb7bb7a173c201a,
title = "Aurophilicity in Action: Fine-tuning the Gold(I)–Gold(I) Distance in the Excited State to Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)–NHC complexes",
abstract = "The solution state emission profiles of a series of dinuclear Au(I) complexes 4 – 6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1–3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and, in the case of 5, which is non-emissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, while the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au–Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a d",
author = "A.A. Penney and V.V. Sizov and E.V. Grachova and D.V. Krupenya and V.V. Gurzhiy and G.L. Starova and S.P. Tunik",
year = "2016",
doi = "10.1021/acs.inorgchem.5b02722",
language = "English",
volume = "55",
pages = "4720–4732",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Aurophilicity in Action: Fine-tuning the Gold(I)–Gold(I) Distance in the Excited State to Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)–NHC complexes

AU - Penney, A.A.

AU - Sizov, V.V.

AU - Grachova, E.V.

AU - Krupenya, D.V.

AU - Gurzhiy, V.V.

AU - Starova, G.L.

AU - Tunik, S.P.

PY - 2016

Y1 - 2016

N2 - The solution state emission profiles of a series of dinuclear Au(I) complexes 4 – 6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1–3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and, in the case of 5, which is non-emissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, while the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au–Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a d

AB - The solution state emission profiles of a series of dinuclear Au(I) complexes 4 – 6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1–3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and, in the case of 5, which is non-emissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, while the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au–Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a d

U2 - 10.1021/acs.inorgchem.5b02722

DO - 10.1021/acs.inorgchem.5b02722

M3 - Article

VL - 55

SP - 4720

EP - 4732

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -