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

Результат исследований: Научные публикации в периодических изданияхстатья

34 Цитирования (Scopus)

Аннотация

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
Язык оригиналаанглийский
Страницы (с-по)4720–4732
ЖурналInorganic Chemistry
Том55
DOI
СостояниеОпубликовано - 2016

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