Abstract
AbstractGroup 14/16 adamantane‐type hybrid clusters of the type [(RT)4E6] (T=group 14 element, E=group 16 element, R=organic group) have been reported to emit white‐light when irradiated in an amorphous state with a continuous‐wave (CW) infrared laser diode. This effect is enhanced if the cluster core is varied from a binary to a more complex composition. To further explore this phenomenon, we synthesized clusters with a multinary R/R’‐T/T’‐E/E’ composition, including isolobal replacement of E with CH2, in [(2‐NpSi){CH2Sn(S)Ph}3] (1, Np=naphthyl). When expanding one of the CH2 moieties to a C2H4 group, thus generating a R/R’‐T/T’‐E/E’/E’’ cluster composition, we unexpectedly observed a dimerization of the initially formed, yet non‐isolable adamantane‐like cluster [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}] (2) to [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}]2 (3), exhibiting a heretofore unprecedented cluster architecture. Both monomeric 1 and dimeric 3, show white‐light emission as thin films. The nonlinear optical response of the compounds was also modelled with DFT methods.
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