Strain‐Induced Structural Rearrangement Towards a White‐Light‐Emitting Adamantane‐Type Cluster Dimer

Group 14/16 adamantane‐type hybrid clusters of the type [(RT) 4 E 6 ] (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 CH 2 , in [(2‐NpSi){CH 2 Sn(S)Ph} 3 ] ( 1 , Np=naphthyl). When expanding one of the CH 2 moieties to a C 2 H 4 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){CH 2 Sn(S)Ph} 2 {C 2 H 4 Sn(S)Ph}] ( 2 ) to [(2‐NpSi){CH 2 Sn(S)Ph} 2 {C 2 H 4 Sn(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.