Introducing Distinct Structural and Optical Properties into Organotin Sulfide Clusters by the Attachment of Perylenyl and Corannulenyl Groups.

We report the introduction of distinct optical properties into organotin sulfide clusters by the attachment of extended polycyclic aromatic organic molecules. This was realized by the reactions of [(RNSn)4S6] (RN = CMe2CH2CMeNNH2) with 3-perylenecarbaldehyde and corannulenecarbaldehyde, respectively. The reaction with the first reactant leads to the formation of two products [(RperylSn)3S4][SnCl3] [1a; Rperyl = CMe2CH2CMeNNCH(C20H11)] and [(RperylSn)3S4Cl] (1b). Structural differences between these two compounds are reflected in their different optical absorption and luminescence behavior, yet in both cases, the main emission is red-shifted relative to 3-perylenecarbaldehyde. The second organic molecule affords the compound [(RcorSn)4Sn2S10] [2; Rcor = CMe2CH2CMeNNCH(C20H9)] with intriguing optical properties, including a broad emission with essentially no shift in λmax compared to corannulenecarbaldehyde. All compounds were obtained as single crystals, and their structures were determined by means of single-crystal X-ray diffraction. The optical properties of the highly luminescent compounds were investigated by means of emission and time-resolved photoluminescence spectroscopy measurements.