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Two diphosphine-protected superatom gold selenido nanoclusters, [Au8Se2(dppm)4]2+ (SD/Au8a, dppm = Ph2PCH2PPh2) and [Au8Se2(dppe)4]2+ (SD/Au8b, dppe = Ph2P(CH2)2PPh2), were obtained by the reduction of [Au(SMe2)Cl] in the presence of Ph3PSe as the selenium ion releasing agents. Both can be regarded as "superatoms" with 1S2 configuration based on the spherical Jellium model. Despite the same metal–ligand binding motifs on the surface and the intrinsic C2 molecular symmetry, the configurations of Au8Se2 kernels in them are different in terms of Au–Au bonded metallic frameworks. SD/Au8a displays a heart-shaped [core + exo] type structure (Au4 tetrahedron core + two exo Au2Se units), whereas the two exo Au2Se counterparts in SD/Au8b are additionally locked by an obvious Au–Au bond, forming a distorted hexagonal Au6 ring with two capping AuSe units appended above and below it. Consequently, they showed different photophysical properties as reflected by their electronic absorption and emission spectra. Especially, both SD/Au8a and SD/Au8b exhibit blue-shifted thermochromic luminescence upon cooling from 293 to 83 K but the latter exhibits anomalous emission intensity evolution trends due to the occurrence of temperature-induced phase transition as revealed by varied-temperature crystallographic analyses. This work not only clearly illustrates the significance of ligands on tuning the kernel structure but also provides two rarely comparable examples for better understanding of the structure-property relationship of gold nanoclusters.
This work was financially supported by the National Natural Science Foundation of China (Nos. 91961105, 21822107, 22001139, and 21827801), the Natural Science Foundation of Shandong Province (Nos. ZR2019ZD45, ZR2020ZD35, ZR2019BB058, JQ201803, and ZR2017MB061), the Taishan Scholar Project of Shandong Province of China (Nos. tsqn201812003 and ts20190908), and the Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province (No. 2019KJC028).