Our efforts have focused on the synthesis of novel chalcogenidometalates, in which M‐phen/bpy complexes are embedded (M = transition metals, phen = 1, 10‐phenanthroline, bpy = 2, 2′‐bipyridine), because the MII‐phen/bpy cations have offered extensive applications in light harvesting and energy conversion. We report herein discrete supertetrahedral Fe4In16S35 clusters (T4) co‐crystallized with [Fe(bpy)3]2+ cations, namely [Fe(bpy)3]3[Fe4H2In16S35]·4Htean·2Hbpy·5H2O. The spectroscopic properties and thermal stability of the compound are discussed. It is the first example of a non‐corner‐capped discrete M4In16S35 T4 cluster. A notable feature of the compound is the soluble discrete nanoscaled thioindiate cluster. The related 1D InS T3 chain [Fe(bpy)3]2[H2In10S19]·2Htean·8H2O is also presented herein in order to understand the effect of the reaction conditions on the formation of the Tn structures.
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