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a,d) Structural evolution from AGS to compound 3 by substituting [Ga7S16] and [K2PbI] for [Ga2S7] and Ag units, respectively. b) 1D infinite [Ga2S7] chain. c) [K2PbI]3+ cationic group chain along the b axis. Green atoms, co‐occupied by Pb2+ and K+ ions with a ratio of 1:1. e) 1D infinite [Ga7S16] chain constructed from double supertetrahedral units. f) [Ga7S16]11− composed of T2‐supertetrahedral by Ga(1)S4‐shared.
