N-Heterocyclic Thione-Protected Ag₄Tetrahedra and Ag₈Cubes Cocrystallized in a Single Crystal

Abstract

Polynuclear silver clusters have attracted intensive attention in the academic community owing to their rich physicochemical properties. The development of thione-protected silver clusters has been lagging behind the well-explored thiolate-protected silver-sulfide clusters. Herein, we report two N-heterocyclic thione-protected silver clusters: [Ag4(2-TBI)6(SO4)3]2– (Ag4 ) and [Br@Ag8(2-TBI)12(SO4)2]3+ (Ag8 ) (2-TBI = 2-thiobenzimidazol), which cocrystallize to form cluster-based molecular crystals with a CaF2-type structure. The cocrystal shows high thermal stability in air. Notably, the two cluster-based layers are alternately assembled to exhibit a unique k-vector-differential crystallographic arrangement. This work may lay a foundation for synthesis of atomically precise and stable silver clusters using readily available N-heterocyclic thione ligands.

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…N [131] [{Mn(bpea)}4O6](X)3 (196)(197)(198)(199)(200), X = [BF4], OTf, [PF6], SCN, Bar'4) TACNMe, [Mn4O6(bpea)4](X)4 (188-192) / MeCN, 5 min S [131] [{Mn(dien)}2{Mn(bpea)}2O6](ClO4)4 (201) [Mn4O6(bpea)4](ClO4)4 (186), dien / MeCN, RT, 3 h Q [129] [{Mn(Medien)}4](ClO4)4 (202) [Mn4O6(bpea)4](ClO4)4 (186), Medien / MeCN, RT, 45 min. Q [129] [{Mn(R-ida)}2{Mn(bpea)}2O6] (203-206, R = Me, Bn, t Bu, C Pe) [Mn4O6(bpea)4](ClO4)4 ( 186), [ t Bu4N]2[R-ida] / MeCN, RT, 30 min.…”

“…Ag2SO4, 2-TBI, [Et4N]Br / MeCN, DMF, sonification, 120 °C, 2 days B/L [202] [Ph4P]2[Ag4(C4H3STe)6] (296) 1. Te, [Ph4P]Br, thiophene, n BuLi / THF 2.…”

“…While the reactants are similar to those used in other reactions leading to thiolate adamantanes, solvothermal conditions and ultrasonic activation are used in this case. 202 The only Te homolog in this compound family is found in [Ph 4 P] 2 [Ag 4 (C 4 H 3 STe) 6 ] ( 296). The ligand of this cluster is made by addition of elemental Te to thiophene in the presence of n BuLi.…”

“…While the reactants are similar to those used in other reactions leading to thiolate adamantanes, solvothermal conditions and ultrasonic activation are used in this case. 202 …”

Ultrastable Anti‐Acid “Shield” in Layered Silver Coordination Polymers

“…[11] In addition, the two N sites of the imidazole group can be deprotonated or protonated depending on the environment, [12] which may enhance the adaptability of 2D CPs to acidic and alkaline environments. Finally, the NÀ H bonds in the imidazole ring are hydrogen-bonding donors; [13] thus, supramolecular interactions can be integrated to provide additional protection to TBI-ligated 2D CPs. TBI ligands have been shown to be effective organic inhibitors for metal corrosion, even in HCl solution.…”