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Complexes [PF6⊂(Ag3(titmb)2](PF6)2 (8) and {SbF6⊂[Ag3(titmb)2](SbF6)2}·H2O·1.5 CH3OH (9) are obtained by reaction of titmb and Ag+ salts with different anions (PF6− and SbF6−), and crystal structures reveal that they are both M3L2 cage complexes with short Ag⋯F interactions between the silver atoms and the fluorine atoms of the anions. In complex 8, a novel cage dimer is formed by weak Ag⋯F contacts; an unique cage tetramer formed via Ag⋯π interactions (Ag⋯η5-imidazole) between dimers and an infinite 1D cage chain is presented. However, each of the external non-disordered SbF6− anions connect with six cage 9s via Ag⋯F contacts, and each cage 9 in turn connects with three SbF6− anions to form a 2D network cage layer; and the layers are connected by π–π interactions to form a 3D network. The anion-exchange reactions of four Ag3L2 type complexes ([BF4⊂(Ag3(titmb)2](BF4)2 (6), [ClO4⊂(Ag3(titmb)2](ClO4)2 (7b), [PF6⊂(Ag3(titmb)2](PF6)2 (8) and [SbF6⊂(Ag3(titmb)2](SbF6)2·1.5CH3OH (9)) with tetrahedral and octahedral anions (ClO4−, BF4−, PF6− and SbF6−) are also reported. The anion-exchange experiments demonstrate that the anion selective order is SbF6− > PF6− > BF4−, ClO4−, and this anion receptor is preferred to trap octahedral and tetrahedral anions rather than linear or triangle anions; SbF6− is the biggest and most preferable one, so far. The dimensions of cage complexes with or without internal anions, anion-exchange reactions, cage assembly and anion inclusions, silver(i) coordination environments, Ag–F and Ag–π interactions of Ag3L2 complexes 1–9 are discussed. [ABSTRACT FROM AUTHOR]

Complexes [PF6⊂(Ag3(titmb)2](PF6)2 (8) and {SbF6⊂[Ag3(titmb)2](SbF6)2}·H2O·1.5 CH3OH (9) are obtained by reaction of titmb and Ag+ salts with different anions (PF6− and SbF6−), and crystal structures reveal that they are both M3L2 cage complexes with short Ag⋯F interactions between the silver atoms and the fluorine atoms of the anions. In complex 8, a novel cage dimer is formed by weak Ag⋯F contacts; an unique cage tetramer formed via Ag⋯π interactions (Ag⋯η5-imidazole) between dimers and an infinite 1D cage chain is presented. However, each of the external non-disordered SbF6− anions connect with six cage 9s via Ag⋯F contacts, and each cage 9 in turn connects with three SbF6− anions to form a 2D network cage layer; and the layers are connected by π–π interactions to form a 3D network. The anion-exchange reactions of four Ag3L2 type complexes ([BF4⊂(Ag3(titmb)2](BF4)2 (6), [ClO4⊂(Ag3(titmb)2](ClO4)2 (7b), [PF6⊂(Ag3(titmb)2](PF6)2 (8) and [SbF6⊂(Ag3(titmb)2](SbF6)2·1.5CH3OH (9)) with tetrahedral and octahedral anions (ClO4−, BF4−, PF6− and SbF6−) are also reported. The anion-exchange experiments demonstrate that the anion selective order is SbF6− > PF6− > BF4−, ClO4−, and this anion receptor is preferred to trap octahedral and tetrahedral anions rather than linear or triangle anions; SbF6− is the biggest and most preferable one, so far. The dimensions of cage complexes with or without internal anions, anion-exchange reactions, cage assembly and anion inclusions, silver(i) coordination environments, Ag–F and Ag–π interactions of Ag3L2 complexes 1–9 are discussed. [ABSTRACT FROM AUTHOR]