Discrete and infinite 1D, 2D/3D cage frameworks with inclusion of anionic species and anion-exchange reactions of Ag3L2 type receptor with tetrahedral and octahedral anions

摘要

Complexes [PF6 subset of( Ag-3( titmb)(2)](PF6)(2)(8) and {SbF6 subset of[Ag-3( titmb)(2)](SbF6)(2)} center dot H2O center dot 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 center dot center dot center dot 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 center dot center dot center dot F contacts; an unique cage tetramer formed via Ag center dot center dot center dot pi interactions (Ag center dot center dot center dot eta(5)- 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 center dot center dot center dot 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 pi-pi interactions to form a 3D network. The anion-exchange reactions of four Ag3L2 type complexes ([BF4 subset of(Ag-3(titmb)(2)](BF4)(2) (6), [ClO4 subset of(Ag-3(titmb)(2)](ClO4)(2) ( 7b), [PF6 subset of(Ag-3(titmb)(2)](PF6)(2) (8) and [SbF6 subset of(Ag-3(titmb)(2)](SbF6)(2) center dot 1.5CH(3)OH ( 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-pi interactions of Ag3L2 complexes 1-9 are discussed.