Two iodoargentate hybrid solids {[Ni(2,2′-bipy)(THF)2(H2O)2](Ag10I12)·2DMF}
n
(1) and {[Cu(2,2′-bipy)3](Ag5I7)}
n
(2) (THF=tetrahydrofuran, DMF=N,N′-dimethyl formamide, 2,2′-bipy =2,2′-bipyridine) have been synthesized in a polar organic solvent, whose one-dimensional iodoargentate polymers are induced by second entrapped metal−organic complexes. In 1, the [Ag5I6]
n
n− chain exhibits a columnar structure based on an Ag5I6 quasi-pentagram building block. In 2, the zigzag chain [Ag5I7]
n
2n− is constructed from an Ag6I11 building block. Two compounds exhibit intriguing semiconducting properties with E
g = 2.74 and 2.80 eV. As indicated by density functional theory calculations, the observed strong photoluminescence in 1 arises from band-edge transitions.
Four novel supramolecular frameworks constructed by complex cation [Ag(INA) 2 ] + (INA 5 isonicotinamide) and 1,5-naphthalenedisulfonate (1,5-NDS, compound 1), 2,6naphthalenedisulfonate(2,6-NDS, compound 2), biphenyldisulfonate (BPDS, compound 3) and 4,49-biphenyletherdisulfonate (PEDS, compound 4) anions were synthesized and characterized by X-ray single crystal diffraction, elemental analyses and IR spectra. The [Ag(INA) 2 ] + building blocks were extended into well-ordered supramolecular frameworks by complementary hydrogen bonds and weak Ag-O interaction with the sulfonate group. Ligand-supported weak argentophilic interactions are observed in compounds 2 and 4. The linkers of the disulfonate groups play an important role in the self-assembly process, and a total of twelve assembly patterns could be predicted for the frameworks constructed by [Ag(INA) 2 ] + and arenedisulfonate anions.
Two new polymeric iodoargentate hybrids induced by rare earth metal complexes and conjugated organic cations, {[Er(DMF)8][Ag6I9]}n (1) and [(MMP)(AgI2)]n (2) (MMP = 1‐methyl‐4‐methylpyridinium) were obtained by the routine synthetic reaction and structurally determined. In compound 1, a (Ag6I9)n3n– chain is defined by edge‐sharing Ag6I12 units, and in 2, the (Ag2I4)n2– chains are constructed by edge‐sharing AgI4 tetrahedra. C–H···I hydrogen bonds between cations and iodoargentate polyanions contribute to their structural extension from 1D to a 2D layer (for 1) and a 3D network (for 2). The UV/Vis spectra indicate that compared with 2, compound 1 exhibits a narrower adsorption scope with an onset at about 360 nm, and it has a much wider bandgap of about 3.50 eV.
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