Role of Spacers and Substituents in the Self-Assembly Process: Syntheses and Characterization of Three Novel Silver(I)/Iodine Polymers

In our effort to systematically investigate the influences of ligand spacers and terminal groups on the Ag/I inorganic framework with large organic cation SDAs (structure-directing agents) ([Et 3 N(CH 2 ) 4 NEt 3 ] 2+, [Et 3 N(CH 2 ) 6 NEt 3 ] 2+, and [Me 3 N(CH 2 ) 6 NMe 3 ] 2+ ), three silver(I) coordination polymers, {[Et 3 N(CH 2 ) 4 NEt 3 ][Ag 4 I 6 ]} n ( 1 ) {[Et 3 N(CH 2 ) 6 NEt 3 ][Ag 5 I 7 ]} n ( 2 ), and {[Me 3 N(CH 2 ) 6 NMe 3 ][Ag 4 I 6 ]} n ( 3 ), have been synthesized in polar organic solvent. 1 − 3 all consist of one-dimensional polymers that could be described as edge-sharing AgI 4 tetrahedrons. Electrostatic interactions between organic countercations and inorganic moieties are presented and contribute to the crystal packing. The structural differences among 1 − 3 show the influences of the spacers and substituents of SDAs on the linkage modes of AgI 4 tetrahedrons. All compounds were further characterized with IR spectra, elemental analysis, thermal measurements, fluorescence analysis, and optical limiting measurements.