12 new cation-templated complexes, {(BMPB)[AgI 3 ]} (BMPB ¼ 1, 4-bis (methylpyridinium) benzene) 12), have been synthesized via the self-assembly reaction in solution. Owing to the cooperative template effects from organic cations and halide/thiocyanate anion compounds 1-11 contain a mononuclear anion structure [AgI 3 ] 2À (1), a dimeric anion [Ag 2 I 6 ] 4À (2), linear chain [Ag 2 X 4 ] 2À (3-10) and a cubanelike based one-dimensional anionic chain [Ag 4 I 6 ] 2À (11) that are enclosed into the different cationic channels formed from the pyridinium, phenanthrolinium and imidazolium. While for 12, the compound possesses an infinite 2D supramolecular polypseudorotaxane penetrated by geminal dicationic groups.

Cation-templated self-assembly of 1,ω-bis(pyridinium)alkanes (ω = 1−6) with cuprous thiocyanate was studied, and six sparse polymeric thiocyanate frameworks were obtained and characterized by X-ray crystallography: {(bpm)[Cu(NCS)4]} n (1), {(bpe)[Cu2(NCS)4]} n (2), {(bppp)[Cu(NCS)3]} n (3), {(bpbt)[Cu(NCS)4]} n (4), {(bppt)[Cu2(NCS)4]} n (5), and {(bph) [Cu2(NCS)4]} n (6) (bpm = 1,1′-bis(pyridinium)methylene, bpe = 1,2-bis(pyridinium)ethane, bppp = 1,3-bis(pyridinium)propane, bpbt = 1,4-bis(pyridinium)butane, bppt = 1,5-bis(pyridinium)pentane, bph = 1,6-bis(pyridinium) hexane). The structures consist of 0−3-dimensional frameworks with the bispyridinium cations trapped within host network cavities. Compound 1 has a 3D porous (6,3)/(6,4) joint topology structure, compounds 2 and 5 have two-dimensional polypseudorotaxane interlocked structures, compound 3 has a dimeric structure, compound 4 has a two-dimensional honeycomb structure, and compound 6 exhibits an interesting 1D hanging ladder-shaped complementary chain structure. The third-order NLO effect of 3 was studied by Z-scan techniques. The dimer exhibits self-focusing optical nonlinearities, and the effective third-order NLO refractive index (n 2) value is 3.03 × 10−11 esu.

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A novel coordination polymer [(Cu 4 I 6 )(BPE)] n (BPE = 1, 2-bis(pyridinium) ethane dication) is obtained and characterized by X-ray crystallography and IR spectroscopy. The complex crystallizes in monoclinic system, space group C2(1)/c with cell parameters of a = 16.5429(19)Å, b = 10.0645(12)Å, c = 11.7139(13) A, α = 90.00 • , β = 99.0910(10) • , γ = 90.00 • . In the polymeric framework, [Cu 4 I 6 ] n dimers are bridged together by the two µ 2 -I ligands to constitute an infinite 1D chain with the organic dication BPE trapped in it. Photoluminescence investigation of the complex reveals that a red shift of 67 nm for the complex takes place, compared with the organic dication.