ABSTRACT
Reactions of [Et4N][Tp*WS3(CuCl)3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv. of AgOTf (OTf- = trifluoromethanesulfonate) and 1 equiv. of several bidentate pyridine ligands including 2,5-bis(pyridine-4-yl)thiazolo[5,4-d]thiazole (L1), 2,7-di(pyridin-4-yl)-9H-fluorene (L2), 2,7-di(pyridin-4-yl)-9H-carbazole (L3), and 2,7-di(pyridin-4-yl)-9H-fluoren-9-one (L4) afforded four W/Cu/S cluster-based supramolecular compounds [(Tp*WS3Cu2Cl)2(L1)] (2), {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L2)2}(OTf)2 (3), {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L3)2}(OTf)2 (4) and {[(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]2(L4)2}(OTf)2 (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray diffraction analysis. The neutral cluster 2 behaves as a supramolecular wire constructed by L1 bridging two butterfly-shaped [Tp*WS3Cu2Cl] cores. The cluster cations of 3-5 contain two [(Tp*WS3Cu3)2(µ-Cl)2(µ4-Cl)]+ cores linked by two L2, L3, or L4 ligands, which finally formed a cationic supramolecular rectangle. The third-order nonlinear-optical (NLO) properties of 3-5 in DMF were also investigated by Z-scan techniques and their NLO responses were enhanced compared to those of their precursor 1.
ABSTRACT
Solvothermal reactions of AgNO3 with N1,N4-bis(5-fluoropyridin-3-yl)succinamide (bfps) in MeCN afforded the one-dimensional cationic coordination polymer {[Ag(bfps)]NO3}n (1). Upon treatment of 1 with the anionic azo dye orange II (NaOII) in aqueous solution, the NO3- anions of 1 could be gradually exchanged by the OII- anions via an anion-exchange process. The resulting OII anion-exchanged products {[Ag(bfps)](NO3)0.85(OII)0.15}n (2) and {[Ag(bfps)](NO3)0.1(OII)0.9}n (3) were formed by different molar ratios of 1 and the newly formed phase "{[Ag(bfps)](OII)}n" (4), confirmed by PXRD patterns. Relative to those of the precursors 1 and NaOII, complexes 2 and 3 demonstrated enlarged photocurrent responses and reduced dielectric constants and dielectric losses, which could be correlated with the OII- contents in their structures. Complex 3 acquired a stable anodic photocurrent of 12.06 µA, which was 4.9 times higher than that of 1. The dielectric constant (εr = 4.2) and dielectric loss (0.002) of 3 were nearly frequency independent in the range from 1 to 106 Hz. The results provide an interesting insight into the rational assembly of CP-dye complexes and their tunable optoelectronic applications.
