Influence of coanions on construction of copper(II)/4,4′-dipyridyl sulfide(dps) coordination polymers

The influence of coanion on self-assembly of CuSO4 and 4,4′-dipyridyl sulfide (dps) was studied in this paper. During the formation of Cu(II)/dps coordination polymers, coanions Cl−, SCN− and PF6- were added in the solution respectively. Three novel coordination polymers were obtained, {[Cu(dps)2 · (SO4)2][Cu(dps) · Cl · (H2O)2]2 · 12H2O}n (1 · 12H2O, a 3D network), {[Cu(SCN)2(dps)(CH3OH)2][Cu(dps)2 · SO4][Cu(dps)(CH3CH2OH)2 · SO4] · 5H2O}n (2 · 5H2O, a 3D network), and {[Cu(dps)2(H2O)2] · (PF6)2 · 3H2O}n (3 · 3H2O, a 2D lattice network). Different coanion shows different influence on framework construction. In 1 and 2, Cl− and SCN− act as terminal ligands and similar 3D frameworks were composed of [Cu(dps)] layer with larger cavity (ca. 400 Å) and sulfate bridge; in 3, PF6- replaces SO42- entirely and the 3D framework was broken due to the removal of bridging SO42- anions. However, a 2D [Cu(dps)]4 undulating grid was preserved in 3.

Graphical abstractSynthesis, properties and structure architecture of {[Cu(dps)2 · (SO4)2][Cu(dps) · Cl · (H2O)2]2 · 12H2O}n, {[Cu(SCN)2(dps)(CH3OH)2][Cu(dps)2 · SO4][Cu(dps)(CH3CH2OH)2 · SO4] · 5H2O}n and {[Cu(dps)2(H2O)2] · (PF6)2 · 3H2O}n.Complexes 1, {[Cu(dps)2 · (SO4)2][Cu(dps) · Cl · (H2O)2]2 · 12H2O}n, 2, {[Cu(SCN)2(dps)(CH3OH)2][Cu(dps)2 · SO4][Cu(dps)(CH3CH2OH)2 · SO4] · 5H2O}n, and 3, {[Cu(dps)2(H2O)2] · (PF6)2 · 3H2O}n were prepared under similar reaction except utilizing different counteranions (Cl−, SCN− and PF6-). The structure analysis revealed that they have obvious different spacial array. Different coanion shows different influence on framework construction. In 1 and 2, Cl− and SCN− act as terminal ligands and similar 3D frameworks were composed of [Cu(dps)] layer with larger cavity (ca. 400 Å) and sulfate bridge; in 3, PF6- replaces SO42- entirely and the 3D framework was broken due to the removal of bridging SO42- anions. However, a 2D [Cu(dps)]4 undulating grid was preserved in 3.Figure optionsDownload full-size imageDownload as PowerPoint slide