A mixture of 2D and 1D metal-organic complexes, [ZnL(H2O)2·G1·DEF·2H2O]n (1a: G1 = naphthalene-2,7-disulfonate; DEF = N,N-diethylformamide) and [ZnL(H2O)3·G1·DEF·2H2O]n (2), has been prepared from a hydrogenated Schiff base L and Zn(II) in a DEF-contained solvent system under mild conditions. The yields of 1a and 2 are equivalent; however, they can be tuned by varying the amount of DEF solvent. Increasing the use of DEF tends to form pure 1a, while decreasing it generates 2. Without DEF, another novel 3D four-connected CdSO4 (cds) framework [ZnL(H2O)2·G1·2H2O]n (3) composed of alternated right-handed and left-handed helical chains has been constructed. The amount of DEF solvent has a significant impact on the diverse coordination architectures of 1-3, which is rare in the preparation of metal-organic complexes. The photoluminescence of complexes 1-3 along with naphthalene-2,7-disulfonate has been investigated in the solid state. The luminescent emission of G1 was enhanced greatly after being confined into metal-organic networks. In addition, complexes 1-3 display second-harmonic generation efficiencies, which are approximately 0.58, 0.42, 0.32, and 0.52 times as much as that of potassium dihydrogen phosphate.

To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe(II)(NC)M(II)(L)2(CN)Fe(II)(dppe) Cp][PF6]2 (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5–7 and two-electron oxidation products 8–11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1–4 suggests that both NC-Os(II)(L)2-CN and NC-Fe(II)(L)2-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M(II) to the terminal Fe(III) and the terminal Fe(II) to the terminal Fe(III) metal to metal charge transfers (MMCTs) in 5-7 and the central M(II) to the terminal Fe(III) MMCTs in 8-11. Moreover, for the two-electron oxidation products the MMCT energy increases with the central metal in the order Fe < Os < Ru. The two-electron oxidation complexes 8 and 9 exhibit a strong antiferromagnetic coupling (J ≈ -26 cm(-1)) between the two distant Fe(III) ions although separated by the diamagnetic cyanidometal NC-Os(II)(L)2-CN bridge. To the best of our knowledge, this is the strongest magnetic coupling between the distant paramagnetic metal ions across a diamagnetic cyanidometal bridge reported by far. For the two-electron oxidation complexes 10 and 11 with the diamagnetic NC-Fe(II)(L)2-CN bridge, however, the distant two Fe(III) ions possess only very weak antiferromagnetic coupling (J = -0.15 and -0.19 cm(-1)). Combined with our previous reported results, it could be found that the magnetic coupling strength between the distant Fe(III) ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.