The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3(CO)_(12) with R-C≡C-R'(R = Fc(Ferrocenyl); R′ = Ph(Phenyl), Fc, H). The hexacarbonyldiiron cluster with ferracyclopentadiene ring(μ_2, η~4-C_4Ph_4)Fe_2(CO)_6(1) and one tetraphenyl substituted cyclopentadienone(Ph_4C_4CO)(2) were simultaneously obtained by the reaction of Fe_3(CO)_(12) with alkyne(Ph-C≡C-Ph). Only one ferrole cluster(μ_2, η~4-C_4Fc_2H_2)Fe_2(CO)_6(3) was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex(η~4-C_4Fc_4CO)Fe(CO)_3(4) and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3(CO)_2](5) were obtained by using Fc-C≡C-Fc as alkyne. A new complex(η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one)-tricarbonyl iron(η~4-C_4Ph_2Fc_2CO)Fe(CO)_3(6) was synthesized by the reaction of Fe_3(CO)_(12) with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
A three-dimensional coordination polymer {[Dy(H2btec)2/4(btec)3/6(H2O)]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy(Ⅲ) coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063(1), b=7.1491(1), c=17.1197(3), α=90, β=97.10, γ=90°, V=1300.31(3)3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F(000)=892, the final R=0.0165 and wR=0.0448 for I > 2σ(I). The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy(Ⅲ) centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand (deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid) in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.
