Metal-organic frameworks (MOFs) have recently received increasing interest due to their potential application in the energy storage and conversion field. Herein, cobalt-based layered MOF ({[Co(Hmt)(tfbdc)(H2O)2]·(H2O)2}n, Co-LMOF; Hmt = hexamethylenetetramine; H2tfbdc = 2,3,5,6-tetrafluoroterephthalic acid) has been evaluated as an electrode material for supercapacitors. The Co-LMOF electrode exhibits a high specific capacitance and excellent cycling stability. Its maximum specific capacitance is 2474 F g(-1) at a current density of 1 A g(-1), and the specific capacitance retention is about 94.3% after 2000 cycles. The excellent electrochemical property may be ascribed to the intrinsic nature of Co-LMOF, enough space available for the storage and diffusion of the electrolyte, and the particles of nanoscale size.

Manganese-based layered coordination polymer ([Mn(tfbdc)(4,4'-bpy)(H2O)2], Mn-LCP) with microporous structure was synthesized by reaction of 2,3,5,6-tetrafluoroterephthalatic acid(H2tfbdc) and 4,4'-bipyridine(4,4'-bpy) with manganese(II) acetate tetrahydrate in water solution. Mn-LCP was characterized by elemental analysis, IR spectra, thermogravimetric analysis, X-ray single-crystal structure analysis, and powder X-ray diffraction. Magnetic susceptibility data from 300 to 1.8K show that there is a weak antiferromagnetic exchange between Mn(II) ions in Mn-LCP. As anode material, the Mn-LCP electrode exhibits an irreversible high capacity in the first discharge process and a reversible lithium storage capacity of up to about 390 mA h/g from the fourth cycle. It might provide a new method for finding new electrode materials in lithium-ion batteries.

A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.

A zinc-based one-dimensional (1D) coordination polymer ([Zn(Hmpca)(tfbdc)(HO)], Zn-ODCP) has been synthesized and characterized by spectroscopic and physicochemical methods, single-crystal X-ray diffraction, and thermogravimetric analysis (Hmpca = 3-methyl-1H-pyrazole-4-carboxylic acid; Htfbdc = 2,3,5,6-tetrafluoroterephthalic acid). Zn-ODCP shows blue luminescence in the solid state. When Zn-ODCP acts as an anode material for lithium ion batteries, it exhibits a good cyclic stability and a higher reversible capacity of 300 mAh g at 50 mA g after 50 cycles. The higher capacity may be mainly ascribed to the metal ion and ligand all taking part in lithium storage. Searching for electrode materials of lithium ion batteries from 1D metal coordination polymers is a new route.

A three-dimensional (3D) copper-based coordination polymer, ([Cu(H 2 mpca)-(tfbdc)], Cu-CP; H 2 mpca = 3-methyl-1H-pyrazole-4-carboxylic acid; H 2 tfbdc = 2,3,5,6tetrafluoroterephthalic acid), has been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analysis, and single-crystal X-ray diffraction. In Cu-CP, each Cu(II) ion is located in a triangular bipyramid geometry, and these Cu(II) ions are linked by tfbdc 2− ligands to produce a 3D network. Variable-temperature magnetic susceptibility data display that weak antiferromagnetic interactions between the adjacent Cu (II) ions exist in Cu-CP. Cu-CP was evaluated as an electrode material for supercapacitors. It displayed a higher specific capacitance of 735 F g −1 in 1 M KOH solution at a current density of 1 A g −1 and remained at 375 F g −1 after 1500 cycles at 2 A g −1 .

Assembly of a family of monomeric, dimeric, and polymeric W/Cu/S clusters from a precursor cluster [Et(4)N][Tp*W(mu(3)-S)(3)(CuBr)(3)] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) and various N-donor ligands was reported. The treatment of 1 with pyridine (py) or aniline (ani) in the presence of NH(4)PF(6) afforded a cationic cluster [Tp*W(mu(3)-S)(3)Cu(3)(py)(3)(mu(3)-Br)](PF(6)) (2) and a neutral cluster [{Tp*W(mu(3)-S)(3)(CuBr)(3)}(mu(6)-Br){Tp*W(mu(3)-S)(3)Cu(3)(ani)(3)}] x 4 ani x 0.5 Et(2)O (3 x 4 ani x 0.5 Et(2)O). On the other hand, the treatment of 1 with excess 4,4'-bipyridine (4,4'-bipy) or 1,2-bis(4-pyridyl)ethylene (bpee) followed by the addition of NH(4)PF(6) led to the formation of a polymeric cluster {[Tp*W(mu(3)-S)(3)Cu(3)(4,4'-bipy)(3)(mu(3)-Br)](PF(6)) x H(2)O}(n) (4) and a neutral cluster [{Tp*W(mu(3)-S)(3)Cu(3)Br(2)}(2)(bpee)] x 0.5 CH(2)Cl(2) (5 x 0.5 CH(2)Cl(2)). Meanwhile, analogous reactions of 1 with excess 1,2-bis(4-pyridyl)ethane (bpe) or 1,3-bis(4-pyridyl)propane (bpp) in DMF under the presence of NH(4)PF(6) resulted in the formation of two polymeric clusters {[{Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)}(2)(bpe)(3)](PF(6))(2) x MeCN}(n) (6) and {[Tp*W(mu(3)-S)(3)Cu(3)Br(mu(3)-Br)(bpp)] x DMF}(n) (7). Compounds 1-7 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, electrospray ionization mass spectra, and X-ray crystallography. The anion of 1 has an incomplete cubanelike [Tp*W(mu(3)-S)(3)(CuBr)(3)] structure, while the cation of 2 has a cubanelike [Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)] structure. Compound 3 may be viewed as having a corner-shared double cubanelike structure that consists of one [Tp*W(mu(3)-S)(3)Cu(3)(ani)(3)](2+) dication and one [Tp*W(mu(3)-S)(3)(CuBr)(3)](-) anion linked by a mu(6)-Br bridge. For 4, each [Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)] unit works as a pyramidal three-connecting node to connect its equivalent ones via three 4,4'-bipy bridges to yield a 2D (6,3) cationic network. Compound 5 has a dimeric structure in which two incomplete cubanelike [Tp*W(mu(3)-S)(3)Cu(3)Br(2)] cores are bridged with one bpee ligand. For 6, each dimeric [{Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)}(2)(bpe)(2)] unit is interconnected via a pair of bpe bridges to form a 1D zigzag cationic chain. Compound 7 has a 1D spiral chain in which each [Tp*W(mu(3)-S)(3)Cu(3)Br(mu(3)-Br)] core is interlinked by a couple of bpp bridges. The formation of 2-7 from the precursor cluster 1 through various N-donor ligands offers a new way to the design and assembly of the W/Cu/S clusters with interesting molecular and supramolecular arrays.

Three isomeric ligands, and four d10 metal CPs were synthesized, varying from 1D to 2D, together with achirality to chirality variation.

[Cd(HMPCA)2(H2O)4] (1), [Co(H2MPCA)2(DMF)2(H2O)2]Cl2(2), and [Cd3Cl2(HMPCA)4(H2O)2]·2H2O (3) have been synthesized. As a bifunctional catalyst, complex2exhibited excellent catalytic activity for OER and certain catalytic activity for ORR.