Thermal Behaviour of Some New Polyoxometalate Complexes of Ciprofloxacin with Keggin-type Heteropoly Acids

Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydrochloride(CPFX·HCl) reacting with H_nXM_~12 O_~40 ·nH_2O(X=P,Si; M=W,Mo) in an aqueous solution, and characterized by elemental analysis, IR spectrometry and TG-DTA. The IR spectrum confirms the presence of Keggin-type anions of heteropoly acids and the characteristic functional groups of ciprofloxacin. The TG/DTA curves show that their thermal decomposition is a multi-step process including simultaneous collapse of the Keggin-type structure. At first, these compounds had a mass loss of water molecules, then several other mass losses occured due to the decomposition of ciprofloxacin hydrochloride and its fragments with the degradation of Keggin anions. The end product of decomposition is the mixture of WO_3(or MoO_3) and SiO_2(or P_2O_5), identified by X-ray diffraction and IR spectroscopy. The possible thermal decomposition mechanisms of these complexes are proposed. This study exemplified that the thermal stability of the complexes containing tungsten is much better than that of the complexes containing molybdenum.

Surfactant-Encapsulated Polyoxometalate Complex as a Cathode Interlayer for Nonfullerene Polymer Solar Cells

An alcohol-soluble,environmentally friendly,and low-cost surfactant-encapsulated polyoxometalate complex[(C8H17)4N]4[SiW_(12)O40](TOASiW_(12))as a cathode interlayer(CIL)has exhibited excellent universality for various active layers and cathodes in nonfullerene polymer solar cells(NF-PSCs).In particular,incorporating TOASiW_(12) as the CIL enhanced power conversion efficiencies(PCEs)of the PM6:Y6-based NF-PSCs with Al or Ag cathode to 16.14%and 15.89%,respectively,and the PCEs of PM6:BTP-BO4Cl-based NF-PSCs with Al or Ag cathode to 17.04%and 17.00%,respectively.More importantly,the performances of the devices with TOASiW_(12) were insensitive to the TOASiW_(12) thickness from 3 to 33 nm.Furthermore,the NF-PSCs with TOASiW_(12) exhibited better device stability.Combined characterization of the photocurrent density versus effective voltage,capacitance versus voltage and electron mobility demonstrated that TOASiW_(12) as the CIL effectively promoted exciton dissociation,charge-carrier extraction,built-in potential,charge-carrier density,and electron mobility in the NF-PSCs.These findings suggest that TOASiW_(12) is a promising,competitive CIL for NF-PSCs fabricated by roll-to-roll processing.

Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

The polyoxometalate complex (CPFX-HCl)(4)H5BW12O40-12H(2)O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a four-step process consisting of the simultaneous collapse of Keggin anion. The intermediate and residue of the decomposition were identified by mean of TG-DTG, IR, and XRD technique. The non-isothermal kinetic data were analyzed by the Achar method and Coats-Redfern method. The apparent activation energy (E) and the pre-exponential factor (In A) of each decomposition were obtained. The most probable thermal decomposition reaction mechanisms were proposed by comparison of the kinetic parameters. The kinetic equation for both the second stage and the third stage can be expressed as d alpha/dt = Ae(-E/RT) -(1 - alpha)(2), and the fourth stage d alpha/dt = Ae(-E/RT) -(1 - alpha). And their mathematic expressions of the kinetic compensation effects of thermal decomposition reaction were also determined.

An Organic-inorganic Hybrid Two-dimensional Bilayer Assembled from 1:2-Type[Er(α-PW11O39)2]^11–Moieties and[Cu(dap)2]^2+Linkers

A new organic-inorganic hybrid phosphotungstate-based Cu^Ⅱ-Er^Ⅲ heterometallic derivative[Cu（dap）2（H2O）][Cu（dap）2]4.5[Er（α-PW11O39）2]·4H2O（1,dap = 1,2-diaminopropane） has been hydrothermally prepared and characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.1 belongs to the triclinic space group P1 with a = 13.453（3）,b =20.137（4）,c = 24.565（4） A,α = 103.468（4）,β = 103.829（4）,γ = 98.296（4）°,V= 6148.0（19） A°3,Z =2,μ = 22.212 mm^-1,GOOF = 1.030,R = 0.0744 and wR = 0.1700.Structural analysis indicates that1 exhibits a special two-dimensional double-layer structure constructed from l：2-type[Er（α-PW11O39）2]^11- moieties and[Cu（dap）2]^2＋ linkers.From the topological viewpoint,1 displays a scare two-dimensional five-connected topology in which the[Er（α-PW11O39）2]^11- moieties function as the five-connected nodes.Furthermore,its thermogravimetric behavior has been studied.