Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches

The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl−}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the electron-rich trans L-ligand to the low-lying unfilled a1g(5s)-orbital of PdL2 were investigated using B3P86/lanl2DZ for Pd and 6-311+G** for other atoms. The pentacoordinate endo-[Pd([9]aneB2A)(L-donor)2]2+ complex with an axial (soft A--Pd) quasi-bond was optimized for stability. The fifth (soft A--Pd) quasi-bond between the σ-donor of soft A and the partially unfilled a1g(5s)-orbital of PdL2 was formed. The pentacoordinate endo-Pd([9]aneB2A)(L-donor)2]2+ complex has been found to be more stable than the corresponding tetracoordinate endo-Pd complexes. Except for the endo-Pd pentacoordinates, the tetracoordinate Pd([9]aneBAB)L2 complex with one equatorial (soft A-Pd) bond is found to be more stable than the Pd([9]aneB2A)L2 isomer without the equatorial (A-Pd) bond. In particular, the geometric configuration of endo-[Pd([9]anePNP)(L-donor)2]2+ could not be optimized

Fabrication and Characterization of Dye-Sensitized Solar Cells for Greenhouse Application

We have developed dye-sensitized solar cells using novel sensitizers with enhanced transmittance of red (625–675 nm) and blue (425–475 nm) wavebands to control the illumination condition in the greenhouse. Novel ruthenium bipyridyl sensitizers with general formulas (Me3PhN)4[Ru(dcbpy)2(NCS)2] (JJ-7) and (Me3BnN)4[Ru(dcbpy)2(NCS)2] (JJ-9) have been synthesized and demonstrated as efficient sensitizers in dye-sensitized solar cells for greenhouse application. Under standard AM 1.5 sunlight, the solar cell of JJ-7 using a liquid-based electrolyte exhibits a short-circuit photocurrent density of 8.49 mA/cm2, an open-circuit voltage of 0.83 V, and a fill factor of 0.71, corresponding to an overall conversion efficiency of 4.96% on 5 μm TiO2 film. The transmittance of JJ-7 and JJ-9 shows 62.0% and 61.0% at 660 nm and 18.0% and 15.0% at 440 nm for cultivation on 5 μm TiO2 film, respectively