A novel type of copper(I)/(II) mixed-valence compound: [CuI(dmp)2]+[CuII(hfac)3]− with dmp=2,9-dimethyl-1,10-phenanthroline and hfac−=hexafluoroacetylacetonate

Blue Copper Model Complexes with Distorted Tetragonal Geometry Acting as Effective Electron-Transfer Mediators in Dye-Sensitized Solar Cells

“…The order of k 22 found in this study is well reflected as the difference in geometries between copper(I) and copper(II) (vide infra). The X-ray crystal structures of [Cu(SP)](mmt)] and [Cu(dmp) 2 ] 2+/+ have been reported previously. ,, The Cu II atom of [Cu(SP)](mmt)] adopts a distorted tetragonal geometry with a dihedral angle of 68° between the N 2 Cu and the S 2 Cu planes …”

“…Materials. [Cu(SP)(mmt)], [Cu(dmp) 2 ](CF 3 SO 3 ) 2 , [Cu(dmp) 2 ](CF 3 SO 3 ), [Cu(phen) 2 ](CF 3 SO 3 ) 2 , and [Cu(phen) 2 ](CF 3 SO 3 ) were prepared and characterized according to the literature. − [Cu(SP)(mmt)]Na was prepared by the reduction of [Cu(SP)(mmt)] using NaSCN aq. The Ru-dye, cis-dithiocyanato- N , N ‘ -bis(4-carboxylato-4-tetrabutylammonoiumcarboxylate-2,2‘-bipyridine)ruthenium(II) (N719), was synthesized from cis -dithiocyanato- N , N ‘ -bis(4,4‘-dicarboxylate-2,2‘-bipyridine)ruthenium(II) as described in the literature .…”

“…The intense bands in the region of 500−1000 nm are assigned to S → Cu(II) charge transfer (CT) bands . A distorted tetragonal geometry is also obtained for bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp) 2 ](CF 3 SO 3 ) 2 ) − by introducing methyl groups in the 2,9 positions of phenanthroline ligand as a result of the steric hindrance provided by two methyl groups . We have examined incident photon-to-current conversion efficiency and the photoelectrochemical responses of DSSCs containing [Cu(SP)(mmt)] 0/- , [Cu(dmp) 2 ] 2+/+ , and Cu(phen) 2 ] 2+/+ in comparison with the electron-transfer properties in solution.…”

The relevance of the fluorine interactions in the supramolecular structure of a complex constructed from copper(II) hexafluoroacetylacetonate and the 4′-(3-pyridyl)-2,2′:6′,2″-terpyridine ligand. Novel C–F/π synthons involving the π-system of the terpyridine moieties and those of the hexafluoroacetylacetonate chelate rings

“…The similarities include the presence of far-from-negligible ''slanting'' angles (defining as such the ''inclination'' with which the ligand approaches the cation and measures by the dihedral angle subtended by the O-Cu-O coordination plane and the ligand mean plane) (range for 1: 4.2(1)-25.2(1)8). These angles are usually significantly different from zero for [Tr(hfacac) 3 ] À units [13][14][15][16] but not, for instance, for their [Tr(acac) 3 ] À counterparts, where acac: acetylacetonato and the terminal groups are CH 3 [17][18][19]. It is tempting to ascribe the reasons behind these different behaviours to the intermolecular interactions to which the terminal CF 3 groups are involved, either as C-HÁ Á ÁF, C-FÁ Á Áp or C-FÁ Á ÁF-C, thus dragging the very labile ligand orientation out of their coordination planes, much in the way as a door is easily moved on its hinges (see Section 2.3.4).…”

A mixed-valence CuII/CuIanion–cation complex: bis[μ-5-sulfosalicylato(3–)]bis[(di-2-pyridylamine)copper(II)] bis[bis(di-2-pyridylamine)copper(I)] dihydrate

“…Mixed-valence Cu I,II complexes are of great importance in the ®elds of structural topology and functional materials (Zhang & Chen, 2003). In general, mixed-valence copper complexes exist as polynuclear species or ion pairs (Pawlowski et al, 2004). Although numerous complexes with cationic Cu II and anionic Cu I components have been prepared, complexes containing cationic Cu I and anionic Cu II motifs have been apparently ignored.…”