Synthesis, structure, and spectroscopic and electrochromic properties of bis(phthalocyaninato)zirconium(IV)

Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2

“…However, after several days a black powder material from the solution was obtained. Elemental analysis of this powder material is consistent with a ZrPc 2 complex that has been characterised earlier [41,50]. Thus it was found that a decomposition process takes place in solution.…”

“…The displacements of the carbon atoms of the benzene rings for some metallodiphthalocyaninato structures [55][56][57][58][59][60][61] are listed in Table 4, for a comparison. As can be seen from Tables 3 and 4 [39], but they are slightly shorter than those observed in the crystal structure of the unoxidized ZrPc 2 complex [41]. This is likely due to the weaker repulsive interaction between Pc 2À and the one-electron oxidized Pc ÀÅ p-radical ligand in relation to the unoxidized ZrPc 2 , in which the PcÁ Á ÁPc interaction is undoubtedly greater, since both Pc rings are 2À.…”

“…In conclusion, most probably the Zr 4+ cation is sandwiched between the two phthalocyaninato macrocyclic rings with a non-integral formal oxidation state of À1.5. , but is smaller than that in the crystal of unoxidized ZrPc 2 , in which the greatest deviation equals 1.47 Å [41]. The distortion of the phthalocyaninato macrocyclic rings of the zirconium diphthalocyaninato complexes, that can be estimated by the bending of the isoindole units with respect to the N 4core and by the ''twisting'' of the peripheral carbon atoms of benzene rings, is collected in Table 3.…”

“…Additionally, the correlation between the crystal structures and charge transport properties of the two iodine-doped different zirconium diphthalocyaninato complexes [ZrPc 2 ](I 3 ) 2/3 , [ZrPc 2 ]I 3 AE I 2 , described earlier [38,39], with the third complex [ZrPc 2 ]IBr 2 , described here, are reported. The crystal structures and properties of the partially oxidized zirconium diphthalocyanine complexes are discussed and compared with the undoped ZrPc 2 complex [41].…”

Phthalocyaninate und Tetraphenylporphyrinate von hochkoordiniertem ZrIV/HfIV mit Hydroxo-, Chloro-, (Di)Phenolato-, (Hydrogen)Carbonato- sowie (Amino)Carboxylato-LigandenProfessor Joachim Strähle zum 65. Geburtstag gewidmet

“…Inzwischen belegen Röntgenstruktura-nalysen verschiedener Folgeprodukte, dass es sich in der Tat mehrheitlich um Zr IV -Komplexe des unsubstituierten Phthalocyanins handelt [3Ϫ6]. Während Monophthalocyaninate beider Metalle erst in letzter Zeit ein gewisses Interesse gefunden haben, sind ihre mononuklearen Diphthalocyaninate [7,8] seit längerem hinreichend gut untersucht. Allerdings steht der heutige Kenntnisstand der Koordinationschemie der Zr-und Hf-Phthalocyaninate noch weit hinter dem ihrer kürzlich referierten gängigen Tetraphenylporphyrinate(2-) (tpp) oder Oktaethylporphyrinate (oep) zurück [9].…”