Darstellung und Eigenschaften von (Acido)(pyridin)phthalocyaninato(2-)ruthenaten(II); Kristallstruktur von Tetra(n-butyl)ammonium(cyano)(pyridin)phthalocyaninato(2-)ruthenat(II)

Abstract

Bis(tetra(n‐butyl)ammonium‐bis(acido)phthalocyaninato(2–)ruthenat(II) reagiert in siedendem Pyridin zu blauviolettem, diamagnetischem Tetra(n‐butyl)ammonium(acido)(pyridin)phthalocyaninato(2–)ruthenat(II), (nBu4N)[Ru(X)(py)pc2–] (X = CN, N3, NCS, NCO, NO2). (nBu4N)[Ru(CN)(py)pc2–] kristallisiert orthorhombisch in der Raumgruppe Pca21 (Nr. 29) mit den Zellparametern a = 28,319(5) Å, b = 29,850(3) Å, c = 24,566(7) Å, Z = 16. In der Elementarzelle sind vier kristallographisch unabhängige Komplexanionen vorhanden. Das Ru‐Atom befindet sich jeweils außerhalb des Zentrums (Ct) der (Niso)4‐Ebene (Niso: Isoindol‐N‐Atom) und koordiniert axial trans‐ständig Pyridin und Cyanid. Die größte vertikale Auslenkung des Ru‐Atoms aus der (Niso)4‐Ebene in Richtung des Cyanids (d(Ru–Ct)) beträgt 0,020 Å. Der (Ru–Niso)‐Abstand variiert zwischen 1,947(2) und 1,992(2) Å. Der (Ru–C)‐Abstand beträgt durchschnittlich 2,00 Å, der (Ru–Npy)‐Abstand 2,19 Å. Der pc2–‐Ligand ist leicht zum Cyanid hin gewölbt. In den Cyclovoltammogrammen und Differenz‐Pulsvoltammogrammen von (nBu4N)[Ru(X)(py)pc2–] ist der erste quasi‐reversible Einelektronenprozeß (in V) bei 0,46 (X = CN), 0,34 (N3), 0,40 (NCO), 0,47 (NO2), 0,50 V (NCS) und der zweite unabhängig von X bei ca. 1,05 V zu beobachten. Der erste Prozeß ist metall‐, der zweite ringgerichtet. Die elektronischen Absorptionsspektren sowie die Schwingungsspektren von (nBu4N)[Ru(X)(py)pc2–] werden diskutiert.

Ruthenium Phthalocyanine-Bipyridyl Dyads as Sensitizers for Dye-Sensitized Solar Cells: Dye Coverage versus Molecular Efficiency

“…Each of these complexes displays one reduction and three oxidation processes (see Figure and the Supporting Information). The reversible one-electron reductions involve the [Pc 2− Ru II ]/[Pc 3− Ru II ] − couple with the E 1/2 values similar to those reported for the macrocycle-based reduction of other peripherally unsubstituted − and tetra- tert -butyl substituted PcRu complexes. The first two oxidations are both macrocycle-centered one-electron processes corresponding to the [Pc 2− Ru II ]/[Pc − Ru II ] + and [Pc − Ru II ] + /[Pc 0 Ru II ] 2+ couples, and the potentials are typical for these types of complexes. ,,, The second oxidations of 6 − 9 are quasi-reversible.…”

Functionalized Dendritic Oligothiophenes: Ruthenium Phthalocyanine Complexes and Their Application in Bulk Heterojunction Solar Cells

“…The E 0 red1 and E 0 ox1 potentials are attributed to a one-electron reduction (Pc 2− Ru II /Pc 3− Ru II ) and a one-electron oxidation (Pc 2− Ru II /Pc − Ru II ) of the Pc macrocycle, respectively. In general, since the CO ligand is a strong π-acceptor, the reduction of the macrocycle in the RuPcCOPy- n T complexes is facilitated (−1.60 V compared to first reduction potentials at around −1.90 V in the case of the RuPc(Py- n T) 2 complexes). , …”

Synthesis, Characterization, and Sensitizing Properties of Heteroleptic RuII Complexes Based on 2,6‐Bis(1‐pyrazolyl)pyr­idine and 2,2′‐Bipyridine‐4,4′‐dicarboxylic Acid Ligands

“…The Ru–Cl bond length of 5· 2CH 3 CN · 0.5CH 3 OH [2.403(2) Å] lies in the expected range for related Ru II complexes, [Ru(bdmpp)(bpy)Cl]Cl · 1.25CHCl 3, [Ru–Cl 2.419(3) Å],37 [Ru(bdmpp)(Me 2 bpy)Cl](PF 6 ) · 1.25CHCl 3 [Ru–Cl 2.445(2) Å],37 [Ru(dcbpyH 2 )(cymene)Cl][NO 3 ] [Ru–Cl 2.3966(10) Å] 34. Likewise, the Ru–C41 bond length of the cyanido ligand in 4· 7.5H 2 O · 0.5CH 3 CN [1.999(4) Å] lies in the range observed for other anionic [Ru(CN)(py)(pc)](NBu 4 ) [pc = phthalocyanine, Ru–C 2.01(2) Å],39 and cationic rutheniumcyano complexes [Ru(terpy)(phen)(CN)](PF 6 ) [Ru–C 2.004(3) Å] 40. The coordination geometry around the Na + cation is distorted octahedron comprised of water solvate molecules, whereas no interactions less than 3 Å are observed between the Na + and the oxygen atoms of the carboxylate groups.…”