Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Novel seven coordination geometry of Sn(IV): crystal structures of phthalocyaninato bis(undecylcarboxylato)Sn(IV), its Si(IV) analogue, and phthalocyaninato bis(chloro)silicon(IV). The electrochemistry of the Si(IV) analogue and related compounds

Three newly elucidated crystal structures of group IV phthalocyaninato complexes are reported, along with data for two further SiPc carboxylate complexes. In one of these crystal structures, bis(undecylcarboxylate)Sn(IV) phthalocyanine, the tin ion is seven coordinate, which is a unique finding for this atom in phthalocyanine ring coordination. Comparison of these structures with other group IV phthalocyaninato and related structures reveals differences, illustrating features significant in the chemistries of Si(IV) and Sn(IV) ions. These differences are thought to originate from their differing sizes and polarizabilities. The structures show that the Sn(IV) ion can only occupy an in-plane location in the phthalocyaninato ring where it elongates toward the two axial ligands. When the axial ligands do not facilitate this elongation cis coordination is preferred and the Sn(IV) ion sits above the phthalocyaninato ring plane. In contrast, the Si(IV) structures, with smaller, harder (i.e., less polarizable) Si(IV) ions, are six coordinate with the Si(IV) ion in the phthalocyaninato ring plane in a distorted octahedral symmetry. The electronic spectra and cyclic voltammetry of some of the Si compounds indicate that on the electrode the oxidized/reduced species behave as though they are in a solid film, rather than a soluble freely diffusing species.     

Two isomorphous complexes: di­chloro­[phthalocyaninato(2–)]­tin(IV) and di­chloro­[phthalocyaninato(2–)]­germanium(IV)

Isomorphous triclinic forms of di­chloro­[phthalocyaninato(2−)]­tin(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and di­chloro­[phthalocyaninato(2−)]­ger­manium(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalo­nitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl₂] and [GePcCl₂] [Pc is phthalocyaninate(2−)] mol­ecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the mol­ecules are additionally inclined. In both cases, the central Sn or Ge atom is six‐coordinated by the four iso­indole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal–bipyramidal structure. The arrangement of [SnPcCl₂] and [GePcCl₂] mol­ecules in the crystal structure is determined mainly by intermolecular C—H⃛Cl, π–π and van der Waals interactions.     

Sandwich-type tetrakis(phthalocyaninato) dysprosium-cadmium quadruple-decker SMM

Homoleptic tetrakis[2,3,9,10,16,17,23,24-octa(butyloxy)phthalocyaninato] dysprosium-cadmium quadruple-decker complex 1 was isolated in relatively good yield of 43% from a simple one-pot reaction. This compound represents the first sandwich-type tetrakis(phthalocyaninato) rare earth-cadmium quadruple-decker SMM that has been structurally characterized.     

Iodo­(phthalocyaninato)­chromium(III)

A new chromium(III)–phthalocyanine complex with the formula [Cr(C₃₂H₁₆N₈)I], or CrPcI where Pc is phthalocyanate(2?), has been obtained by the reaction of pure Cr powder with phthalo­nitrile under a stream of iodine vapour. The five‐coordinate Cr atom is bonded to the four iso­indole N atoms of the phthalocyaninate(2?) ligand and to one apical iodine ligand, and has a square‐pyramidal coordination geometry. The Cr^III cation is significantly displaced [0.456 (2) Å] from the N₄‐iso­indole plane towards the I atom. The Cr—I bond is tilted 2.51 (4)° to the N₄‐iso­indole plane.     

Optically Active Oxo(phthalocyaninato)vanadium(IV) with Geometric Asymmetry: Synthesis and Correlation between the Circular Dichroism Sign and Conformation

Oxovanadium(IV) phthalocyanines (VOPcs) with a single‐handed rotation have been prepared, and their right‐ and left‐handed enantiomers resolved on a chiral HPLC column. These enantiomers gave circular dichroism (CD) spectra of opposite signs; the correlation between the CD sign and conformation was obtained by time‐dependent density functional theory (TDDFT) calculations: an enantiomer showing a negative sign in the Q band was suggested to be the right‐handed conformer viewing from the axial oxygen side, whereas that giving a positive CD sign was assigned to the left‐handed conformer. Although silicon phthalocyanines (SiPcs) with two different alkoxy axial ligands have been resolved similarly, the absence of a meaningful CD difference probably reflects the flat character of the SiPc plane compared to the VOPc plane. Changes in the Q‐band CD, depending on the relative orientation of the peripheral substituents, have been worked out theoretically and the origin of the chiroptical properties is discussed.     

trans‐Bis(hexafluoroantimonato)(phthalocyaninato)copper(II)

The title compound, trans‐bis­(hexa­fluoro­antimonato‐F)(phthalocyaninato‐κ⁴N^29,30,31,32)copper(II), [Cu(SbF₆)₂(C₃₂­H₁₆N₈)] or Cu(pc)(SbF₆)₂ (pc is phthalocyaninate), comprises a six‐coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF₆^? groups. The compound is presumed to consist of a Cu^II center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO₄)₂.     

Darstellung und spektroskopische Eigenschaften der gemischtvalenten Di(phthalocyaninato)lanthanide(III)

Synthesis and Spectroscopical Properties of the Mixed-Valent Di(phthalocyaninato)lanthanides(III) Green di(phthalocyaninato)lanthanide(III), [M(Pc)₂] (M = rare earth metal ion: La‥(-Ce, Pm)‥Lu) is prepared by anodic oxidation of (ⁿBu₄N)[M(Pc^2?)₂] dissolved in CH₂Cl₂/(ⁿBu₄N)ClO₄. The UV-Vis-NIR spectra show intense π-π* transitions at ? 15000 cm^?1 and 31000 cm^?1, typical for Pc^2? ligands. Bands at ? 11000 cm^?1 and 22000 cm^?1 indicate the equal presence of a Pc^? π-radical. The metal dependent NIR band between 4000 and 9000 cm^?1 is characteristic for these mixed-valent complexes and assigned to an intervalence transition (b₁ → a₂; D_4d symmetry). Most bands are shifted linearly with the M^III radius. In the IR and resonance Raman (r.r.) spectra the typical vibrations of the Pc^? π-radical are dominant. These are essentially metal independent excepting the C? C and C? N vibrations of the inner (CN)₈ ring. The sym. M? N stretching vibration between 141 (La) and 168 cm^?1 (Lu) is selectively r.r.-enhanced when excited with 1064 nm.     

Synthesis, electrochemical and photophysical properties of phthalocyaninato oxotitanium(IV) complexes tetra-substituted at the alpha and beta positions with arylthio groups

The synthesis, electrochemical and photophysical properties of the following tetra-substituted thiol oxotitanium phthalocyanines are reported for the first time: 1,(4)-(tetraphenylthiophthalocyaninato)titanium(IV)oxide (); 1,(4)-(tetrabenzylthiophthalocyaninato)titanium(IV)oxide (); 2,(3)-(tetraphenylthiophthalocyaninato)titanium(IV)oxide () and 2,(3)-(benzylthiophthalocyaninato)titanium(IV)oxide (). Cyclic voltammograms of all four complexes are similar, with three reversible reduction couples each involving a one electron transfer process. The first two reductions were confirmed by spectroelectrochemistry to be metal-based reductions due to TiIVPc-2/TiIIIPc-2 and TiIIIPc-2/TiIIPc-2 redox processes, while the last reduction was confirmed to be a ring-based reduction due to TiIIPc-2/TiIIPc-3. Low fluorescence quantum yields (0.05-0.14), relatively long triplet lifetimes (150-210 micros) and triplet yields (0.31 to 0.82) were observed.     

Aqua­(phthalocyaninato)­magnesium

The title compound, [Mg(C₃₂H₁₆N₈)(H₂O)], crystallizes with two MgPc(H₂O) mol­ecules (Pc is phthalocyaninate) in the asymmetric unit. The geometries of the two mol­ecules are very similar, with the Mg atoms each 4+1‐coordinated by four iso­indole N atoms at the base and by the O atom of the water mol­ecule. The Mg atoms are displaced by 0.447 (1) and 0.468 (1) Å from the basal coordination planes towards the water O atoms. O—H?N hydrogen bonds form dimers stacked along the b axis in a herring‐bone fashion.     

Why magnesium is five‐coordinate in methanol(phthalocyaninato)magnesium(II)

The square‐pyramidal Mg center in the title compound, [Mg(C₃₂H₁₆N₈)(CH₄O)], is five‐coordinate due to the formation of back‐to‐back π–π dimers that saturate the vacant apical site of the metal coordination sphere. Each complex is a member of a back‐to‐back and a face‐to‐face dimer; the latter are tethered by two strong O—H⋯N hydrogen bonds. The dimers form columns that likely determine the solid‐state packing. The phthalocyaninate ligands are essentially planar, with a slight `hat visor' conformation character.