An experimental and computational study on isomerically pure, soluble azaphthalocyanines and their complexes and boron azasubphthalocyanines of a varying number of aza units.

Herein, we present a series of isomerically pure, peripherally alkyl substituted, soluble and low aggregating azaphthalocyanines as well as their new, smaller hybrid homologues, azasubphthalocyanines. The focus lies on the effect of the systematically increasing number of aza building blocks [-N[double bond, length as m-dash]] replacing the non-peripheral [-CH[double bond, length as m-dash]] units and their influence on the physical and photophysical properties of these chromophores. The absolute and relative HOMO-LUMO energies of azaphthalocyanines were analyzed using UV-Vis and CV and compared to the density functional theory calculations (B3LYP, TD-DFT).

Soluble molybdenum(V) imido phthalocyanines and pyrazinoporphyrazines: crystal structure, UV-vis and electron paramagnetic resonance spectroscopic studies.

Soluble alkyl and aryl imido phthalocyanines [Pc(#)Mo(NR)Cl] (R = tBu, Mes) with molybdenum(V) as central metal were prepared and studied by UV-vis and electron paramagnetic resonance (EPR) spectroscopy. As structural analogue to the weakly aggregating, soluble alkyl substituted Pc(#) ligand, a new, more electron deficient octaazaphthalocyanine, the pyrazinoporphyrazine ligand Ppz(#), was designed. The respective alkyl and aryl imido complexes [Ppz(#)Mo(NR)Cl] are the first examples of molybdenum pyrazinoporphyrazines.

Axial functionalization of sterically hindered titanium phthalocyanines.

Several axially functionalized, weakly aggregating titanium phthalocyanines (Pc) have been synthesized and characterized. Soluble titanium dichlorido tetrakis-(1,1,4,4-tetramethyl-6,7-tetralino)-porphyrazine [Pc(#)TiCl(2)] (5) has been prepared by reductive cyclotetramerization of the respective dinitrile precursor in the presence of TiCl(4). 5 and the analogous oxido compound [Pc(#)TiO] (1) are versatile starting materials for the formation of other axially functionalized titanium phthalocyanines such as organoimido (6, 7), alkoxido and aryloxido (8, 9), peroxido (10), sulfido (12), disulfido (11), selenido (14) or diselenido (13) species.

Synthesis and X-ray crystal structures of imido and ureato derivatives of titanium(IV) phthalocyanine and their application in the catalytic formation of carbodiimides by metathesis from isocyanates.

The imido titanium phthalocyanine complex [PcTi(NDip)] (Dip = 2,6-diisopropylphenyl) 2a was synthesized from [PcTiO] 1 and one eq. of DipNCO. Due to the steric demand of the Dip group, addition of another isocyanate molecule to the Ti = N functionality of 2a does not occur even at high molar ratios of DipNCO.

Synthetic, spectroscopic, and structural studies on organoimido molybdenum, tungsten, and rhenium phthalocyanines.

Unprecedented imido phthalocyaninato complexes of pentavalent refractory metals [PcM(NR)Cl] (M = Mo, W, Re; R = tBu: 1, 3, 6, Mes: 2, 4, 7 or Ts: 5) have been synthesized by reductive cyclotetramerization of phthalonitrile in the presence of appropriate bis(imido) complexes of Mo, W and Re as templates. While d(1) Mo(V) and W(V) species 1-5 show distinctive EPR spectra corresponding to metal centered radicals with hyperfine coupling of two magnetically non-equivalent nitrogen atoms (4 equatorial and 1 axial N), corresponding d(2) Re(V) compounds 6 and 7 are diamagnetic. [PcMo(NtBu)Cl] 1 crystallizes from 1-chloronaphthalene in the tetragonal space group P4/n.