Crystalline salts of anionic free-base tetrapyrazinoporphyrazines with alkyl-substituents or an extended π-electron system

Abstract

Free-base octamethyltetrapyrazinoporphyrazine (H2TPyzPzMe8), octaethyltetrapyrazonoporphirazine (H2TPyzPzEt8), and tetra-2,3-[5,6-(9,10-phenanthro)pyrazino]porphyrazine (H2T(PhnPyz)Pz) have been synthesized by cyclic tetramerization of corresponding dinitriles followed by demetallation of the obtained magnesium complexes. Reduction or deprotonation of these...

Synthesis, X-ray Structures, and Optical and Magnetic Properties of Cu(II) Octafluoro-octakisperfluoro(isopropyl)phthalocyanine: The Effects of Electron Addition and Fluorine Accretion

“…A good fitting of the experimental data (Figure ) using g (Cu II ) = 2.19 and g = 2.0000 for F 64 Pc •3– yielded J = −0.56 cm –1 . The ligand-only g = 2.0000 value is consistent with g = 2.003–2.009 measured for the solution, ligand-only signal of [Zn­(F 64 Pc •3– )] − . , Compared with F 64 Pc •3– , the intramolecular couplings between Cu II and F x Pc •3– , x = 8 and 16, namely, −10.8 and −5.6 cm –1 , respectively (Table ) are at least 1 order of magnitude larger. , As the degree of fluorination increases, the intramolecular magnetic coupling decreases, a trend consistent with the notion of enhanced spin density transfer to acceptor fluoro-substituents as x increases. Thus, the weakest coupling in [Cu II (F 64 Pc) •3– ] − could be explained by the extreme electron deficiency of its Pc core. , The geometry around the copper­(II) atoms most probably does not affected the J values since, according to the SHAPE 2.1, estimation, for all three anions with x = 8, 16, and 64, the geometry of copper­(II) is very close to square-planar, D 4 h symmetry.…”

“…The ligand-only g = 2.0000 value is consistent with g = 2.003–2.009 measured for the solution, ligand-only signal of [Zn(F 64 Pc •3– )] − . 16 , 44 Compared with F 64 Pc •3– , the intramolecular couplings between Cu II and F x Pc •3– , x = 8 and 16, namely, −10.8 and −5.6 cm –1 , respectively ( Table 4 ) are at least 1 order of magnitude larger. 28 , 29 As the degree of fluorination increases, the intramolecular magnetic coupling decreases, a trend consistent with the notion of enhanced spin density transfer to acceptor fluoro-substituents as x increases.…”

“…The Cu–N bond distances do not vary significantly, despite the fact that the Cu is six-coordinated in 0 but four-coordinated in 1 – 3 . The most statistically significant changes are observed for the lengths of the N meso –C bonds. ,,− Shorter and longer N meso –C bonds, relative to the parent macrocycle, Cu II (F 64 Pc), for which the bonds are the same, are present in the reduced macrocycles with x = 8, 16. The common pattern is illustrated in Figure .…”

“…Weak NIR absorptions of the radical anion and dianion are present at 868–871 and 1005–1006 nm, consistent with bands observed for all reduced phthalocyanines, ,,,, including [Zn II (F 64 Pc •3– )] − , and tetrapyrazinoporphyrazine − macrocycles. Such bands are more intense relative to those of 1 and 2 , but the bands for the related Cu II (F 8 Pc) and Cu II (F 16 Pc) are also weak (see Table ).…”

Perchlorinated vanadyl tetrapyrazinoporphyrazine: spectral, redox and magnetic properties

“…[7][8][9] Compounds based on reduced phthalocyanines and related derivatives have also been extensively studied since they can potentially form compounds with coupling of spins. [10][11][12][13][14][15][16][17][18][19][20][21] Among such macrocycles vanadium complexes are interesting primarily due to the presence of an axial ligand, which promotes stacking in crystals, and paramagnetic properties of the central metal. [14][15][16][17][18] Hadt and colleagues have shown that vanadyl phthalocyanine, when mixed with titanyl phthalocyanine, and copper phthalocyanine mixed with zinc phthalocyanine, are potential options for use in quantum computing.…”