Untitled

Abstract

Potassium diphthalocyaninato(2±)metallate(III), K[M(pc 2± ) 2 ] (M = Bi, La, Ce, Pr, Sm, Sb, In) has been prepared by melting the metal chloride, iodide or acetate with 1,2-dicyanobenzene in the presence of potassium methylate. Crystallisation with tetra(n-butyl)ammonium bromide or hydroxide (( n Bu 4 N)Br/OH), tetra(n-pentyl)ammonium chloride (( n Pe 4 N)Cl) or bis(triphenylphosphine)iminium halide ((PNP)X; X = Br, I) yields the corresponding red-purple complex salt ( n Bu 4 N)[M(pc 2± ) 2 ] (M = Bi (1), La (3), Ce (2)), ( n Bu 4 N)[M(pc 2± ) 2 ]´x CH 3 OH (M = Bi (5), Pr (6), Sm (7); 0 9 x 9 1), ( n Pe 4 N)[La(pc 2± ) 2 ] (4), ( n Bu 4 N)[Pr(pc 2± ) 2 ]´2 py (10), ( n Bu 4 N)[Sb(pc 2± ) 2 ]´2 thf (11), (PNP) 2 [M(pc 2± ) 2 ]Br2 Et 2 O (M = Sb (12), Bi (13)), and (PNP) 2 [In(pc 2± ) 2 ]I´2 Et 2 O (14). Bronze coloured diphthalocyaninato(1±)metal(III) polyiodide, [M(pc ± ) 2 ]I 2 (M = Sc, Y) has been prepared similarly in the presence of ammonium iodide. Reduction with ( n Bu 4 N)OH provides ( n Bu 4 N)[M(pc 2± ) 2 ]´x CH 3 OH (M = Y (8), Sc (9); 0 9 x 9 1). Spectral properties (UV/VIS/NIR; IR; resonance Raman) of diphthalocyaninates in their different ring oxidation states (2±/2±; 2±/1±; 1±/1±) are discussed. 1±3 crystallise in the tetragonal (P4/ncc), 5±9 in the orthorhombic (Pna2 1 ), 10, 11 in the triclinic (P-1), and 4, 12± 14 in the monoclinic crystal system (4: P2 1 /m; 12: C2/c; 13, 14: P2/c). Ecliptic rotamers with skew angles ranging from 4.1°to 6.0°are found in 1±3, and staggered rotamers with skew angles ranging from 35.8°to 45.0°are found in 4±14. The mean M±N i bond lengths and interplanar distances increase monotonically with the ionic radius of the metal ion. Both distances deviate notably from this linear correlation in the Sb III and Bi III derivatives. The discrepancy is presumably due to the sterical dominance of the ns 2 lone-pair character. The actual size of eight co-ordinated Sb III and Bi III is estimated to be R 8 » 1.02(Sb)/1.11(Bi) A Ê . In every complex salt, the pc ligand is severely distorted from planarity and can adopt domed, saddled, waved and mixed non-planar conformations; the crystal symmetry is the most important factor for the conformational heterogeneity.

Tetrapyrazinoporphyrazines and their metal derivatives. Part I: Synthesis and basic structural information

“…In the case of 2,6-diisopropylphenoxy substituted Zn II complex [TPyz65PzZn(H 2 O)] (Fig. 16, left) the presence of coordinated water molecule leads to a dome-type distortion of the TPyzPz macrocycle typical for five coordinated Zn II complexes, e.g., with phthalocyanine [230]. Much stronger steric interaction between of 2,6-diphenyl substituted phenoxy groups in [TPyz69PzZn(H 2 O)] results in a peculiar saddle type distortion of the macrocycle (Fig.…”

Chiral Phthalocyanine with Unambiguous Absolute Molecular Structures for Both Enantiomers

“…This value is comparable to that observed in sandwich-type bis(phthalocyaninato) lanthanum complex La(Pc) 2 , 3.20 Å. [16] This demonstrates that there is an intense π-π interaction between the two phthalocyanine rings. Neither a plane nor centre of symmetry could be found in either of the rings, Figure 2(a), confirming the chiral nature of the structure.…”

Orientation-induced redox transformations in Langmuir monolayers of double-decker cerium bis[tetra-(15-crown-5)-phthalocyaninate] and multistability of its Langmuir-Blodgett films

“…1), ultrathin films of which are studied in this work. Ce(R 4 Pc) 2 differs from other substituted bis(phthalocyaninates) in the fact that the oxidation state of the metal center can be equal not only to 3+, which is typical for lanthnides series, but also to 4+ [6][7][8][9][10][11]. This circumstance makes it possible to increase the number of the stable states of the com plex, that widens the functional potential of supramo lecular devices assembled on its basis.…”