Spectral study of the positive ions of metal phthalocyanines in oleum

Conductive molecular crystals. Structural, electrical, and magnetic properties of partially oxidized octamethyltetrabenzporphyrinatonickel(II)

“…If the oxidation in Ni(OMTBP)(I3)p is metal centered, the reference g values for the hypothetical (Ni(OMTBP))p-i+ fragment would be expected to be gx « 2.29 and gj 2.11 as is found for (NimPc)+. 24 No consistent fit of our experimental results is possible if such reference g values are employed. This confirms the qualitative argument for the oxidation being ligand centered.…”

“…However, if we take the oxidation to be ligand centered, then the reference g values should be those of the cation radical ( ( )+), which are expected to be gx ill * ge-Within the accuracy of these considerations it is sufficient to take gx ~g § ~ge, since the g tensor for the related compound (NinPc+) is roughly isotropic and close to the free-electron value (2.0023). 24 We thus arrive at the equation for gy in (ML)(I3)P ill = i= + 2a2 From the measured g values, the degree of back charge transfer from an I3~ion to the macrocyclic stack in both Ni(OMTBP)(I3)0 36 and Ni(OMTBP)(I3)0 97 is a2 = 0.004.…”

ChemInform Abstract: CRYSTAL STRUCTURE AND ELECTRICAL CONDUCTIVITY OF NICKEL 6,13‐DI(P‐TOLYL)‐5,14‐DIHYDRODIBENZO(B,I)‐1,4,8,11‐TETRAAZA(14)ANNULENE IODIDE (NI (DTDBTAA)I2.58)

“…Introduction. -It has recently been shown [l-31 that partial oxidation of metallotetraaza [ 14]annulenes by iodine leads to a large new class of highly conductive materials in which the properties can be manipulated by variation of the substituents and/or the central metal ion. In order to understand the effect of various substituents and metal atoms on the conductivity (and other physical properties) it is essential to obtain the data of single crystals of appropriate size and quality.…”

“…Only rarely have single crystals been obtained [l] [2] and examples where crystals grew to dimensions suitable for X-ray work are even more scarce. The structures of only two isomorphous iodides, Ni (dbtaa)12 and Pd (dbtaa)12 (dbtaa = dibenzo [b, i]-l,4,8,1l-tetraaza [ 14]annulene), are currently known [2].…”