This paper presents a detailed study of the solid-state chemical, spectral, structural, and charge transport properties of the materials which result from treating nickel phthalocyanine (NiPc) with elemental iodine. A range of NiPcI* stoichiometries is obtained where x = 0 to ca. 3.0; electrical conductivities of compressed polycrystalline samples are comparable with those of other "molecular metals". Single crystals were obtained for NiPcI10. These crystallize in the space group D^-PA/mcc,

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This paper reports on chemical and spectral studies of the macrocyclic uranyl complexes dioxocyclopentakis( 1 -iminoisoindolinato)uranium(VI), SPcUOa, and dioxocyclopentakis(l-imino-5-methylisoindolinato)uranium(VI), Me5SPcU02. These expanded, five-subunit analogues of phthalocyanines were synthesized in template reactions from uranyl salts and the corresponding phthalonitriles. The conditions for a high-yield synthesis are critical and include a polar solvent (e.g., dimethylformamide), high temperatures, and strict exclusion of water. Phthalocyanine, PcH2, is a side product of the reaction with the source of protons being the solvent. Attempts to displace the uranyl ion from SPcU02 with acids or other metal ions (M'!+) invariably result in macrocycle contraction to produce PcH2 or PcM"-2 and phthalonitrile.NMR studies reveal the fivesubunit macrocycle to be stereochemically dynamic. The analysis of ring current induced NMR shifts indicates considerably reduced electron delocalization in SPcU02 compared to PcM derivatives. The electronic spectrum of SPcU02 exhibits strong absorption maxima at 4240 and 9140 Á. With the aid of Pariser-Parr-Pople SCF LCAO Cl electron molecular orbital calculations, the electronic structure of the macrocycle and the origin of the spectral transitions can be shown to be closely analogous to phthalocyanine systems. Many of the chemical and spectral properties of SPcU02 and MesSPcUCh reflect the severe buckling and strain within the macrocyclic ligand.The application of transition metal ion "templates" to the construction of macrocyclic organic molecules is an area of synthetic chemistry which is rapidly growing in sophistication.2•3 It is clear that the presence of a metal ion can exert a profound control over the course of a number of types of condensation reactions, and can selectively promote the formation Journal of the American Chemical Society / 100:6 / March 15, coordinative specificity) are promoted by the unique coordinative properties of the uranyl ion.13 In this contribution we describe chemical studies relating to the synthesis and reactions of uranyl superphthalocyanine and related complexes, as well as spectral investigations of molecular and electronic structure. Experimental SectionAll operations involving air-sensitive reagents were carried out under nitrogen in Schlenk ware or in a glove box with rigorous exclusion of oxygen and moisture. Where necessary, solvents were refluxed over the appropriate drying agent and were freshly distilled under nitrogen. M/V-Dimethylformamide (Burdick and Jackson "distilled in glass") was stored over molecular sieves, then vacuum distilled twice from BaO. It was handled under nitrogen at all times.Infrared spectra were recorded on a Perkin-Elmer 267 spectrophotometer, and UV-visible spectra on Cary 14 or Cary 17D instruments.Proton nuclear magnetic resonance spectra were recorded on Perkin-Elmer R20B (60 MHz, CW), Bruker HFX-90 (90 MHz, CW), or Varían CFT-20 (80 MHz, FT) instruments. Elemental analyses were performed by Micro-Tech La...

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