ChemInform Abstract Sapphyrin acts as an efficient sensitizer for the in vitro photoeradication of both herpes simplex virus and HIV-1. The sapphyrin derivative (IIIa) shows the typical spectroscopic features of decaalkyl sapphyrins. An X-ray analysis of the mixed hexafluorophosphate fluoride salt of (IIIa) (space group P21/c with Z=4) shows that the 22π electron system is suitable for the binding of anions.

Mono‐ and binuclear Rh and Ir complexes are easily obtained by reaction of sapphyrins with [{RhCl(CO)2}2] and/or [IrCl(CO)2(py)]. In these binuclear complexes (e.g., 1), the two [M(CO)2] fragments are no different sides of the ruffled 22 π‐electron ligands. Complex 1 catayzes the hydrogenation of cyclohexenes.

Detailed studies of the structure, conductivitity, magnetoresistance, optical spectra, and magnetic properties (susceptibility, EPR) for the new molecular metal tetrabenzporphyrin iodide (H(2)(tbp)I) and the electrical, spectral, and magnetic properties of Ni(tbp)I are reported. Paramagnetic transition-ion impurities were carefully excluded during the synthesis of H(2)(tbp)I and Ni(tbp)I, and both materials show much higher, metal-like conductivites than previously seen for less-pure Ni(tbp)I. Comparison of the specular reflectance data for Ni(tbp)I and H(2)(tbp)I allows a distinction between purely ring pi-transitions and metal-involved charge-transfer transitions, and the spectra fix the energy levels of the pi orbitals involved in conduction. Transport, magnetic, and optical properties show that both H(2)(tbp)I and Ni(tbp)I are ring-based conductors that have metal-like conductivities, varying as approximately 1/T, down to ca. 30-40 K. However, the remaining level of defects is higher in the tbp conductors than in H(2)(pc)I, and whereas the latter is metallic down to the mK temperature range, the defects in the (tbp) compounds localize the conduction electrons at approximately 10 K (Ni(tbp)I) and approximately 30 K (H(2)(tbp)I), leading to transport through one-dimensional variable-range hopping. EPR g-values for H(2)(tbp)I and Ni(tbp)I are close to that for the free electron and are nearly temperature-independent. The line widths for both samples are extremely narrow and also are nearly temperature-independent. These results show that Ni(tbp)I does not display doubly-mixed valence, as thought earlier: Paramagnetic impurities significantly altered the EPR signals of the prior samples. H(2)(tbp)I crystallizes in the space group P4/mcc with cell constants of a = 14.173(10) Å and c = 6.463(4) Å. Full-matrix least-squares refinement of 63 variables gave an R index of 0.061 on F(o)(2).

Electrochemical oxidation of (5, IO, I5,20-tetramethylporphyrinato)copper(II), Cu(tmp), in the presence of the perrhenate ion affords the new molecular conductor [Cu(tmp)12 [Re04]. The compound is composed of partially oxidized Cu(tmp) cations stacked metal-over-metal and surrounded by chains of Reo, anions. Single-crystal, room-temperature conductivity along the needle (crystallographic c) axis averages 40 Q-' cm-I, lower than the values previously reported for Ni(tmp)-based conductors. The conductivity is thermally activated and may be fit to an expression that describes a semiconductor with temperature-dependent carrier mobility: u = a , , F exp(-AE/kBr) (AE = 0.126 (2) eV, a = 3.8 (2)). Magnetic studies show that the local Cu(l1) moments and thc itincrant T-carrier electrons participate in strong spin exchange. This intramolecular Cu-T coupling is shown to mediate Cu-Cu spin cxchange along the linear chains of Cu(l1) ions found in this compound. These magnetic interactions depend on the thermally activated carrier concentration. The angular variation of the line width indicates that exchange is highly one-dimensional. Thc compound crystallizes in space group C&-P4/n of the tetragonal system with two formula units in a cell of dimensions a = 16.774 (9) 8, and c = 6.746 (4) 8, ( V = 1898 A3) at 1 I O K. Full-matrix least-squares refinement of 144 variables gives a final valuc of 0.069 for the R index on for 4695 unique observations and a value of 0.043 for the R index on F for the 2582 observations having Fo2 > 3u(F:). IntroductionPartial oxidation of metalloporphyrins yields a variety of electronically conductive solids.'-I2 Many of these exhibit the same basic structural motif chains of anions surrounding metal-over-metal stacks of metal lo macro cycle^.^^ One such conductor may be prepared by chemical oxidation of Ni(pc) (pc = phthalocyaninato) with molecular iodine and has the composition Ni(pc)l.' The phthalocyaninato ligand is partially oxidized in this compound, and the iodine is present as linear chains of 1,anions. Ni(pc)I is a highly conductive molecular metal (uRT = (a) Schramm, C. J.; Scaringe, R. P.: Stojakovic, D. R.; Hoffman, B. M.; Ibers, J. A.; Marks, T. J. J. Am. Chem. Soc. 1980,102,6702-6713. (b) Martinsen. J.; Greene, R. L.; Palmer, S. M.; Hoffman, B. M.; Ibers, J. A. J . Am. Chem. SOC. 1983, 105, 677-678. (c) Martinsen, J.; Palmer, S. M.; Tanaka, J.; Greene, R. L.; Hoffman, B. M. Phys. Reo. B 1984, (a) Ogawa, M. Y.; Martinsen, J.; Palmer, S. M.: Stanton, J. L.: Tanaka, J.; Greene, R. L.: Hoffman, B. M.; Ibers, J. A. J. Am. Chem. Sot. 1987, 109, 1 1 15-1 121. (b) Ogawa, M. Y.; Hoffman, B. M.: Lee, S.: Yudkowsky. M.: Halperin, W. P. Phys. Rev. Lett. 1986, 57, 1177-1180. Tatbp = triazatetrabenzoporphyrinato dianion. (a) Liou, K. K.; Ogawa, M. Y.: Newcomb, T. P.; Quirion, G.; Lee, M.; Poirier, M.: Halperin, W. P.; Hoffman, B. M.; Ibers, J. A. Inorg. Chem. 1989,28,3889-3896. (b) Quirion, G.; Poirier, M.; Ogawa, M. Y.: Hoffman, B. M. Solid State Commun. 1987,64,613-616. ( e ) Quirion, G.; Poirier...