2024-03-29T11:25:40Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/687392022-11-17T02:08:08Zhdl_2115_20039hdl_2115_116Structural and transport properties of neutral radical crystals of Co-III(tmp)(CN)(2) (tmp=5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co-III( tmp)(CN)](n)Kurokawa, MasashiJose-Larong, Judy Fe F.Hasegawa, HiroyukiTakahashi, YukihiroHarada, JunInabe, Tamotsu430An axially ligated Co(tmp) (tmp = 5,10,15,20-tetramethylporphyrinato) anion, [Co-III(tmp)(CN)(2)](-), has been prepared and subjected to electrochemical oxidation to obtain the open shell tmp pi-ligand. With acetone as the solvent, solvent-free neutral radical crystals of Co-III(tmp)(CN)(2) are obtained, whereas solvent-inclusive crystals of Co-III(tmp)(CN)(2)center dot 2CH(3)CN are obtained with CH3CN as the solvent. In both crystals, the open shell tmp ring deforms into a ruffled form, which makes the pi-pi interactions in the crystal weak. Thus, the electrical conductivity is low, and the crystals behave as semiconductors with a room temperature resistivity of 10(6) Omega cm and an activation energy of about 0.3 eV. When the solvent is acetone, non-oxidized crystals of the CN-bridged polymer {[Co-III(tmp)(CN)](acetone)}(n) are obtained as a byproduct. The closed shell tmp ring deforms into a ruffled form, and there pi-pi interactions in the crystal are negligible. The room temperature resistivity is rather high at about 10(8) Omega cm.Royal Society of ChemistryJournal Articleapplication/pdfhttp://hdl.handle.net/2115/68739https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/68739/1/Co%28tmp%29%28CN%292revision170216.pdf1477-9226Dalton transactions4613442244292017-04-07enginfo:pmid/28300234info:doi/10.1039/c6dt04418bauthor