Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Fluorinated Tetraphenylporphyrins as Cocrystallizing Agents for C₆₀ and C₇₀

Four new cocrystals of fullerenes C60 and C70 have been prepared and characterized by X-ray crystallography, C60·1.5H2F20TPP·6benzene, C70·H2F20TPP·8benzene, C60·NiF20TPP·8benzene, and C70·ClFe(F20TPP) (F20TPP = 5,10,15,20-pentafluorophenylporphyrin). These structures reveal a marked encapsulation of the fullerene molecule by both the porphyrin and numerous C−F···C(fullerene) interactions

Unexpected Rearrangement of a Borneol-Derived <i>O-</i>Benzylated Hydroxamic Acid: Facile Synthesis of an Optically Active Multidentate Ligand

Unexpected Rearrangement of a Borneol-Derived O-Benzylated Hydroxamic Acid:  Facile Synthesis of an Optically Active Multidentate Ligan

Effect of Spin-Ladder Topology on 2D Charge Ordering: Toward New Spin-Antiferroelectric Transitions

The low-temperature structures of M(pyz)V4O10 (M = Co, Zn) in the spin-gapped state have been investigated by single-crystal X-ray diffraction and electronic structure calculations and provide evidence for a new type of spin-antiferroelectric transition for M = Zn. This new type of phase transition involves the onset of charge ordering within spin ladders that can be mediated by the metal-organic chains via a modification of the inter-ladder interactions

Copper(I) and -(II) Complexes of Neutral and Deprotonated <i>N</i>-(2,6-Diisopropylphenyl)-3-[bis(2-pyridylmethyl)amino]propanamide

As part of a study of atom-transfer radical polymerization (ATRP) catalysts, four new copper(I) and -(II) compounds of a new monoanionic, tripodal tetradentate ligand, N-(2,6-diisopropylphenyl)-3-[bis(2-pyridylmethyl)amino]propanamide (DIPMAP), were prepared. Ligand synthesis followed from the addition−elimination reaction of 2,6-diisopropylaniline with acryloyl chloride and then a Lewis acid catalyzed Michael addition of bis(2-pyridylmethyl)amine to this product. The ligand was complexed to CuCl to yield monomeric Cu(DIPMAP)Cl featuring an intramolecular hydrogen bond between the free amide hydrogen and the coordinated chloride ligand. Deprotonation of the amide hydrogen in Cu(DIPMAP)Cl using n-BuLi led to the incorporation of LiCl in the resulting product, Li2Cu2(DIPMAP)2Cl2. This complex exhibited an unusual dimeric structure, with the amine nitrogens of one ligand coordinated to a lithium ion, the amide oxygen of the same ligand bridging between the lithium ions, and the amidate nitrogen of that ligand coordinated to a CuCl unit that has a structure analogous to dihalocuprate ions. Deprotonation of Cu(DIPMAP)Cl using KOtBu yielded an alkali-metal chloride free product, Cu2(DIPMAP)2, that also exhibited a dimeric structure in which the three amine nitrogens of one ligand were coordinated to one CuI ion and the amidate nitrogen of the same ligand was coordinated to the other CuI ion. Cu2(DIPMAP)2 was effective in abstracting halogen atoms from organic halides, but in the attempted ATRP of tert-butyl acrylate, molecular weight versus conversion behavior reminiscent of a redox-initiated polymerization was observed. DIPMAP was coordinated to CuBr2 to yield [Cu(DIPMAP)Br]Br with a square-pyramidal structure. The amide hydrogen in this complex could be deprotonated using KOtBu to form complex [DIPMAP]CuBr (6). Spectral characterization of complex 6 confirmed deprotonation of the ligand and that it most likely had an axially distorted trigonal-bipyramidal structure, although crystals suitable for X-ray analysis could not be obtained. Solution oxidation of Cu2(DIPMAP)2 using CBr4 yielded a product, complex 4, whose spectral signatures did not match those of complex 6. The dimeric structure of Cu2(DIPMAP)2 might be a significant contributing factor to the slow rate of deactivation observed in atom-transfer reactions using Cu2(DIPMAP)2 as the catalyst