J. Appl. Cryst.の発刊に際して

This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

/pdf/secondary-building-units-nets-and-bonding-in-the-chemistry-o0m4ttzsgz.pdf

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

Double-decker phthalocyanine complexes with Tb3+ or Dy3+ showed slow magnetization relaxation as a single-molecular property. The temperature ranges in which the behavior was observed were far higher than that of the transition-metal-cluster single-molecule magnets (SMMs). The significant temperature rise results from a mechanism in the relaxation process different from that in the transition-metal-cluster SMMs. The effective energy barrier for reversal of the magnetic moment is determined by the ligand field around a lanthanide ion, which gives the lowest degenerate substate a large |Jz| value and large energy separations from the rest of the substates in the ground-state multiplets.

Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level

Synthesis of 3d metallic single-molecule magnets

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

The dependence of iron oxide nanoparticle formation on the structure and thermal properties of Fe oleate complexes has been studied using FTIR, elemental analysis, X-ray photoelectron spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution TEM. The combination of FTIR, elemental analysis, and DSC allowed us to reveal differences between Fe oleate structures for as-synthesized and postsynthesis treated (drying and extraction with polar solvents) compounds. As-synthesized Fe oleate was found to contain a significant fraction of oleic acid, which works as a modifier altering the decomposition process and as an extra stabilizer during iron oxide nanoparticle formation. The thermal treatment of as-synthesized Fe oleate at 70 °C leads to removal of the crystal hydrate water and dissociation of oleic acid dimers, leading to a more thermally stable iron oleate complex whose final decomposition occurs at about 380 °C. Extraction of...

Influence of Iron Oleate Complex Structure on Iron Oxide Nanoparticle Formation

(-)-Sparteine-mediated asymmetric synthesis of di-n-octyl-substituted carbon-sulfur [11]helicene, a helical (C2S)n beta-undecathiophene, is described. The atom-efficient routes rely on one-step tri-annelation or two-step di- and mono-annelation to provide enantiomeric excess of (+)- or (-)-[11]helicene, respectively. X-ray structures for homologous [11] and [7]helicenes indicate similar helical curvatures. The optical band gap, Eg approximately 3.5 eV, is estimated for the (C2S)n helix polymer, with onset of electron localization at n </= 7.

Cross-Conjugated Oligothiophenes Derived from the (C2S)n Helix: Asymmetric Synthesis and Structure of Carbon−Sulfur [11]Helicene

The Mn12Ac single-molecule magnet has been converted for the first time into a form that contains non-carboxylate ligands. Reaction of Mn12Ac with diphenylphosphinic acid converts it into the title compound in which eight of the acetate (Ac) groups have been replaced with Ph2PO2 (P) groups. The Mn12AcP product retains the S=10 ground state and single-molecule magnetism properties of Mn12Ac, and displays hysteresis loops containing steps due to quantum tunneling of the magnetization. The crystal structures show that Mn12AcP can exist in three Jahn-Teller isomeric forms differing in the relative arrangement of the Mn(III) Jahn-Teller distortion axes.

Single-Molecule Magnets: Ligand-Induced Core Distortion and Multiple Jahn−Teller Isomerism in [Mn12O12(O2CMe)8(O2PPh2)8(H2O)4]

The three-coordinate, T-shaped Co(I) complex, PNPCo (PNP = [(tBu2PCH2SiMe2)2N-], is readily synthesized by magnesium reduction of divalent PNPCoCl. Triplet (S = 1) PNPCo is coordinatively and electronically unsaturated and undergoes a thermally reversible oxidative addition reaction with H2, producing trivalent PNPCo(H)2. In contrast, the reaction with excess primary silane PhSiH3 quantitatively generates the base-stabilized silylene Co(V) compound

Maren Pink

Papers

Influence of Iron Oleate Complex Structure on Iron Oxide Nanoparticle Formation

Cross-Conjugated Oligothiophenes Derived from the (C2S)n Helix: Asymmetric Synthesis and Structure of Carbon−Sulfur [11]Helicene

Single-Molecule Magnets: Ligand-Induced Core Distortion and Multiple Jahn−Teller Isomerism in [Mn12O12(O2CMe)8(O2PPh2)8(H2O)4]

Three-Coordinate Co(I) Provides Access to Unsaturated Dihydrido-Co(III) and Seven-Coordinate Co(V)

Catalytic Hydrosilylation of the Carbonyl Functionality via a Transient Nickel Hydride Complex