title: Preparation, X-ray Structures, Spectroscopic, and Redox Properties of Di- and Trinuclear Iron-Zirconium and Iron-Hafnium Porphyrinoclathrochelates.
abstract: The first hybrid di- and trinuclear iron(II)-zirconium(IV) and iron(II)-hafnium(IV) macrobicyclic complexes with one or two apical 5,10,15,20-tetraphenylporphyrin fragments were obtained using transmetalation reaction between n-butylboron-triethylantimony-capped or bis(triethylantimony)-capped iron(II) clathrochelate precursors and dichlorozirconium(IV)- or dichlorohafnium(IV)-5,10,15,20-tetraphenylporphyrins under mild conditions. New di- and trinuclear porphyrinoclathrochelates of general formula FeNx3((Bn-Bu)(MTPP)) and FeNx3(MTPP)2[M = Zr, Hf; TPP = 5,10,15,20-tetraporphyrinato(2-); Nx = nioximo(2-)] were characterized by one-dimensional (1H and13C{1H}) and two-dimensional (COSY and HSQC) NMR, high-resolution electrospray ionization mass spectrometry, UV-visible, and magnetic circular dichroism spectra, single-crystal X-ray diffraction experiments, as well as elemental analyses. Redox properties of all complexes were probed using electrochemical and spectroelectrochemical approaches. Electrochemical and spectroelectrochemical data suggestive of a very weak, if any, long-range electronic coupling between two porphyrin π-systems in FeNx3(MTPP)2complexes. Density functional theory and time-dependent density functional theory calculations were used to correlate spectroscopic signatures and redox properties of new compounds with their electronic structures.
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.|Department of Technology of Organic Substances & Polymer Materials, Tomsk Polytechnic University , 634050 Tomsk, Russia.|Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991 Moscow, Russia.
authors: Semyon V
authors: SV
authors: Dudkin
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors: Nathan R
authors: NR
authors: Erickson
authors: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991 Moscow, Russia.
authors: Anna V
authors: AV
authors: Vologzhanina
authors: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991 Moscow, Russia.
authors: Valentin V
authors: VV
authors: Novikov
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors: Hannah M
authors: HM
authors: Rhoda
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors: Cole D
authors: CD
authors: Holstrom
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.|Department of Chemistry, University of Manitoba , Winnipeg, Manitoba R3T 2N2, Canada.
authors: Yuriy V
authors: YV
authors: Zatsikha
authors: Department of Technology of Organic Substances & Polymer Materials, Tomsk Polytechnic University , 634050 Tomsk, Russia.
authors: Mekhman S
authors: MS
authors: Yusubov
authors: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991 Moscow, Russia.
authors: Yan Z
authors: YZ
authors: Voloshin
authors: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.|Department of Chemistry, University of Manitoba , Winnipeg, Manitoba R3T 2N2, Canada.
authors: Victor N
authors: VN
authors: Nemykin