Preparation, X-ray Structures, Spectroscopic, and Redox Properties of Di- and Trinuclear Iron–Zirconium and Iron–Hafnium Porphyrinoclathrochelates; Inorganic Chemistry; Vol. 55, iss. 22
| Parent link: | Inorganic Chemistry Vol. 55, iss. 22.— 2016.— [P. 11867–11882] |
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| Other Authors: | , , , , , , , , , |
| Summary: | Title screen 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 and 13C{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)2 complexes. 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. Режим доступа: по договору с организацией-держателем ресурса |
| Language: | English |
| Published: |
2016
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| Subjects: | |
| Online Access: | http://dx.doi.org/10.1021/acs.inorgchem.6b01936 |
| Format: | Electronic Book Chapter |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=652408 |