open access

https://hdl.handle.net/2115/8297

Magnetic Interactions of (μ-Pyrazolato)-Bridged Copper(II) Complexes Determined by Solid-State MAS NMR

英語

distribution of electron spin density

2005-11-17

Elsevier

Polyhedron

24(16-17)

2431-2436

http://www.sciencedirect.com/science/journal/02775387

We investigated electron spin densities of pyrazolato-bridged complexes [Cu(pz)2]n 1 and [Cu2(pz)2(NO3)(H2O)(phen)2]NO3 2 (Hpz = pyrazole, phen = 1, 10-phenanthroline) using solid-state high-resolution NMR to elucidate the magnetic interaction paths with the help of molecular orbital theory. We prepared deuterated analogue of these complexes, 1-d6 and 2-d6, to measure temperature dependence of 2H- and 13C-NMR shifts between 190 K and 350 K. The hyperfine coupling constants (HFCCs) and electron spin densities were determined from the slopes of the shifts as a function of the magnetic susceptibilities. The derived spin densities were all positive, which indicates the dominant magnetic interaction paths of these complexes are not π but σ orbitals of the pyrazolate ligand. The NMR results reasonably agreed with those of density functional theory (DFT) calculations for molecular models of 1 and 2.

学術雑誌論文

Accepted Manuscript

0277-5387