Accurate molecular structure of nickel phthalocyanine (NiN8C32H16): Gas-phase electron diffraction and quantum-chemical calculations

作者：Tverdova Natalya V; Pimenov Oleg A; Girichev Georgiy V^*; Shlykov Sergey A; Giricheva Nina I; Mayzlish Vladimir E; Koifman Oscar I

来源：Journal of Molecular Structure, 2012, 1023: 227-233.

DOI：10.1016/j.molstruc.2012.05.066

• Nickel phthalocyanine
• Electron diffraction
• Mass spectrum
• DFT calculations
• Molecular structure

The molecular structure of the nickel phthalocyanine (NiPc) was determined using the combination of gas-phase electron diffraction (GED), mass spectrometry and quantum chemical calculations. The DFT calculations with employing different functionals and basis sets found the molecular structure with D-4h symmetry that agrees satisfactorily to the one found in experiment at 776 +/- 5 K. The important bond lengths and bond angles according to GED (total errors in parentheses) are: r(h1)(Ni-N) = 1.913(5) angstrom, r(hi)(N- C-p) = 1.385(4) angstrom, r(h1)(C-p-N-m) = 1.327(5) angstrom, r(h1)(C-p-C-p) = 1.462(6) angstrom, r(h1)(C-p-C)= 1.399(3) angstrom, r(h1)(C-C) = 1.395(3) angstrom, angle NiNCp = 126.6(2)degrees, angle NCpNm = 128.4(4)degrees, angle CpNmCp = 120.1(5)degrees, angle NCpCp = 110.0(4)degrees, angle CpCpC= 121.2(1)degrees. The nickel-nitrogen bond distance obtained is by 0.04 angstrom longer than the one found for this compound in the literature. The structures of the crystalline and gaseous NiPc complex are compared. The effect of the metal (Ni, Cu, Zn) on structural features of the MPc complexes is discussed. Using NBO-analysis, the correlation between the metal-ligand bond distance and the total energy of donor-acceptor orbital interactions per one M-N bond was found in the MPc complexes.

• 出版日期2012-9-12