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Spectroscopic and computational studies on self‐assembly complexes of bis(pyrrol‐2‐ ylmethyleneamine) ligands linked by alkyl spacers with Cu(II)
Author(s) -
Li Wei,
Wang Yibo,
Yang Lanying,
Szeghalmi Adriana,
Ye Yong,
Ma Jinshi,
Luo Mingdao,
Hu Jiming,
Kiefer Wolfgang
Publication year - 2007
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1670
Subject(s) - chemistry , density functional theory , raman spectroscopy , crystallography , basis set , hydrogen bond , alkyl , bond length , monomer , wavenumber , intermolecular force , molecule , crystal structure , computational chemistry , organic chemistry , physics , optics , polymer
Bis(pyrrol‐2‐ylmethyleneamine) ligands and their mononuclear monomeric and dinuclear dimeric self‐assembly complexes with Cu(II) were investigated by means of IR and Raman spectroscopies and density functional theory. The ground‐state geometries were calculated by using the BeckeLeeYangParr composite exchange‐correlation functional (B3LYP) and a combined basis set (LanL2DZ for Cu; 6–31G(d) for C, H, N), and they were compared with the single‐crystal X‐ray diffraction (XRD) structures. The DFT‐calculated CuN bond lengths are generally higher by 0.001–0.040 Å than those determined through XRD. The vibrational spectra were also calculated at the same level of theory for the optimized geometries. The calculated wavenumbers were scaled by a uniform scaling factor and compared with the experimental fundamentals. The predicted spectra are in good agreement with the experimental ones with the deviations generally less than 30 cm −1 . In comparison with the spectra of the ligands, the coordination effect shifts the υ(CN) wavenumber by about 50 cm −1 toward a lower value. Because of the weak intermolecular CH···Cu hydrogen bond, the CuN stretching mode is shifted toward a lower wavenumber. Copyright © 2006 John Wiley & Sons, Ltd.