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Issue 28, 2011
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Cu(I) and Pb(II) complexes containing new tris(7-naphthyridyl)methane derivatives: Synthesis, structures, spectroscopy and geometric conversion

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Abstract

Two novel facial-capping tris-naphthyridyl compounds, 2-chloro-5-methyl-7-((2,4-dimethyl-1,8-naphthyridin-7(1H)-ylidene)(2,4-dimethyl-1,8-naphthyridin-7-yl))methyl-1,8-naphthyridine (L1) and 2-chloro-7-((2-methyl-1,8-naphthyridin-7(1H)-ylidene)(2-methyl-1,8-naphthyridin-7-yl))methyl-1,8-naphthyridine (L2), as well as their Cu(I) and Pb(II) complexes, [CuLa(PPh3)]BF4 (1) (PPh3 = triphenylphosphine, La = bis(2,4-dimethyl-1,8-naphthyridin-7-yl)(2-chloro-5-methyl-1,8-naphthyridin-7-yl)methane), [CuLb(PPh3)]BF4 (2) (Lb = bis(2-methyl-1,8-naphthyridin-7-yl)(2-chloro-1,8-naphthyridin-7-yl)methane), [Pb(OLa)(NO3)2] (3) (OLa = bis(2,4-dimethyl-1,8-naphthyridin-7-yl)(2-chloro-5-methyl-1,8-naphthyridin-7-yl)methanol) and [Pb(Lb)2][Pb(CH3OH)(NO3)4] (4), have been synthesized and characterized by X-ray diffraction analysis, MS, NMR and elemental analysis. The structural investigations revealed that the transfer of the H-atom at the central carbon to an adjacent naphthyridine-N atom affords L1 and L2 possessing large conjugated architectures, and the central carbon atoms adopt the sp2 hybridized bonding mode. The reversible hydrogen transfer and a geometric configuration conversion from sp2 to sp3 of the central carbon atom were observed when Pb(II) and Cu(I) were coordinated to L1 or L2. The molecular energy changes accompanying the hydrogen migration and titration of H+ to different receptor-N at L1 were calculated by density functional theory (DFT) at the SCRF-B3LYP/6-311++G(d,p) level in a CH2Cl2 solution, and the observed lowest-energy absorption and emission for L1 and L2 can be tentatively assigned to an intramolecular charge transfer (ICT) transition in nature.

Graphical abstract: Cu(i) and Pb(ii) complexes containing new tris(7-naphthyridyl)methane derivatives: Synthesis, structures, spectroscopy and geometric conversion

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Publication details

The article was received on 12 Dec 2010, accepted on 27 Apr 2011 and first published on 17 Jun 2011


Article type: Paper
DOI: 10.1039/C0DT01747G
Citation: Dalton Trans., 2011,40, 7365-7374
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    Cu(I) and Pb(II) complexes containing new tris(7-naphthyridyl)methane derivatives: Synthesis, structures, spectroscopy and geometric conversion

    X. Gan, S. Chi, W. Mu, J. Yao, L. Quan, C. Li, Z. Bian, Y. Chen and W. Fu, Dalton Trans., 2011, 40, 7365
    DOI: 10.1039/C0DT01747G

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