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Issue 65, 2016
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Inorganic–organic hybrid materials based on PbBr2 and pyridine–hydrazone blocks – structural and theoretical study

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Abstract

Five lead(II) coordination compounds based on PbBr2 and a series of neutral hydrazone and hydrazine ligands (L1–L5) were prepared and structurally characterised, namely [Pb(μ2-Br)(Br)(L1)]2 (1), [Pb(μ2-Br)(Br)(μ2-L2)]n (2), [Pb(μ2-Br)(Br)(μ3-L3)]n (3), [Pb(μ2-Br)(Br)(μ2-L4)]n (4) and [Pb33-Br)22-Br)4(L5)2]n (5). In all compounds, there are bridging bromide ligands that interconnect Pb(II) centres and generate either [PbBr2]2 dimers (in 1, 2 and 3) or [PbBr2]n chain motifs (in 4) and [Pb3Br6]n ribbons (in 5). These correspond to three structural fragments present in the lead(II) bromide structure. Depending on the terminal (in 1 and 5) or μ2- and μ3-bridging (in 2, 3 and 4) coordination modes of organic building blocks, the [PbBr2]n fragments constitute discrete molecules (1) or extend to structurally distinct 1D (2 and 5) or 2D (3 and 4) metal–organic networks. Topological analysis and classification of these networks in 2–5 were performed, disclosing underlying chains or layers with the 2C1, 3,4L83, hcb topologies, and a trinodal 3,4,6-connected net of unprecedented topology, respectively. Theoretical calculations (DFT) were employed to analyze some relevant noncovalent interactions observed in the solid state. In particular the inter-ligand π–π stacking interactions in 1 and the influence of the metal coordination on their strength were analyzed. In 3, the role of intramolecular tetrel and π–hole unconventional interactions in the solid state architecture was demonstrated.

Graphical abstract: Inorganic–organic hybrid materials based on PbBr2 and pyridine–hydrazone blocks – structural and theoretical study

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Publication details

The article was received on 24 May 2016, accepted on 14 Jun 2016 and first published on 15 Jun 2016


Article type: Paper
DOI: 10.1039/C6RA13462A
Citation: RSC Adv., 2016,6, 60385-60393
  • Open access: Creative Commons BY-NC license
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    Inorganic–organic hybrid materials based on PbBr2 and pyridine–hydrazone blocks – structural and theoretical study

    G. Mahmoudi, V. Stilinović, A. Bauzá, A. Frontera, A. Bartyzel, C. Ruiz-Pérez and A. M. Kirillov, RSC Adv., 2016, 6, 60385
    DOI: 10.1039/C6RA13462A

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