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Photoluminescent lead(II) coordination polymers stabilised by bifunctional organoarsonate ligands

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ABSTRACT

1234123412,4314: Four lead(II) coordination polymers were isolated under hydro(solvo)thermal conditions. The applied synthetic methodology takes advantage of the coordination behaviour of a new bifunctional organoarsonate ligand, 4-(1, 2, 4-triazol-4-yl)phenylarsonic acid (H2TPAA) and involves the variation of lead(II) reactants, metal/ligand mole ratios, and solvents. The constitutional composition of the four lead(II) coordination polymers can be formulated as [Pb2(TPAA)(HTPAA)(NO3)]·6H2O (), [Pb2(TPAA)(HTPAA)2]·DMF·0.5H2O (DMF = N, N-Dimethylformamide) (), [Pb2Cl2(TPAA)H2O] (), and [Pb3Cl(TPAA)(HTPAA)2H2O]Cl (). The compounds were characterized by single-crystal and powder x-ray diffraction techniques, thermogravimetric analyses, infra-red spectroscopy, and elemental analyses. Single-crystal x-ray diffraction reveals that and represent two-dimensional (2D) layered structures whilst and form three-dimensional (3D) frameworks. The structures of , and contain one-dimensional (1D) {PbII/AsO3} substructures, while is composed of 2D {PbII/AsO3} arrays. Besides their interesting topologies, – all exhibit photoluminescence properties in the solid state at room temperature.

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(a) The coordination environment of Pb(II) ions and the coordination mode of the ligand in 3. Symmetry codes: (i) −x + 1, −y + 1, −z + 2; (ii) −x + 3/2, −y + 3/2, z; (iii) −x + 1, y−1/2, −z + 3/2; (iv) −x + 1, y + 1/2, −z + 3/2. (b) Polyhedral representation of two-dimensional layer structure in 3 comprising Pb(II) ions and the {As1O3} functionalities (view in the direction of the crystallographic a-axis). (c) Polyhedral representation of the three-dimensional framework of 3 (view in the direction of the crystallographic b-axis).
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Figure 3: (a) The coordination environment of Pb(II) ions and the coordination mode of the ligand in 3. Symmetry codes: (i) −x + 1, −y + 1, −z + 2; (ii) −x + 3/2, −y + 3/2, z; (iii) −x + 1, y−1/2, −z + 3/2; (iv) −x + 1, y + 1/2, −z + 3/2. (b) Polyhedral representation of two-dimensional layer structure in 3 comprising Pb(II) ions and the {As1O3} functionalities (view in the direction of the crystallographic a-axis). (c) Polyhedral representation of the three-dimensional framework of 3 (view in the direction of the crystallographic b-axis).

Mentions: In 3, the LAs1 ligand adopts a (κO1, O1-κO2-κO3, O3-κN1-κN2)-μ6 coordination mode (figure 3(a)). The AsO3 functionalities from LAs1 link Pb(II) ions into 2D layers that extend parallel to the ac-plane (figure 3(b)) and which are connected to each other by the LAs1 spacer to form a 3D framework (figure 3(c)). Intramolecular hydrogen-bond interaction occurs in 3 between the coordinated water molecule and the {AsO3} group (O3) to give a O4W—H4WB···O3v distance of 2.751(10) Å [Symmetry code: (v) x, y−1, z].


Photoluminescent lead(II) coordination polymers stabilised by bifunctional organoarsonate ligands
(a) The coordination environment of Pb(II) ions and the coordination mode of the ligand in 3. Symmetry codes: (i) −x + 1, −y + 1, −z + 2; (ii) −x + 3/2, −y + 3/2, z; (iii) −x + 1, y−1/2, −z + 3/2; (iv) −x + 1, y + 1/2, −z + 3/2. (b) Polyhedral representation of two-dimensional layer structure in 3 comprising Pb(II) ions and the {As1O3} functionalities (view in the direction of the crystallographic a-axis). (c) Polyhedral representation of the three-dimensional framework of 3 (view in the direction of the crystallographic b-axis).
© Copyright Policy - open-access
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC5036471&req=5

Figure 3: (a) The coordination environment of Pb(II) ions and the coordination mode of the ligand in 3. Symmetry codes: (i) −x + 1, −y + 1, −z + 2; (ii) −x + 3/2, −y + 3/2, z; (iii) −x + 1, y−1/2, −z + 3/2; (iv) −x + 1, y + 1/2, −z + 3/2. (b) Polyhedral representation of two-dimensional layer structure in 3 comprising Pb(II) ions and the {As1O3} functionalities (view in the direction of the crystallographic a-axis). (c) Polyhedral representation of the three-dimensional framework of 3 (view in the direction of the crystallographic b-axis).
Mentions: In 3, the LAs1 ligand adopts a (κO1, O1-κO2-κO3, O3-κN1-κN2)-μ6 coordination mode (figure 3(a)). The AsO3 functionalities from LAs1 link Pb(II) ions into 2D layers that extend parallel to the ac-plane (figure 3(b)) and which are connected to each other by the LAs1 spacer to form a 3D framework (figure 3(c)). Intramolecular hydrogen-bond interaction occurs in 3 between the coordinated water molecule and the {AsO3} group (O3) to give a O4W—H4WB···O3v distance of 2.751(10) Å [Symmetry code: (v) x, y−1, z].

View Article: PubMed Central - PubMed

ABSTRACT

1234123412,4314: Four lead(II) coordination polymers were isolated under hydro(solvo)thermal conditions. The applied synthetic methodology takes advantage of the coordination behaviour of a new bifunctional organoarsonate ligand, 4-(1, 2, 4-triazol-4-yl)phenylarsonic acid (H2TPAA) and involves the variation of lead(II) reactants, metal/ligand mole ratios, and solvents. The constitutional composition of the four lead(II) coordination polymers can be formulated as [Pb2(TPAA)(HTPAA)(NO3)]·6H2O (), [Pb2(TPAA)(HTPAA)2]·DMF·0.5H2O (DMF = N, N-Dimethylformamide) (), [Pb2Cl2(TPAA)H2O] (), and [Pb3Cl(TPAA)(HTPAA)2H2O]Cl (). The compounds were characterized by single-crystal and powder x-ray diffraction techniques, thermogravimetric analyses, infra-red spectroscopy, and elemental analyses. Single-crystal x-ray diffraction reveals that and represent two-dimensional (2D) layered structures whilst and form three-dimensional (3D) frameworks. The structures of , and contain one-dimensional (1D) {PbII/AsO3} substructures, while is composed of 2D {PbII/AsO3} arrays. Besides their interesting topologies, – all exhibit photoluminescence properties in the solid state at room temperature.

No MeSH data available.