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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 the Pb(II) ions and the coordination modes of the ligands in 4. Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y, −z + 1; (iv) −x, −y + 1, −z + 1; (v) x + 1, y, z. (b) Polyhedral representation of the one-dimensional sub-structure in 4 involving Pb(II) ions and the three different {AsO3} functionalities (view in the direction of the crystallographic b-axis). (c) Polyhedral representation of the two-dimensional layer sub-structure in 4 in which LAs21 moieties link between the adjacent one-dimensional subunits (view in the direction of the crystallographic b-axis). (d) Polyhedral representation of the three-dimensional framework structure in 4 in which LAs31 moieties pillar between the adjacent two-dimensional layers (view in the direction of the crystallographic a-axis). (e) The NaCl-type network representing the topology of the 3D framework in 4.
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Figure 4: (a) The coordination environment of the Pb(II) ions and the coordination modes of the ligands in 4. Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y, −z + 1; (iv) −x, −y + 1, −z + 1; (v) x + 1, y, z. (b) Polyhedral representation of the one-dimensional sub-structure in 4 involving Pb(II) ions and the three different {AsO3} functionalities (view in the direction of the crystallographic b-axis). (c) Polyhedral representation of the two-dimensional layer sub-structure in 4 in which LAs21 moieties link between the adjacent one-dimensional subunits (view in the direction of the crystallographic b-axis). (d) Polyhedral representation of the three-dimensional framework structure in 4 in which LAs31 moieties pillar between the adjacent two-dimensional layers (view in the direction of the crystallographic a-axis). (e) The NaCl-type network representing the topology of the 3D framework in 4.

Mentions: In 4, LAs11, LAs21, and LAs31 adopt (κO11-κO12)-μ2, (κO21, O21-κO22-κO23-κN21)-μ4, and (κO31, O31-κO32, O32-κO33-κN31)-μ6 coordination modes, respectively (figure 4(a)). The three different {AsO3} functionalities from LAs11, LAs21, and LAs31 link the Pb(II) ions into 1D chains that extend in the direction of the crystallographic b-axis (figure 4(b)), and which are connected to each other by the LAs21 spacer to form a 2D layer structure (figure 4(c)). These 2D layers are further linked by the LAs31 spacer to form a 3D framework. The lattice chloride anions are located in the channels of the 3D framework (figure 4(d)). From the topological point of view, the resulting Pb6 clusters (two Pb1, two Pb2, and two Pb3, denoted as S) can be viewed as nodes. Connectors between adjacent S nodes are provided by LAs21 and LAs31 (17.480(4) and 13.708(3) Å) and through inter-node linkages within the 1D chain (7.2305(14) Å (see SI, figures S4(b) and (c))). Consequently, the 3D framework of 4 can be abstracted as a six-connected network with the Schläfli and vertex symbols being (41263) and 4·4·4·4·4·4·4·4·4·4·4·4·∗·∗·∗, respectively. This topology is consistent with a pcu-type network, according to the Reticular Chemistry Structure Resource (RCSR) notation (figure 4(e)). There are two distinct, strong intramolecular hydrogen-bond interactions in 4 within the 3D framework: one type of interaction occurs between OH functionalities (O23) of the {As21O3} groups and deprotonated oxygen atoms (O33) of neighbouring {As31O3} groups; the other type of interaction prevails between the coordinated water (O51W) and the neighbouring N11 atom. These H-bonds are characterized by O23–H23···O33iii and O51W–H51A···N11vi distances of 2.527(8) and 2.880(10) Å, respectively [symmetry codes: (iii) −x, −y, −z + 1; (vi) x−1, y, z + 1].


Photoluminescent lead(II) coordination polymers stabilised by bifunctional organoarsonate ligands
(a) The coordination environment of the Pb(II) ions and the coordination modes of the ligands in 4. Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y, −z + 1; (iv) −x, −y + 1, −z + 1; (v) x + 1, y, z. (b) Polyhedral representation of the one-dimensional sub-structure in 4 involving Pb(II) ions and the three different {AsO3} functionalities (view in the direction of the crystallographic b-axis). (c) Polyhedral representation of the two-dimensional layer sub-structure in 4 in which LAs21 moieties link between the adjacent one-dimensional subunits (view in the direction of the crystallographic b-axis). (d) Polyhedral representation of the three-dimensional framework structure in 4 in which LAs31 moieties pillar between the adjacent two-dimensional layers (view in the direction of the crystallographic a-axis). (e) The NaCl-type network representing the topology of the 3D framework in 4.
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Figure 4: (a) The coordination environment of the Pb(II) ions and the coordination modes of the ligands in 4. Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y, −z + 1; (iv) −x, −y + 1, −z + 1; (v) x + 1, y, z. (b) Polyhedral representation of the one-dimensional sub-structure in 4 involving Pb(II) ions and the three different {AsO3} functionalities (view in the direction of the crystallographic b-axis). (c) Polyhedral representation of the two-dimensional layer sub-structure in 4 in which LAs21 moieties link between the adjacent one-dimensional subunits (view in the direction of the crystallographic b-axis). (d) Polyhedral representation of the three-dimensional framework structure in 4 in which LAs31 moieties pillar between the adjacent two-dimensional layers (view in the direction of the crystallographic a-axis). (e) The NaCl-type network representing the topology of the 3D framework in 4.
Mentions: In 4, LAs11, LAs21, and LAs31 adopt (κO11-κO12)-μ2, (κO21, O21-κO22-κO23-κN21)-μ4, and (κO31, O31-κO32, O32-κO33-κN31)-μ6 coordination modes, respectively (figure 4(a)). The three different {AsO3} functionalities from LAs11, LAs21, and LAs31 link the Pb(II) ions into 1D chains that extend in the direction of the crystallographic b-axis (figure 4(b)), and which are connected to each other by the LAs21 spacer to form a 2D layer structure (figure 4(c)). These 2D layers are further linked by the LAs31 spacer to form a 3D framework. The lattice chloride anions are located in the channels of the 3D framework (figure 4(d)). From the topological point of view, the resulting Pb6 clusters (two Pb1, two Pb2, and two Pb3, denoted as S) can be viewed as nodes. Connectors between adjacent S nodes are provided by LAs21 and LAs31 (17.480(4) and 13.708(3) Å) and through inter-node linkages within the 1D chain (7.2305(14) Å (see SI, figures S4(b) and (c))). Consequently, the 3D framework of 4 can be abstracted as a six-connected network with the Schläfli and vertex symbols being (41263) and 4·4·4·4·4·4·4·4·4·4·4·4·∗·∗·∗, respectively. This topology is consistent with a pcu-type network, according to the Reticular Chemistry Structure Resource (RCSR) notation (figure 4(e)). There are two distinct, strong intramolecular hydrogen-bond interactions in 4 within the 3D framework: one type of interaction occurs between OH functionalities (O23) of the {As21O3} groups and deprotonated oxygen atoms (O33) of neighbouring {As31O3} groups; the other type of interaction prevails between the coordinated water (O51W) and the neighbouring N11 atom. These H-bonds are characterized by O23–H23···O33iii and O51W–H51A···N11vi distances of 2.527(8) and 2.880(10) Å, respectively [symmetry codes: (iii) −x, −y, −z + 1; (vi) x−1, y, z + 1].

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.