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. 2022 Jan 3;27(1):280.
doi: 10.3390/molecules27010280.

Investigation of Metastable Low Dimensional Halometallates

Navindra Keerthisinghe  1 , Matthew S Christian  1 , Anna A Berseneva  1 , Gregory Morrison  1 , Vladislav V Klepov  1 , Mark D Smith  1 , Hans-Conrad Zur Loye  1
Affiliations

Investigation of Metastable Low Dimensional Halometallates

Navindra Keerthisinghe et al. Molecules. .

Abstract

The solvothermal synthesis, structure determination and optical characterization of five new metastable halometallate compounds, [1,10-phenH][Pb3.5I8] (1), [1,10-phenH2][Pb5I12]·(H2O) (2), [1,10-phen][Pb2I4] (3), [1,10-phen]2[Pb5Br10] (4) and [1,10-phenH][SbI4]·(H2O) (5), are reported. The materials exhibit rich structural diversity and exhibit structural dimensionalities that include 1D chains, 2D sheets and 3D frameworks. The optical spectra of these materials are consistent with bandgaps ranging from 2.70 to 3.44 eV. We show that the optical behavior depends on the structural dimensionality of the reported materials, which are potential candidates for semiconductor applications.

Keywords: dimensional reduction; halometallate; hydrothermal synthesis.

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Conflict of interest statement

The authors declare no known competing financial interest or conflict of interest.

Figures

Figure 1
Figure 1
The structures of compounds [1,10-phenH][Pb3.5I8] (1), [1,10-phenH2][Pb5I12]·(H2O) (2), [1,10-phen][Pb2I4] (3), [1,10-phen]2[Pb5Br10] (4) and [1,10-phenH][SbI4]·(H2O) (5) categorized according to structural dimensionality.
Figure 2
Figure 2
Schematic diagram of the reaction conditions used in synthesis of 1–5. * For material 2, all reaction conditions were the same as material 1, and it was produced only when the solvent was evaporated during synthesis.
Figure 3
Figure 3
View of [1,10-phenH][Pb3.5I8] down the c axis; unit cell shown in black dashed lines (left). View of single [Pb3.5I8]− layer down the a axis (top right) and the disordered 1,10-phenanthroline molecule and its two orientations (bottom right). Pb(1) is shown in partially filled dark gray color spheres. Pb(2), I, C, N and H shown in yellow, purple, black, blue and pink spheres, respectively.
Figure 4
Figure 4
View of chain 1 (orange), view of chain 2 (yellow), the top view from b-axis (top middle), the side view from a-axis (bottom middle) and the view from c-axis of [1,10-phenH2][Pb5I12]·(H2O) 3D structure (left). Pb(1) and Pb(2) shown in orange octahedra, Pb(3) in yellow octahedra; I and C atoms are shown in purple and black spheres, respectively. H and O atoms are not shown for clarity.
Figure 5
Figure 5
View of [1,10-phen][Pb2I4] down the c-axis (left). View of one 2D chain of [1,10-phen][Pb2I4] down the a-axis (top right). The two Pb sites (bottom right). Pb in yellow octahedra; I, C and N shown in purple, black and blue spheres, respectively. H atoms are not shown for clarity.
Figure 6
Figure 6
View of [1,10-phen]2[Pb5Br10] down the c-axis (left). View of single layer (right). Pb1 shown in purple polyhedra, Pb2 and Pb3 in beige octahedra. Br, C and N are shown in yellow, black and blue spheres. H atoms are not shown for clarity.
Figure 7
Figure 7
View of [1,10-phenH][SbI4]·(H2O) down the a-axis (top left); SbI4 chains running along a-axis (bottom left). View of SbI3 layered structure (top right) and a single layer of SbI3 (bottom right). Sb, I, C and N are shown in beige, purple, black and blue spheres. H and O atoms are not shown for clarity.
Figure 8
Figure 8
FTIR spectra for pure 1,10-phenanthroline (top left), 1 (top middle), 2 (top right), 3 (bottom left), 4 (bottom middle) and 5 (bottom right).
Figure 9
Figure 9
FTIR spectra for 1,10-phenanthroline (dark blue), 1 (green), 2 (brown), 3 (yellow), 4 (pink) and 5 (light blue) in the range 600–900 cm−1.
Figure 10
Figure 10
(a) UV-vis spectra for 1,10-phenanthroline (black), 1 (green), 2 (brown), 4 (pink) and 5 (light blue). (b) The emission spectrum of [1,10-phen]2[Pb5Br10] obtained at an excitation wavelength of 375 nm.
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