Inorganica Chimica Acta
Volume 554,
1 September 2023
, 121566
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Abstract
Three novel coordination polymers (CPs), [Pb(bpbp)X2]n (X=Cl (1), Br (2), I (3), bpbp=4,4′-bis(4-pyridyl)-biphenyl), were synthesized via solvothermal synthesis method. The three CPs are isostructural complexes exhibiting 2D inorganic-organic layer structures with (4, 4) topology which are constructed by Bpbp ligands connecting neutral [PbX2]n chains. The results of photoluminescence experiments and DFT calculations indicate that both the conjugated Bpbp ligands and halide anions show important roles in the emission process of CPs, and halide anions may slightly tune the structures and luminescence properties of CPs.
Graphical abstract
Three 2D lead halides coordination polymers with neutral [PbX2]n chains are synthesized via solvothermal methods, and the relationships between their structures and photoluminescence were well explored.
Three 2D inorganic-organic hybrid lead halides with neutral [PbX2]n chains are synthesized via solvothermal methods, and the relationships between their structures and photoluminescence were well explored.
Introduction
Since coordination polymers (CPs) are built from inorganic solids and functional organic ligands, it is feasible to design separately inorganic parts with low dimensions and organic parts as linkers or templates at the molecular engineering level.[1] The integration of the two parts will lead to various coordination polymers with diversified structures and fascinating physical properties. The design of inorganic parts is very important because the preferred backbones of inorganic parts may determine the topologies as well as the physical properties of the CPs, especially for isostructural complexes containing various similar organic ligands. Among various inorganic parts in CPs, various anionic lead halide [PbxXy](y−2x)− skeletons have been extensively structurally characterized due to their potential electrical, magnetic and optical property,[2], [2](a), [2](b), [2](c), [2](d), [2](e) while neutral lead halide [PbX2]n skeletons are seldom investigated,[3], [3](a), [3](b), [3](c), [3](d), [3](e) especially for 1D chain [PbX2]n skeletons. Only two complexes with 1D chain [PbX2]n skeletons[4], [4](a), [4](b) were reported until now according to the survey of the latest Cambridge Structural Database (CSD v5.43, Nov 2022 update).[5].
On the other hand, the selection or design of organic ligands is another key role in preparing CPs with specific topologies and desirable properties. Conjugated organic ligands, for examples, bipyridyl-based linkers with linear rigid backbones have attracted considerable interest in construction of CPs with diverse intriguing networks.[6], [6](a), [6](b), [6](c), [6](d) Moreover, conjugated ligands are usually possessing good potential ability to enhance photoelectron transfer due to their extended π-electron conjugated systems.[7], [7](a), [7](b), [7](c), [7](d) Accordingly, the integration of inorganic neutral lead halide [PbX2]n skeletons and conjugated organic ligands may lead to a novel class of lead halide CPs with special topologies and excellent properties. In this paper, lead halides and 4,4′-bis(4-pyridyl)-biphenyl (bpbp) were selected to assemble three CPs, [Pb(bpbp)X2]n (X=Cl (1), Br (2), I (3)) exhibiting 2D inorganic-organic layer structures with (4, 4) topology which are constructed by Bpbp ligands connecting neutral [PbX2]n chains. In addition, crystal structures, photoluminescent properties, the relationships between the structures and photoluminescence, thermal stabilities, and photocatalytic property of the three CPs were also investigated.
Section snippets
Experimental section
Materials and instrumentation. All chemicals were obtained from commercial sources and were used without further purification. The FT-IR spectra were recorded from KBr pellets on a FT-IR 8400S (CE) in the range 4000–400cm−1. C, H, and N elemental analyses were carried out on a Vario EL III elemental analyzer. X-ray powder diffraction data were recorded with Cu Kα radiation (λ=1.5406Å) on a XRD-6100 with a scan speed of 2°/min. Thermogravimetric analyses were performed on a HENVEN-HJ HCT-3
Results and discussion
Synthesis and general characterization. As described above, the three CPs were synthesized in similar methods except for the addition of different potassium halides, and they crystallize in different shapes while exhibit isomorphic crystal structures. CP 3 could be obtained in the mixed solution of CH3CH2OH/H2O (10mL, v/v=4:6) or CH3CN/H2O (10mL, v/v=4:6), while yellow crystals obtained in CH3CH2OH/H2O are not suitable for the determination by X-ray single crystal analysis due to their
Conclusions
In summary, three novel CPs constructed by Bpbp ligands connecting neutral [PbX2]n chains were synthesized, and the relationships between their structures and photoluminescence were well explored via DFT analysis. The synthesis strategy of the three CPs may be spread to prepare the family of metal-halide-bipyridine CPs constructed by conjugated organic bipyridine ligands bridging neutral metal halides/pseudohalides chains. In the three CPs, both the conjugated Bpbp ligands and halide anions
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
We gratefully acknowledge financial support by the National Natural Science Foundation of China (21071156), and the Natural Science Foundation of Chongqing (cstc2019jcyj-msxmX0170).
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