Blending Ionic and Coordinate Bonds in Hybrid Semiconductor Materials: A General Approach toward Robust and Solution-Processable Covalent/Coordinate Network Structures

Xiuze Hei, Wei Liu, Kun Zhu, Simon J. Teat, Stephanie Jensen, Mingxing Li, Deirdre M. O'Carroll, Kevin Wei, Kui Tan, Mircea Cotlet, Timo Thonhauser, Jing Li

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Inorganic semiconductor materials are best known for their superior physical properties, as well as their structural rigidity and stability. However, the poor solubility and solution-processability of these covalently bonded network structures has long been a serious drawback that limits their use in many important applications. Here, we present a unique and general approach to synthesize robust, solution-processable, and highly luminescent hybrid materials built on periodic and infinite inorganic modules. Structure analysis confirms that all compounds are composed of one-dimensional anionic chains of copper iodide (CumIm+2 2-) coordinated to cationic organic ligands via Cu-N bonds. The choice of ligands plays an important role in the coordination mode (μ1-MC or μ2-DC) and Cu-N bond strength. Greatly suppressed nonradiative decay is achieved for the μ2-DC structures. Record high quantum yields of 85% (λex = 360 nm) and 76% (λex = 450 nm) are obtained for an orange-emitting 1D-Cu4I6(L6). Temperature dependent PL measurements suggest that both phosphorescence and thermally activated delayed fluorescence contribute to the emission of these 1D-AIO compounds, and that the extent of nonradiative decay of the μ2-DC structures is much less than that of the μ1-DC structures. More significantly, all compounds are remarkably soluble in polar aprotic solvents, distinctly different from previously reported CuI based hybrid materials made of charge-neutral CumXm (X = Cl, Br, I), which are totally insoluble in all common solvents. The greatly enhanced solubility is a result of incorporation of ionic bonds into extended covalent/coordinate network structures, making it possible to fabricate large scale thin films by solution processes.

Original languageEnglish
JournalJournal of the American Chemical Society
Publication statusAccepted/In press - Jan 1 2020


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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