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

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

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+22-) 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
Pages (from-to)4242-4253
Number of pages12
JournalJournal of the American Chemical Society
Volume142
Issue number9
DOIs
Publication statusPublished - Mar 4 2020

ASJC Scopus subject areas

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

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