Ligand Control of Structural Diversity in Luminescent Hybrid Copper(I) Iodides

Shuxin Wang, Emily E. Morgan, Shobhana Panuganti, Lingling Mao, Pratap Vishnoi, Guang Wu, Quanlin Liu, Mercouri G. Kanatzidis, Richard D. Schaller, Ram Seshadri*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

39 Scopus citations

Abstract

Copper(I) iodide hybrids are of interest for next-generation lighting technologies because of their efficient luminescence in the absence of rare-earth elements. Here, we report 10 structurally diverse hybrid copper(I) iodides that emit in the green-red region with quantum yields reaching 67%. The compounds display a diversity of structures including ones with one-dimensional (1D) Cu-1 chains, Cu2I2 rhomboid dimers, and structures with two different arrangements of Cu4I4 tetramers. The compounds with Cu2I2 rhomboid dimers or Cu4I4 cubane tetramers have higher photoluminescence quantum yields than those with Cu-I 1D chains and octahedral Cu4I4 tetramers, owing to the optimal degree of condensation of the inorganic motifs, which suppresses nonradiative processes. Electronic structure calculations on these compounds point out the critical influence of the inorganic motif and organic ligand on the nature of the band gaps and thus the excitation characteristics. Temperature-dependent photoluminescence spectra are presented to better understand the nature of luminescence in compounds with different inorganic motifs. The emerging understanding of composition-structure-property correlations in this family provides inspiration for the rational design of hybrid phosphors for general lighting applications.

Original languageEnglish (US)
Pages (from-to)3206-3216
Number of pages11
JournalChemistry of Materials
Volume34
Issue number7
DOIs
StatePublished - Apr 12 2022

Funding

This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the grant DE-SC-0012541. We thank Anthony K. Cheetham for useful discussions. S.W. thanks the China Scholarship Council for a State Scholarship Fund. P.V. thanks the Science and Engineering Research Board (SERB) of the Govt. of India for a Ramanujan Fellowship (Award No. RJF/2020/000106) and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for financial support and research infrastructure. This work made use of the facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara supported by the National Science Foundation (DMR 1720256). SMLT has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE- 1650114. S.P. has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1842165 and the Ryan Fellowship at Northwestern University. The ultrafast laser system used for the PLLT measurements was funded by DURIP ARO grant 66886LSRIP. This work was performed in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the grant DE-SC-0012541. We thank Anthony K. Cheetham for useful discussions. S.W. thanks the China Scholarship Council for a State Scholarship Fund. P.V. thanks the Science and Engineering Research Board (SERB) of the Govt. of India for a Ramanujan Fellowship (Award No. RJF/2020/000106) and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for financial support and research infrastructure. This work made use of the facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara supported by the National Science Foundation (DMR 1720256). SMLT has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE- 1650114. S.P. has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1842165 and the Ryan Fellowship at Northwestern University. The ultrafast laser system used for the PLLT measurements was funded by DURIP ARO grant 66886LSRIP. This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry

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