Study on photoluminescence and structure of copper nanoclusters

Background: During the past few decades, metal nanoclusters have received considerable research interests for their distinct optical, catalytic and electronic properties. However, till today, most studies are focused on the synthesis, structure and properties of Au and Ag clusters, while the studies on Cu nanoclusters are rather rare because of its inherent instability. Purpose: We aim to synthesize the Cu nanocluster that has the tunable photoluminescence. Methods: Through varying the initial legend molar ratio of 2-mercapto-5-n-propylpyrimidine and dodecanethiol, a series of Cu nanoclusters with different emission wavelength were prepared. The photoluminescence property and structure of these nanoclusters were studied by the photoluminescence spectrometry (PL), X-ray absorption fine structure (XAFS) and Matrix Assisted Laser Desorption Ionization Time of Flight Spectrometer (MALDI-TOF) mass spectrometry. Results: (1) PL spectra showed that with the increase of the proportion of dodecanethiol, the maximum emission wavelength of Cu nanoclusters shifted from 618 nm to 571 nm. (2) Mass spectra results indicated that the main products were changed from Cu₅MPP₃ (MPP: 2-mercapto-5-n-propylpyrimidine) in the presence of MPP alone to Cu₄[MPP][C₁₂SH] when the dodecanethiol was introduced, and remains unchanged with increasing the dodecanethiol. (3) XAFS results showed that with the increase of dodecanethiol, the Cu-S bond length was shortened from 0.228 nm to 0.224 nm. Conclusion: The reduction of the amount of Cu atomic number would lead to the shift of emission wavelength from 618 nm to 597 nm, and the shortening of Cu-S bond length pushed down the HOMO level which was formed by the Cu(I)-S. With the increase of the HOMO-LUMO band gap, the emission wavelength of the products shifted from 597 nm to 571 nm. (authors)