Chlorine-passivated superatom Al<sub>37</sub> clusters for nonlinear optics

Haiming Wu; Zhixun Luo

doi:10.1007/s11426-018-9316-4

SCIENCE CHINA Chemistry

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SCIENCE CHINA Chemistry, Volume 61, Issue 12: 1619-1623(2018) https://doi.org/10.1007/s11426-018-9316-4

Chlorine-passivated superatom Al₃₇ clusters for nonlinear optics

Haiming Wu^1,2, Zhixun Luo^1,2,*

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ReceivedMay 7, 2018
AcceptedJun 21, 2018
PublishedSep 21, 2018

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Abstract

Utilizing a facile top-down synthetic procedure, here we report the finding of a chlorine-passivated Al₃₇ superatom cluster. It is demonstrated that the presence of electrophilic groups, severing as protecting ligands, alters the valence electron count of the metallic core and stabilize the as-prepared aluminum clusters especially when even-numbered chlorine atoms are located at equilibrium positions. Following the discussion regarding their reasonable stabilities, we illustrate the feasible reaction pathways in forming such chlorine-passivated Al₃₇ superatom clusters which bear delocalized superatomic orbitals with five valence 3P⁵ electrons shifting to the chlorine ligands indicative of a closed electron shell 2F¹⁴ of the metal core. The successful synthesis of such chlorine-protected aluminum clusters evidences the compatibility of general theory of cluster chemistry in both gas phase and wet chemistry. Such simple-ligand-protected aluminum clusters exhibit reverse-saturated-absorption (RSA) nonlinear optical property pertaining to electronic transitions within the discrete energy states of cluster materials.

Funded by

the Key Research Program of Frontier Sciences(QYZDB-SSW-SLH024)

the National Natural Science Foundation of China(21722308)

the National Thousand Youth Talents Program.

Acknowledgment

This work was supported by the Key Research Program of Frontier Sciences (QYZDB-SSW-SLH024), the National Natural Science Foundation of China (21722308) and the National Thousand Youth Talents Program.

Interest statement

The authors declare that they have no conflict of interest.

Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Figure 1
UV/Vis absorption spectra of the as-prepared aluminum clusters (a), with a comparison to that of the commercial Al powders dispersed in CH₂Cl₂ (b). The inset shows a photograph of the CH₂Cl₂ solvent, Al powder and the cluster sample (color online).
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Scheme 1
(a) A sketch showing the homemade setup for laser ablation of aluminium (LAL) rod in liquid. (b) The customized experimental setup for Z-scan nonlinear optics measurements (color online).
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Figure 2
Typical high-resolution electrospray ionization mass spectra (ESI-MS) of the aluminum clusters, in negative mode, with methanol as the mobile phase (color online).
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Figure 3
Millikan charge distribution, electrostatic potential, and frontier molecular orbitals of the neutral clusters Al₃₇ (a) and Al₃₇Cl₆ (b) at the pbepbe/tzvp level of theory (color online).
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Figure 4
(A) Reaction coordinate for the formation of Al₃₇Cl clusters at the pbepbe/tzvp level of theory. (B) NBO donor-acceptor interactions in Al₃₇-Cl-CH₂Cl complex of (a) initial adsorbed state I (b) transition state (TS) (c) desorption product (P). Pink, green, dark grey and light grey atoms refer to Al, Cl, C and H, respectively (color online).
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Figure 5
Normalized transmittance of aluminium chloride clusters (~1.17×10^?4?mol? dm^?3) plotted by Z-scan measurement under the conditions of open aperture (a), and closed aperture (b) conditions, along with the fitted curves (color online).