All-Metal Antiaromatic Molecule: Rectangular Al44- in the Li3Al4- Anion

doi:10.1126/science.1082477

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Science 25 April 2003:
Vol. 300. no. 5619, pp. 622 - 625
DOI: 10.1126/science.1082477

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All-Metal Antiaromatic Molecule: Rectangular Al₄^4- in the Li₃Al₄^- Anion

Aleksey E. Kuznetsov,¹ K. Alexander Birch,¹ Alexander I. Boldyrev,¹^* Xi Li,²^,3 Hua-Jin Zhai,²^,3 Lai-Sheng Wang²^,3^*

We report the experimental and theoretical characterizationof antiaromaticity in an all-metal system, Li₃Al₄^–, whichwe produced by laser vaporization and studied with the use ofphotoelectron spectroscopy and ab initio calculations. The moststable structure of Li₃Al₄^– found theoretically containeda rectangular Al₄^4– tetraanion stabilized by the threeLi⁺ ions in a capped octahedral arrangement. Molecular orbitalanalyses reveal that the rectangular Al₄^4– tetraanionhas four ${pi}$ electrons, consistent with the 4n Hückel rulefor antiaromaticity.

¹ Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322, USA.
² Department of Physics, Washington State University, 2710 University Drive, Richland, WA 99352, USA.
³ W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Mail Stop K8-88, Post Office Box 999, Richland, WA 99352, USA.

^* To whom correspondence should be addressed. E-mail: boldyrev{at}cc.usu.edu, ls.wang{at}pnl.gov

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