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Title: Realization of an Al≡Al Triple Bond in the Gas-Phase Na 3Al 2 - Cluster via Double Electronic Transmutation

Abstract

We report the discovery of homodinuclear multiple bonds composed of Group 13 elements represents one of the most challenging frontiers in modern chemistry. A classical triple bond such as N≡N and HC≡CH contains one σ bond and two π bonds constructed from the p orbitals perpendicular to the σ bond. However, the traditional textbook triple bond between two Al atoms has remained elusive. Here we report an Al≡Al triple bond in the designer Na 3Al 2 - cluster predicted in silico, which was subsequently generated by pulsed arc discharge followed by mass spectrometry and photoelectron spectroscopy characterizations. Being effectively Al 2- due to the electron donation from Na, the Al atoms in Na 3Al 2 - undergo a double electronic transmutation into Group 15 elements, thus the Al 2-≡Al 2- kernel mimics the P≡P and N≡N molecules. Lastly, we anticipate this work will stimulate more endeavors in discovering materials using Al 2-≡Al 2- as a building block in the gas phase and in the solid state.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [1];  [1];  [5];  [3]; ORCiD logo [4]
  1. Nankai University, Tianjin (China)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Utah State Univ., Logan, UT (United States)
  4. Johns Hopkins Univ., Baltimore, MD (United States)
  5. Karlsruhe Institute of Technology (Germany)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1481997
Report Number(s):
LA-UR-18-22726
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 43; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; Al≡Al triple bonds; double electronic transmutation; gas-phase clusters; photoelectron spectroscopy

Citation Formats

Zhang, Xinxing, Popov, Ivan Aleksandrovich, Lundell, Katie A., Wang, Haopeng, Mu, Chaonan, Wang, Wei, Schnöckel, Hansgeorg, Boldyrev, Alexander I., and Bowen, Kit H. Realization of an Al≡Al Triple Bond in the Gas-Phase Na3Al2- Cluster via Double Electronic Transmutation. United States: N. p., 2018. Web. doi:10.1002/anie.201806917.
Zhang, Xinxing, Popov, Ivan Aleksandrovich, Lundell, Katie A., Wang, Haopeng, Mu, Chaonan, Wang, Wei, Schnöckel, Hansgeorg, Boldyrev, Alexander I., & Bowen, Kit H. Realization of an Al≡Al Triple Bond in the Gas-Phase Na3Al2- Cluster via Double Electronic Transmutation. United States. doi:10.1002/anie.201806917.
Zhang, Xinxing, Popov, Ivan Aleksandrovich, Lundell, Katie A., Wang, Haopeng, Mu, Chaonan, Wang, Wei, Schnöckel, Hansgeorg, Boldyrev, Alexander I., and Bowen, Kit H. Mon . "Realization of an Al≡Al Triple Bond in the Gas-Phase Na3Al2- Cluster via Double Electronic Transmutation". United States. doi:10.1002/anie.201806917. https://www.osti.gov/servlets/purl/1481997.
@article{osti_1481997,
title = {Realization of an Al≡Al Triple Bond in the Gas-Phase Na3Al2- Cluster via Double Electronic Transmutation},
author = {Zhang, Xinxing and Popov, Ivan Aleksandrovich and Lundell, Katie A. and Wang, Haopeng and Mu, Chaonan and Wang, Wei and Schnöckel, Hansgeorg and Boldyrev, Alexander I. and Bowen, Kit H.},
abstractNote = {We report the discovery of homodinuclear multiple bonds composed of Group 13 elements represents one of the most challenging frontiers in modern chemistry. A classical triple bond such as N≡N and HC≡CH contains one σ bond and two π bonds constructed from the p orbitals perpendicular to the σ bond. However, the traditional textbook triple bond between two Al atoms has remained elusive. Here we report an Al≡Al triple bond in the designer Na3Al2- cluster predicted in silico, which was subsequently generated by pulsed arc discharge followed by mass spectrometry and photoelectron spectroscopy characterizations. Being effectively Al2- due to the electron donation from Na, the Al atoms in Na3Al2- undergo a double electronic transmutation into Group 15 elements, thus the Al2-≡Al2- kernel mimics the P≡P and N≡N molecules. Lastly, we anticipate this work will stimulate more endeavors in discovering materials using Al2-≡Al2- as a building block in the gas phase and in the solid state.},
doi = {10.1002/anie.201806917},
journal = {Angewandte Chemie (International Edition)},
number = 43,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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