Spherical trihedral metallo-borospherenes

Chen, Teng-Teng; Li, Wan-Lu; Chen, Wei-Jia; Yu, Xiao-Hu; Dong, Xin-Ran; Li, Jun; Wang, Lai-Sheng

doi:10.1038/s41467-020-16532-x

Title: Spherical trihedral metallo-borospherenes

Journal Article · Tue Jun 02 00:00:00 EDT 2020 · Nature Communications

DOI:https://doi.org/10.1038/s41467-020-16532-x· OSTI ID:1695731

^[1]; Li, Wan-Lu ^[2]; Chen, Wei-Jia ^[1];

^[3]; Dong, Xin-Ran ^[4];

^[5];

^[1]

Brown Univ., Providence, RI (United States)
Tsinghua Univ., Beijing (China)
Shaanxi Univ. of Technology, Hanzhong (China)
Southern Univ. of Science and Technology, Shenzhen (China)
Tsinghua Univ., Beijing (China); Southern Univ. of Science and Technology, Shenzhen (China)

The discovery of borospherenes unveiled the capacity of boron to form fullerene-like cage structures. While fullerenes are known to entrap metal atoms to form endohedral metallofullerenes, few metal atoms have been observed to be part of the fullerene cages. Here we report the observation of a class of remarkable metallo-borospherenes, where metal atoms are integral parts of the cage surface. We have produced La₃B₁₈^- and Tb₃B₁₈^- and probed their structures and bonding using photoelectron spectroscopy and theoretical calculations. Global minimum searches revealed that the most stable structures of Ln₃B₁₈^- are hollow cages with D_3h symmetry. The B₁₈-framework in the Ln₃B₁₈^- cages can be viewed as consisting of two triangular B6 motifs connected by three B₂ units, forming three shared B₁₀ rings which are coordinated to the three Ln atoms on the cage surface. These metallo-borospherenes represent a new class of unusual geometry that has not been observed in chemistry heretofore.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1695731

Journal Information:: Nature Communications, Vol. 11, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Ab initio prediction of stable boron sheets and boron nanotubes: Structure, stability, and electronic properties Yang, Xiaobao; Ding, Yi; Ni, Jun Physical Review B, Vol. 77, Issue 4 https://doi.org/10.1103/PhysRevB.77.041402	journal	January 2008
Probing the structures and bonding of size-selected boron and doped-boron clusters Jian, Tian; Chen, Xuenian; Li, Si-Dian Chemical Society Reviews, Vol. 48, Issue 13 https://doi.org/10.1039/C9CS00233B	journal	January 2019
Boron: Elementary Challenge for Experimenters and Theoreticians Albert, Barbara; Hillebrecht, Harald Angewandte Chemie International Edition, Vol. 48, Issue 46 https://doi.org/10.1002/anie.200903246	journal	November 2009
Proposed Boron Nanotubes ^† Gindulytė, Asta; Lipscomb, William N.; Massa, Lou Inorganic Chemistry, Vol. 37, Issue 25 https://doi.org/10.1021/ic980559o	journal	December 1998
Bond Multiplicity in Transition-Metal Complexes: Applications of Two-Electron Valence Indices Michalak, Artur; DeKock, Roger L.; Ziegler, Tom The Journal of Physical Chemistry A, Vol. 112, Issue 31 https://doi.org/10.1021/jp800139g	journal	August 2008
A combination of quasirelativistic pseudopotential and ligand field calculations for lanthanoid compounds Dolg, M.; Stoll, H.; Preuss, H. Theoretica Chimica Acta, Vol. 85, Issue 6 https://doi.org/10.1007/BF01112983	journal	June 1993
Experimental realization of two-dimensional boron sheets Feng, Baojie; Zhang, Jin; Zhong, Qing Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2491	journal	March 2016
”Developing paradigms of chemical bonding: adaptive natural density partitioning Zubarev, Dmitry Yu.; Boldyrev, Alexander I. Physical Chemistry Chemical Physics, Vol. 10, Issue 34 https://doi.org/10.1039/b804083d	journal	January 2008
Bond orders and valences from ab initio wave functions Mayer, I. International Journal of Quantum Chemistry, Vol. 29, Issue 3 https://doi.org/10.1002/qua.560290320	journal	March 1986
New boron based nanostructured materials Boustani, Ihsan; Quandt, Alexander; Hernández, Eduardo The Journal of Chemical Physics, Vol. 110, Issue 6 https://doi.org/10.1063/1.477976	journal	February 1999
Observation of an all-boron fullerene Zhai, Hua-Jin; Zhao, Ya-Fan; Li, Wei-Li Nature Chemistry, Vol. 6, Issue 8 https://doi.org/10.1038/nchem.1999	journal	July 2014
Cage substitution in metal–fullerene clusters Branz, W.; Billas, I. M. L.; Malinowski, N. The Journal of Chemical Physics, Vol. 109, Issue 9 https://doi.org/10.1063/1.477410	journal	September 1998
Physical and chemical evidence for metallofullerenes with metal atoms as part of the cage Clemmer, David E.; Hunter, Joanna M.; Shelimov, Konstantin B. Nature, Vol. 372, Issue 6503 https://doi.org/10.1038/372248a0	journal	November 1994
Ionic high-pressure form of elemental boron Oganov, Artem R.; Chen, Jiuhua; Gatti, Carlo Nature, Vol. 457, Issue 7231 https://doi.org/10.1038/nature07736	journal	January 2009
Crystal Structure of Novel Ni–Zn Borides: First Observation of a Boron–Metal Nested Cage Unit: B ₂₀ Ni ₆ Malik, Zahida P.; Sologub, Oksana; Grytsiv, Andriy Inorganic Chemistry, Vol. 50, Issue 16 https://doi.org/10.1021/ic2007167	journal	August 2011
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi Computer Physics Communications, Vol. 167, Issue 2 https://doi.org/10.1016/j.cpc.2004.12.014	journal	April 2005
Photoelectron spectroscopy of size-selected boron clusters: from planar structures to borophenes and borospherenes Wang, Lai-Sheng International Reviews in Physical Chemistry, Vol. 35, Issue 1 https://doi.org/10.1080/0144235X.2016.1147816	journal	January 2016
Experimental and Theoretical Evidence of an Axially Chiral Borospherene Chen, Qiang; Li, Wei-Li; Zhao, Ya-Fan ACS Nano, Vol. 9, Issue 1 https://doi.org/10.1021/nn506262c	journal	December 2014
Aromatic Metal-Centered Monocyclic Boron Rings: Co©B8− and Ru©B9− Romanescu, Constantin; Galeev, Timur R.; Li, Wei-Li Angewandte Chemie International Edition, Vol. 50, Issue 40 https://doi.org/10.1002/anie.201104166	journal	August 2011
Nucleus-Independent Chemical Shifts: A Simple and Efficient Aromaticity Probe Schleyer, Paul von Ragué; Maerker, Christoph; Dransfeld, Alk Journal of the American Chemical Society, Vol. 118, Issue 26 https://doi.org/10.1021/ja960582d	journal	January 1996
A diuranium carbide cluster stabilized inside a C80 fullerene cage Zhang, Xingxing; Li, Wanlu; Feng, Lai Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05210-8	journal	July 2018
Ti ₈ C ₁₂ : Barrierless Transformation of the T _h Isomer to the T _d Isomer Dance, Ian Journal of the American Chemical Society, Vol. 118, Issue 26 https://doi.org/10.1021/ja9608196	journal	January 1996
Heterofullerenes Vostrowsky, Otto; Hirsch, Andreas Chemical Reviews, Vol. 106, Issue 12 https://doi.org/10.1021/cr050561e	journal	December 2006
Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets Piazza, Zachary A.; Hu, Han-Shi; Li, Wei-Li Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4113	journal	January 2014
Valency. I. A quantum chemical definition and properties Gopinathan, M. S.; Jug, Karl Theoretica Chimica Acta, Vol. 63, Issue 6 https://doi.org/10.1007/BF02394809	journal	September 1983
La ₃ B ₁₄ ⁻ : an inverse triple-decker lanthanide boron cluster Chen, Teng-Teng; Li, Wan-Lu; Chen, Wei-Jia Chemical Communications, Vol. 55, Issue 54 https://doi.org/10.1039/C9CC03807H	journal	January 2019
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Hydrocarbon analogues of boron clusters — planarity, aromaticity and antiaromaticity Zhai, Hua-Jin; Kiran, Boggavarapu; Li, Jun Nature Materials, Vol. 2, Issue 12 https://doi.org/10.1038/nmat1012	journal	November 2003
From planar boron clusters to borophenes and metalloborophenes Li, Wan-Lu; Chen, Xin; Jian, Tian Nature Reviews Chemistry, Vol. 1, Issue 10 https://doi.org/10.1038/s41570-017-0071	journal	September 2017
Molecular calculations of excitation energies and (hyper)polarizabilities with a statistical average of orbital model exchange-correlation potentials Schipper, P. R. T.; Gritsenko, O. V.; van Gisbergen, S. J. A. The Journal of Chemical Physics, Vol. 112, Issue 3 https://doi.org/10.1063/1.480688	journal	January 2000
Au20: A Tetrahedral Cluster Li, J. Science, Vol. 299, Issue 5608 https://doi.org/10.1126/science.1079879	journal	February 2003
Borophene as a prototype for synthetic 2D materials development Mannix, Andrew J.; Zhang, Zhuhua; Guisinger, Nathan P. Nature Nanotechnology, Vol. 13, Issue 6 https://doi.org/10.1038/s41565-018-0157-4	journal	June 2018
A Combined Charge and Energy Decomposition Scheme for Bond Analysis Mitoraj, Mariusz P.; Michalak, Artur; Ziegler, Tom Journal of Chemical Theory and Computation, Vol. 5, Issue 4 https://doi.org/10.1021/ct800503d	journal	March 2009
Unexpected Synergy between Magnetic Iron Chains and Stacked B ₆ Rings in Nb ₆ Fe _{1− x} Ir _{6+ x} B ₈ Mbarki, Mohammed; St. Touzani, Rachid; Fokwa, Boniface P. T. Angewandte Chemie International Edition, Vol. 53, Issue 48 https://doi.org/10.1002/anie.201406397	journal	August 2014
Transition-Metal-Centered Monocyclic Boron Wheel Clusters (M©B _n ): A New Class of Aromatic Borometallic Compounds Romanescu, Constantin; Galeev, Timur R.; Li, Wei-Li Accounts of Chemical Research, Vol. 46, Issue 2 https://doi.org/10.1021/ar300149a	journal	December 2012
Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters? Guo, B. C.; Kerns, K. P.; Castleman, A. W. Science, Vol. 255, Issue 5050 https://doi.org/10.1126/science.255.5050.1411	journal	March 1992
Boron: Enabling Exciting Metal-Rich Structures and Magnetic Properties Scheifers, Jan P.; Zhang, Yuemei; Fokwa, Boniface P. T. Accounts of Chemical Research, Vol. 50, Issue 9 https://doi.org/10.1021/acs.accounts.7b00268	journal	August 2017
All-boron aromatic clusters as potential new inorganic ligands and building blocks in chemistry Alexandrova, Anastassia N.; Boldyrev, Alexander I.; Zhai, Hua-Jin Coordination Chemistry Reviews, Vol. 250, Issue 21-22 https://doi.org/10.1016/j.ccr.2006.03.032	journal	November 2006
Efficient and accurate approximations to the local coupled cluster singles doubles method using a truncated pair natural orbital basis Neese, Frank; Hansen, Andreas; Liakos, Dimitrios G. The Journal of Chemical Physics, Vol. 131, Issue 6 https://doi.org/10.1063/1.3173827	journal	January 2009
Novel Precursors for Boron Nanotubes: The Competition of Two-Center and Three-Center Bonding in Boron Sheets Tang, Hui; Ismail-Beigi, Sohrab Physical Review Letters, Vol. 99, Issue 11 https://doi.org/10.1103/PhysRevLett.99.115501	journal	September 2007
[La(η ^x -B _x )La] ⁻ ( x = 7–9): a new class of inverse sandwich complexes Chen, Teng-Teng; Li, Wan-Lu; Li, Jun Chemical Science, Vol. 10, Issue 8 https://doi.org/10.1039/C8SC05443F	journal	January 2019
Current status and future developments of endohedral metallofullerenes Lu, Xing; Feng, Lai; Akasaka, Takeshi Chemical Society Reviews, Vol. 41, Issue 23 https://doi.org/10.1039/c2cs35214a	journal	January 2012
The Planar CoB ₁₈ ⁻ Cluster as a Motif for Metallo-Borophenes Li, Wan-Lu; Jian, Tian; Chen, Xin Angewandte Chemie International Edition, Vol. 55, Issue 26 https://doi.org/10.1002/anie.201601548	journal	April 2016
Structural-Distortion-Driven Magnetic Transformation from Ferro- to Ferrimagnetic Iron Chains in B ₆ -based Nb ₆ FeIr ₆ B ₈ Sharma, Neetika; Mbarki, Mohammed; Zhang, Yuemei Angewandte Chemie International Edition, Vol. 57, Issue 32 https://doi.org/10.1002/anie.201804841	journal	July 2018
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
A multicentre-bonded [ZnI]8 cluster with cubic aromaticity Cui, Ping; Hu, Han-Shi; Zhao, Bin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7331	journal	February 2015
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
Cobalt-centred boron molecular drums with the highest coordination number in the CoB16− cluster Popov, Ivan A.; Jian, Tian; Lopez, Gary V. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9654	journal	October 2015
Planar B ₄₁ ⁻ and B ₄₂ ⁻ clusters with double-hexagonal vacancies Bai, Hui; Chen, Teng-Teng; Chen, Qiang Nanoscale, Vol. 11, Issue 48 https://doi.org/10.1039/C9NR09522E	journal	January 2019
Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs Mannix, A. J.; Zhou, X. -F.; Kiraly, B. Science, Vol. 350, Issue 6267 https://doi.org/10.1126/science.aad1080	journal	December 2015
Observation of highly stable and symmetric lanthanide octa-boron inverse sandwich complexes Li, Wan-Lu; Chen, Teng-Teng; Xing, Deng-Hui Proceedings of the National Academy of Sciences, Vol. 115, Issue 30 https://doi.org/10.1073/pnas.1806476115	journal	July 2018
All-boron analogues of aromatic hydrocarbons: B ₁₇ ⁻ and B ₁₈ ⁻ Sergeeva, Alina P.; Averkiev, Boris B.; Zhai, Hua-Jin The Journal of Chemical Physics, Vol. 134, Issue 22 https://doi.org/10.1063/1.3599452	journal	June 2011
TGMin: A global-minimum structure search program based on a constrained basin-hopping algorithm Zhao, Yafan; Chen, Xin; Li, Jun Nano Research, Vol. 10, Issue 10 https://doi.org/10.1007/s12274-017-1553-z	journal	July 2017
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
The Boranes and Their Relatives Lipscomb, W. N. Science, Vol. 196, Issue 4294 https://doi.org/10.1126/science.196.4294.1047	journal	June 1977
Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A. Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400310g	journal	February 2014
QUICKSTEP: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, J.; Krack, M.; Mohamed, F. Elsevier https://doi.org/10.5167/uzh-3175	text	January 2005

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