skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Polar Intermetallics Pr5Co2Ge3 and Pr7Co2Ge4 With Planar Hydrocarbon-Like Metal Clusters

Abstract

Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr5Co2Ge3 and Pr7Co2Ge4, both of which feature such planar metal clusters, viz., ethylene-like [Co2Ge4] clusters plus the concatenated forms and polyacene-like [Co2Ge2]n ribbons in Pr5Co2Ge3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr7Co2Ge4. Just as in the related planar organic structures, these metal-metalloid species are dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr5Co2Ge3 via a series of transitions below 150 K; and Pr7Co2Ge4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr7Co2Ge4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [1];  [1];  [4];  [4]
  1. Ames Lab., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
  3. Ames Lab., Ames, IA (United States); Univ. of California, Davis, CA (United States)
  4. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1368045
Report Number(s):
IS-J-9333
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 44; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polar intermetallic; single crystal; X-ray diffraction; metallorganic cluster; spin-orbit coupling

Citation Formats

Lin, Qisheng, Aguirre, Kaiser, Saunders, Scott M., Hackett, Timothy A., Liu, Yong, Taufour, Valentin, Paudyal, Durga, Budko, Sergey, Canfield, Paul C., and Miller, Gordon J. Polar Intermetallics Pr5Co2Ge3 and Pr7Co2Ge4 With Planar Hydrocarbon-Like Metal Clusters. United States: N. p., 2017. Web. doi:10.1002/chem.201702798.
Lin, Qisheng, Aguirre, Kaiser, Saunders, Scott M., Hackett, Timothy A., Liu, Yong, Taufour, Valentin, Paudyal, Durga, Budko, Sergey, Canfield, Paul C., & Miller, Gordon J. Polar Intermetallics Pr5Co2Ge3 and Pr7Co2Ge4 With Planar Hydrocarbon-Like Metal Clusters. United States. doi:10.1002/chem.201702798.
Lin, Qisheng, Aguirre, Kaiser, Saunders, Scott M., Hackett, Timothy A., Liu, Yong, Taufour, Valentin, Paudyal, Durga, Budko, Sergey, Canfield, Paul C., and Miller, Gordon J. Mon . "Polar Intermetallics Pr5Co2Ge3 and Pr7Co2Ge4 With Planar Hydrocarbon-Like Metal Clusters". United States. doi:10.1002/chem.201702798. https://www.osti.gov/servlets/purl/1368045.
@article{osti_1368045,
title = {Polar Intermetallics Pr5Co2Ge3 and Pr7Co2Ge4 With Planar Hydrocarbon-Like Metal Clusters},
author = {Lin, Qisheng and Aguirre, Kaiser and Saunders, Scott M. and Hackett, Timothy A. and Liu, Yong and Taufour, Valentin and Paudyal, Durga and Budko, Sergey and Canfield, Paul C. and Miller, Gordon J.},
abstractNote = {Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr5Co2Ge3 and Pr7Co2Ge4, both of which feature such planar metal clusters, viz., ethylene-like [Co2Ge4] clusters plus the concatenated forms and polyacene-like [Co2Ge2]n ribbons in Pr5Co2Ge3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr7Co2Ge4. Just as in the related planar organic structures, these metal-metalloid species are dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr5Co2Ge3 via a series of transitions below 150 K; and Pr7Co2Ge4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr7Co2Ge4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.},
doi = {10.1002/chem.201702798},
journal = {Chemistry - A European Journal},
number = 44,
volume = 23,
place = {United States},
year = {2017},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ca3Al2Ge3, eine Zintlphase mit einer AlGe4-Tetraeder-Ger�ststruktur
journal, July 1982

  • Cordier, Gerhard; Sch�fer, Herbert
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 490, Issue 1
  • DOI: 10.1002/zaac.19824900116

Conduction electron polarization in ferromagnetic rare earth crystals
journal, October 1976


All-Metal Aromaticity: Revisiting the Ring Current Model among Transition Metal Clusters
journal, October 2013

  • Badri, Zahra; Pathak, Shubhrodeep; Fliegl, Heike
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct4007184

On the existence and the crystal structure of novel R3TSi3 intermetallic phases (R = rare earth; T = Fe, Co, Ni)
journal, January 2005


Gd 13 Fe 10 C 13 : Indications of Fe–Fe Multiple Bonding Emerging from Chemical Frustration
journal, June 2012

  • Hadler, Amelia B.; Fredrickson, Daniel C.
  • Journal of the American Chemical Society, Vol. 134, Issue 25
  • DOI: 10.1021/ja3034944

Observation of All-Metal Aromatic Molecules
journal, February 2001


Crystal structure of the compound Ce7Pd4Ge2
journal, August 1993


Exo-bonded six-membered heterocycle in the crystal structures of RE 7 Co 2 Ge 4 (RE = La–Nd)
journal, January 2016

  • Ponou, Siméon; Lidin, Sven
  • Dalton Transactions, Vol. 45, Issue 46
  • DOI: 10.1039/C6DT03302D

Metal clusters inside out
journal, March 2010

  • Simon, Arndt
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1915
  • DOI: 10.1098/rsta.2009.0271

Covalently-Controlled Properties by Design in Group IV Graphane Analogues
journal, December 2014

  • Jiang, Shishi; Arguilla, Maxx Q.; Cultrara, Nicholas D.
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar500296e

π-Conjugation in Gd 13 Fe 10 C 13 and Its Oxycarbide: Unexpected Connections between Complex Carbides and Simple Organic Molecules
journal, August 2014

  • Hadler, Amelia B.; Yannello, Vincent J.; Bi, Wenli
  • Journal of the American Chemical Society, Vol. 136, Issue 34
  • DOI: 10.1021/ja505868w

Zintl-Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe
journal, March 2011

  • Scharfe, Sandra; Kraus, Florian; Stegmaier, Saskia
  • Angewandte Chemie, Vol. 123, Issue 16
  • DOI: 10.1002/ange.201001630

Crystallographic data and magnetic properties of new RCoGe (RLa-Nd) compounds from susceptibility measurements and neutron diffraction study
journal, November 1993


Multiple magnetic transitions in R3CoGe2 compounds (R=Ce, Pr and Nd)
journal, March 2004


Multilayer Germanenes Formed in Zintl-Phase CaGe 2 by Fluoride Diffusion
journal, October 2016

  • Yaokawa, Ritsuko; Ohsuna, Tetsu; Hayasaka, Yuichiro
  • ChemistrySelect, Vol. 1, Issue 17
  • DOI: 10.1002/slct.201601489

The temperature dependence of magnetic ordering in the heavy rare earth metals
journal, July 1964


A multicentre-bonded [ZnI]8 cluster with cubic aromaticity
journal, February 2015

  • Cui, Ping; Hu, Han-Shi; Zhao, Bin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7331

A Low-Temperature Solution Phase Route for the Synthesis of Silicon Nanoclusters
journal, January 1996

  • Bley, Richard A.; Kauzlarich, Susan M.
  • Journal of the American Chemical Society, Vol. 118, Issue 49
  • DOI: 10.1021/ja962787s

An All-Metal Aromatic Sandwich Complex [Sb 3 Au 3 Sb 3 ] 3–
journal, August 2015

  • Pan, Fu-Xing; Li, Lei-Jiao; Wang, Ying-Jin
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b07730

Aromaticity in all-metal annular systems: the counter-ion effect
journal, January 2011

  • Chakraborty, Arindam; Giri, Santanab; Duley, Soma
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 33
  • DOI: 10.1039/c1cp21430f

On the nature of chemical bonding in the all-metal aromatic [Sb 3 Au 3 Sb 3 ] 3− sandwich complex
journal, January 2016

  • You, Xue-Rui; Tian, Wen-Juan; Li, Da-Zhi
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 19
  • DOI: 10.1039/C6CP00101G

Superzone boundary effects in the electrical resistivity of dysprosium
journal, May 1965


Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

  • Dronskowski, Richard; Bloechl, Peter E.
  • The Journal of Physical Chemistry, Vol. 97, Issue 33
  • DOI: 10.1021/j100135a014

Polyatomic Zintl anions of the post-transition elements
journal, October 1985


Single-crystal structure validation with the program PLATON
journal, January 2003


La 8 Br 7 Ni 4 : Ribbons of Ni Hexagons in Condensed La 6 Trigonal Prisms
journal, November 2008

  • Zheng, Chong; Mattausch, Hansjürgen; Hoch, Constantin
  • Inorganic Chemistry, Vol. 47, Issue 22
  • DOI: 10.1021/ic801227e

Aromatic Mercury Clusters in Ancient Amalgams
journal, September 2001


[ZnBi 4 ] 3– Pentagon in K 6 ZnBi 5 : Aromatic All-Metal Heterocycle
journal, January 2014

  • Qin, Qian; Zhou, Liujiang; Wang, Yi
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic4029113

Comparison of Density Functional and MP2 Calculations on the Water Monomer and Dimer
journal, October 1994

  • Kim, K.; Jordan, K. D.
  • The Journal of Physical Chemistry, Vol. 98, Issue 40
  • DOI: 10.1021/j100091a024

Neue Sr-Verbindungen mit planaren Al-Si/Ge-Anionen und eine Korrektur zu SrSi-II und SrGe0.76
journal, January 2008

  • Eisenmann, Brigitte; Rhode, Michael; Wendorff, Marco
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 634, Issue 1
  • DOI: 10.1002/zaac.200700347

All-Metal Aromaticity and Antiaromaticity
journal, October 2005

  • Boldyrev, Alexander I.; Wang, Lai-Sheng
  • Chemical Reviews, Vol. 105, Issue 10
  • DOI: 10.1021/cr030091t

Kondensierte Al6-Ringe in den Subiodiden La3Al2I2 und La2Al2I
journal, July 2001


Direct Space Decomposition of ELI-D: Interplay of Charge Density and Pair-Volume Function for Different Bonding Situations
journal, October 2008

  • Wagner, Frank R.; Kohout, Miroslav; Grin, Yuri
  • The Journal of Physical Chemistry A, Vol. 112, Issue 40
  • DOI: 10.1021/jp8022315

Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties
journal, September 2015


Zintl Ions, Cage Compounds, and Intermetalloid Clusters of Group 14 and Group 15 Elements
journal, March 2011

  • Scharfe, Sandra; Kraus, Florian; Stegmaier, Saskia
  • Angewandte Chemie International Edition, Vol. 50, Issue 16
  • DOI: 10.1002/anie.201001630

Ca 3 AI 2 SI 2 : An Inorganic Structure Analogous to but not Isoelectronic with Polyacene
journal, February 1988

  • Li, Jing; Hoffman, Roald
  • The Journal of Physical Chemistry, Vol. 92, Issue 4
  • DOI: 10.1021/j100315a600

Crystal and magnetic structures of PrCo2Ge2 and HoCo2Ge2
journal, March 1980

  • Szytula, A.; Leciejewicz, J.; Bińczycka, H.
  • Physica Status Solidi (a), Vol. 58, Issue 1
  • DOI: 10.1002/pssa.2210580107

Homoatomic Bonding of Main Group Elements
journal, January 1981

  • von Schnering, Hans Georg
  • Angewandte Chemie International Edition in English, Vol. 20, Issue 1
  • DOI: 10.1002/anie.198100331

Rationalization of the π−σ (Anti)aromaticity in All Metal Molecular Clusters
journal, September 2005

  • Datta, Ayan; Pati, Swapan K.
  • Journal of Chemical Theory and Computation, Vol. 1, Issue 5
  • DOI: 10.1021/ct0501351

A Stochastic Search for the Structures of Small Germanium Clusters and Their Anions: Enhanced Stability by Spherical Aromaticity of the Ge 10 and Ge 12 2− Systems
journal, March 2011

  • Tai, Truong Ba; Nguyen, Minh Tho
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 4
  • DOI: 10.1021/ct1006482

Aromatic Mercury Clusters in Ancient Amalgams
journal, September 2001


Darstellung und Kristallstruktur von Ca3Al2Ge2, Sr3Al2Ge2 und Ba3Al2Ge2 / Preparation and Crystal Structure of Ca3Al2Ge2, Sr3Al2Ge2 and Ba3Αl2Ge2
journal, December 1976

  • Widera, Axel; Eisenmann, Brigitte; Schäfer, Herbert
  • Zeitschrift für Naturforschung B, Vol. 31, Issue 12
  • DOI: 10.1515/znb-1976-1207