DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Microwave assisted synthesis of heterometallic 3d–4f M4 Ln complexes

Abstract

Here, we describe the synthesis and magnetic properties of a series of 3d–4f complexes of general formula [M4Ln(OH)2(chp)4(SALOH)5(H2O)(MeCN)(Solv)] (Solv = MeOH, MeCN, H2O; chp stands for deprotonated 6-chloro-2-hydroxypyridine (C5H3ClNO), SALOH stands for monodeprotonated 3,5-ditert-butylsalicylic acid (C15H21O3)) obtained by a solvent-free microwave assisted synthesis method. The Ni(II) complexes (Ni4Gd, Solv = MeOH; Ni4Dy, Solv = MeCN) are not SMMs in the absence of an applied dc field. The replacement of Ni(II) by Co(II) (Co4La, Solv = MeOH; Co4Gd, Solv = H2O; Co4Gd-MeCN, Solv = MeCN; Co4Tb, Solv = MeOH; Co4Dy, Solv = H2O) results in improved SMM properties.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. de Barcelona (Spain)
  2. Indian Inst. of Technology Bombay, Mumbai (India)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Spanish Government
OSTI Identifier:
1581606
Grant/Contract Number:  
AC02-05CH11231; CTQ2015-68370-P
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 33; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rosado Piquer, L., Dey, S., Castilla-Amorós, L., Teat, S. J., Cirera, J., Rajaraman, G., and Sañudo, E. C. Microwave assisted synthesis of heterometallic 3d–4f M4 Ln complexes. United States: N. p., 2019. Web. doi:10.1039/c9dt02567g.
Rosado Piquer, L., Dey, S., Castilla-Amorós, L., Teat, S. J., Cirera, J., Rajaraman, G., & Sañudo, E. C. Microwave assisted synthesis of heterometallic 3d–4f M4 Ln complexes. United States. https://doi.org/10.1039/c9dt02567g
Rosado Piquer, L., Dey, S., Castilla-Amorós, L., Teat, S. J., Cirera, J., Rajaraman, G., and Sañudo, E. C. Fri . "Microwave assisted synthesis of heterometallic 3d–4f M4 Ln complexes". United States. https://doi.org/10.1039/c9dt02567g. https://www.osti.gov/servlets/purl/1581606.
@article{osti_1581606,
title = {Microwave assisted synthesis of heterometallic 3d–4f M4 Ln complexes},
author = {Rosado Piquer, L. and Dey, S. and Castilla-Amorós, L. and Teat, S. J. and Cirera, J. and Rajaraman, G. and Sañudo, E. C.},
abstractNote = {Here, we describe the synthesis and magnetic properties of a series of 3d–4f complexes of general formula [M4Ln(OH)2(chp)4(SALOH)5(H2O)(MeCN)(Solv)] (Solv = MeOH, MeCN, H2O; chp stands for deprotonated 6-chloro-2-hydroxypyridine (C5H3ClNO), SALOH stands for monodeprotonated 3,5-ditert-butylsalicylic acid (C15H21O3)) obtained by a solvent-free microwave assisted synthesis method. The Ni(II) complexes (Ni4Gd, Solv = MeOH; Ni4Dy, Solv = MeCN) are not SMMs in the absence of an applied dc field. The replacement of Ni(II) by Co(II) (Co4La, Solv = MeOH; Co4Gd, Solv = H2O; Co4Gd-MeCN, Solv = MeCN; Co4Tb, Solv = MeOH; Co4Dy, Solv = H2O) results in improved SMM properties.},
doi = {10.1039/c9dt02567g},
journal = {Dalton Transactions},
number = 33,
volume = 48,
place = {United States},
year = {Fri Jul 19 00:00:00 EDT 2019},
month = {Fri Jul 19 00:00:00 EDT 2019}
}

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

Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Synthesis scheme showing methods a, b and c and their products. * reported in reference 44.

Save / Share:

Works referenced in this record:

Serendipitous assembly of polynuclear cage compounds
journal, December 2001

  • Winpenny, Richard E. P.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/b107118c

Heterometallic 3d–4f single-molecule magnets
journal, January 2015

  • Rosado Piquer, Lidia; Sañudo, E. Carolina
  • Dalton Transactions, Vol. 44, Issue 19
  • DOI: 10.1039/C5DT00549C

Al, Ga and In heterometallic wheels and their by-products
journal, January 2007

  • Sañudo, E. Carolina; Muryn, Christopher A.; Helliwell, Madeleine A.
  • Chem. Commun., Issue 8
  • DOI: 10.1039/B613877B

Self-Assembled Monolayer of Cr 7 Ni Molecular Nanomagnets by Sublimation
journal, August 2011

  • Ghirri, Alberto; Corradini, Valdis; Bellini, Valerio
  • ACS Nano, Vol. 5, Issue 9
  • DOI: 10.1021/nn201800e

Verdazyl Radical, a Building Block for a Six-Spin-Center 2p–3d–4f Single-Molecule Magnet
journal, November 2016


Solid state synthesis of [V5O2(Me3CCO2)9Cl2]
journal, January 2007

  • Sañudo, E. Carolina; Ribas, Joan; Winpenny, Richard E. P.
  • New Journal of Chemistry, Vol. 31, Issue 8
  • DOI: 10.1039/b704191h

PHI: A powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d - and f -block complexes
journal, February 2013

  • Chilton, Nicholas F.; Anderson, Russell P.; Turner, Lincoln D.
  • Journal of Computational Chemistry, Vol. 34, Issue 13
  • DOI: 10.1002/jcc.23234

Synthesis, Structure, and Magnetic Properties of a Mn 21 Single-Molecule Magnet
journal, July 2004

  • Sañudo, E. Carolina; Wernsdorfer, Wolfgang; Abboud, Khalil A.
  • Inorganic Chemistry, Vol. 43, Issue 14
  • DOI: 10.1021/ic0353864

Microwave assisted synthesis of polynuclear Ni(II) complexes
journal, September 2019


A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
journal, July 2017

  • Guo, Fu-Sheng; Day, Benjamin M.; Chen, Yan-Cong
  • Angewandte Chemie International Edition, Vol. 56, Issue 38
  • DOI: 10.1002/anie.201705426

Empirical parameters for calculating cation–oxygen bond valences
journal, July 1976

  • Brown, I. D.; Wu, K. K.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 32, Issue 7
  • DOI: 10.1107/S0567740876006869

Strategies towards single molecule magnets based on lanthanide ions
journal, October 2009


Lanthanides in molecular magnetism: old tools in a new field
journal, January 2011

  • Sorace, Lorenzo; Benelli, Cristiano; Gatteschi, Dante
  • Chemical Society Reviews, Vol. 40, Issue 6
  • DOI: 10.1039/c0cs00185f

Magnetic bistability in a metal-ion cluster
journal, September 1993

  • Sessoli, R.; Gatteschi, D.; Caneschi, A.
  • Nature, Vol. 365, Issue 6442
  • DOI: 10.1038/365141a0

New Nanostructured Materials: Synthesis of Dodecanuclear Ni II Complexes and Surface Deposition Studies
journal, May 2013

  • Pons-Balagué, Alba; Piligkos, Stergios; Teat, Simon J.
  • Chemistry - A European Journal, Vol. 19, Issue 27
  • DOI: 10.1002/chem.201204081

Molecular magnetic hysteresis at 60 kelvin in dysprosocenium
journal, August 2017

  • Goodwin, Conrad A. P.; Ortu, Fabrizio; Reta, Daniel
  • Nature, Vol. 548, Issue 7668
  • DOI: 10.1038/nature23447

Toward Rapid, “Green”, Predictable Microwave-Assisted Synthesis
journal, August 2005

  • Roberts, Brett A.; Strauss, Christopher R.
  • Accounts of Chemical Research, Vol. 38, Issue 8
  • DOI: 10.1021/ar040278m

High-spin molecules: [Mn12O12(O2CR)16(H2O)4]
journal, March 1993

  • Sessoli, Roberta; Tsai, Hui Lien; Schake, Ann R.
  • Journal of the American Chemical Society, Vol. 115, Issue 5
  • DOI: 10.1021/ja00058a027

Microwave-Enhanced Reaction Rates for Nanoparticle Synthesis
journal, November 2005

  • Gerbec, Jeffrey A.; Magana, Donny; Washington, Aaron
  • Journal of the American Chemical Society, Vol. 127, Issue 45
  • DOI: 10.1021/ja052463g

Single-molecule magnetism in cyclopentadienyl-dysprosium chlorides
journal, January 2012

  • Sulway, Scott A.; Layfield, Richard A.; Tuna, Floriana
  • Chem. Commun., Vol. 48, Issue 10
  • DOI: 10.1039/C1CC14643B

Spin-enhanced magnetocaloric effect in molecular nanomagnets
journal, August 2005

  • Evangelisti, Marco; Candini, Andrea; Ghirri, Alberto
  • Applied Physics Letters, Vol. 87, Issue 7
  • DOI: 10.1063/1.2010604

Microwave assisted synthesis and magnetic properties of octanuclear and enneanuclear Ni(ii) complexes: an unprecedented coordination mode for the NO2− ligand
journal, January 2011

  • Pons-Balagué, Alba; Ioanidis, Nicoleta; Wernsdorfer, Wolfgang
  • Dalton Transactions, Vol. 40, Issue 44
  • DOI: 10.1039/c1dt10993f

Mononuclear Single-Molecule Magnets: Tailoring the Magnetic Anisotropy of First-Row Transition-Metal Complexes
journal, April 2013

  • Gomez-Coca, Silvia; Cremades, Eduard; Aliaga-Alcalde, Núria
  • Journal of the American Chemical Society, Vol. 135, Issue 18
  • DOI: 10.1021/ja4015138

Microwave-Assisted Synthesis of Metal–Organic Frameworks
journal, January 2011

  • Klinowski, Jacek; Almeida Paz, Filipe A.; Silva, Patrícia
  • Dalton Trans., Vol. 40, Issue 2
  • DOI: 10.1039/C0DT00708K

Single molecule magnets: a new class of magnetic materials
journal, April 2001


Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet
journal, October 2018


Clusters from Vertex- and Face-Sharing Adamantane-Like Units: A New Topology for Multinuclear Complexes
journal, October 1997

  • Brechin, Euan K.; Harris, Steven G.; Parsons, Simon
  • Angewandte Chemie International Edition in English, Vol. 36, Issue 18
  • DOI: 10.1002/anie.199719671

A family of heterometallic wheels containing potentially fourteen hundred siblings
journal, January 2005

  • Laye, Rebecca H.; Larsen, Finn K.; Overgaard, Jacob
  • Chem. Commun., Issue 9
  • DOI: 10.1039/B416770H

Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

  • Brown, I. D.; Altermatt, D.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4
  • DOI: 10.1107/S0108768185002063

Field Supported Slow Magnetic Relaxation in a Mononuclear Cu(II) Complex
journal, January 2017


Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level
journal, July 2003

  • Ishikawa, Naoto; Sugita, Miki; Ishikawa, Tadahiko
  • Journal of the American Chemical Society, Vol. 125, Issue 29
  • DOI: 10.1021/ja029629n

From Serendipitous Assembly to Controlled Synthesis of 3d–4f Single-Molecule Magnets
journal, May 2014

  • Ledezma-Gairaud, M.; Grangel, L.; Aromí, G.
  • Inorganic Chemistry, Vol. 53, Issue 12
  • DOI: 10.1021/ic500418e

Polynuclear vanadium complexes from thermal decomposition of [V 3 O(O 2 CPh) 6 (H 2 O) 3 ]Cl
journal, January 2006

  • Sañudo, E. Carolina; Smith, Andrew A.; Mason, Pamela V.
  • Dalton Trans., Issue 16
  • DOI: 10.1039/B510105K

Magnetostructural D Correlations in Hexacoordinated Cobalt(II) Complexes
journal, November 2011

  • Titiš, Ján; Boča, Roman
  • Inorganic Chemistry, Vol. 50, Issue 22
  • DOI: 10.1021/ic202108j

Single-Molecule Magnets: Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator (Adv. Mater. 26/2016)
journal, July 2016

  • Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita
  • Advanced Materials, Vol. 28, Issue 26
  • DOI: 10.1002/adma.201670180

A Ferromagnetically Coupled Mn19 Aggregate with a RecordS=83/2 Ground Spin State
journal, July 2006

  • Ako, Ayuk M.; Hewitt, Ian J.; Mereacre, Valeriu
  • Angewandte Chemie International Edition, Vol. 45, Issue 30
  • DOI: 10.1002/anie.200601467

Hybrid molecular-inorganic materials: a heterometallic [Ni 4 Tb] complex grafted on superparamagnetic iron oxide nanoparticles
journal, January 2017

  • Rosado Piquer, L.; Jiménez Romero, E.; Lan, Y.
  • Inorganic Chemistry Frontiers, Vol. 4, Issue 4
  • DOI: 10.1039/C6QI00468G

Quantum computing in molecular magnets
journal, April 2001

  • Leuenberger, Michael N.; Loss, Daniel
  • Nature, Vol. 410, Issue 6830
  • DOI: 10.1038/35071024

Single-Molecule Magnets
journal, November 2000

  • Christou, George; Gatteschi, Dante; Hendrickson, David N.
  • MRS Bulletin, Vol. 25, Issue 11
  • DOI: 10.1557/mrs2000.226

Weak Dy III –Dy III Interactions in Dy III –Phthalocyaninato Multiple-Decker Single-Molecule Magnets Effectively Suppress Magnetic Relaxation
journal, November 2016


Magnetic Anisotropy of Cr7Ni Spin Clusters on Surfaces
journal, May 2012

  • Corradini, Valdis; Ghirri, Alberto; Garlatti, Elena
  • Advanced Functional Materials, Vol. 22, Issue 17
  • DOI: 10.1002/adfm.201200478

Microwave assisted synthesis: A Mn/Ni reaction system affording Mn5Ni4, Mn2Ni2 and Mn7 complexes
journal, November 2013


Quantum Tunneling of Magnetization in Lanthanide Single-Molecule Magnets: Bis(phthalocyaninato)terbium and Bis(phthalocyaninato)dysprosium Anions
journal, May 2005

  • Ishikawa, Naoto; Sugita, Miki; Wernsdorfer, Wolfgang
  • Angewandte Chemie International Edition, Vol. 44, Issue 19
  • DOI: 10.1002/anie.200462638

Microwave-Assisted Synthesis of a Hexanuclear Mn III Single-Molecule Magnet
journal, July 2006

  • Milios, Constantinos J.; Vinslava, Alina; Whittaker, A. Gavin
  • Inorganic Chemistry, Vol. 45, Issue 14
  • DOI: 10.1021/ic0606678

New polynuclear nickel complexes with a variety of pyridonate and carboxylate ligands
journal, January 1995

  • Blake, Alexander J.; Brechin, Euan K.; Codron, Arnaud
  • Journal of the Chemical Society, Chemical Communications, Issue 19
  • DOI: 10.1039/c39950001983

What Controls the Magnetic Exchange and Anisotropy in a Family of Tetranuclear {Mn 2 II Mn 2 III } Single-Molecule Magnets?
journal, February 2017


Microwave assisted synthesis in coordination chemistry
journal, March 2013


Molecular vs. inorganic spintronics: the role of molecular materials and single molecules
journal, January 2009

  • Camarero, Julio; Coronado, Eugenio
  • Journal of Materials Chemistry, Vol. 19, Issue 12
  • DOI: 10.1039/b819594n

Molecular spintronics using single-molecule magnets
journal, March 2008

  • Bogani, Lapo; Wernsdorfer, Wolfgang
  • Nature Materials, Vol. 7, Issue 3
  • DOI: 10.1038/nmat2133

Giant Single-Molecule Magnets: A{Mn84} Torus and Its Supramolecular Nanotubes
journal, April 2004

  • Tasiopoulos, Anastasios J.; Vinslava, Alina; Wernsdorfer, Wolfgang
  • Angewandte Chemie International Edition, Vol. 43, Issue 16
  • DOI: 10.1002/anie.200353352

Facile and Efficient Guanylation of Amines Using Thioureas and Mukaiyama's Reagent
journal, March 1997

  • Yong, Yaw Fui; Kowalski, Jennifer A.; Lipton, Mark A.
  • The Journal of Organic Chemistry, Vol. 62, Issue 5
  • DOI: 10.1021/jo962196k

Synthesis, structure and properties of {M 4 O 4 } cubanes containing nickel( ii ) and cobalt( ii )
journal, January 2007

  • Isele, Katharina; Gigon, Fabienne; Williams, Alan F.
  • Dalton Trans., Issue 3
  • DOI: 10.1039/B614424A

Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen
journal, September 2015

  • Gagné, Olivier Charles; Hawthorne, Frank Christopher
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 71, Issue 5
  • DOI: 10.1107/S2052520615016297

The Drosophila of single-molecule magnetism: [Mn12O12(O2CR)16(H2O)4]
journal, January 2009

  • Bagai, Rashmi; Christou, George
  • Chemical Society Reviews, Vol. 38, Issue 4
  • DOI: 10.1039/b811963e

Quantum Tunneling of Magnetization in a New [Mn 18 ] 2+ Single-Molecule Magnet with S = 13
journal, August 2002

  • Brechin, Euan K.; Boskovic, Colette; Wernsdorfer, Wolfgang
  • Journal of the American Chemical Society, Vol. 124, Issue 33
  • DOI: 10.1021/ja026407g

A ring cycle: studies of heterometallic wheels
journal, January 2007

  • Affronte, Marco; Carretta, Stefano; Timco, Grigore A.
  • Chemical Communications, Issue 18
  • DOI: 10.1039/b615543j

Microwave processing: fundamentals and applications
journal, September 1999


Synthesis, structures and magnetic properties of linear {CoII2LnIII2} coordination clusters
journal, January 2018

  • Chen, Sihuai; Mereacre, Valeriu; Zhao, Zhiying
  • New Journal of Chemistry, Vol. 42, Issue 2
  • DOI: 10.1039/C7NJ04022A

Origin of slow magnetic relaxation in Kramers ions with non-uniaxial anisotropy
journal, July 2014

  • Gómez-Coca, Silvia; Urtizberea, Ainhoa; Cremades, Eduard
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5300

Field influence on the slow magnetic relaxation of nickel-based single ion magnets
journal, January 2018

  • Titiš, Ján; Rajnák, Cyril; Valigura, Dušan
  • Dalton Transactions, Vol. 47, Issue 24
  • DOI: 10.1039/C8DT01445K

Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands
journal, July 2015

  • Pugh, Thomas; Tuna, Floriana; Ungur, Liviu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8492

Discrete {Gd III 4 M} (M = Gd III or Co II ) pentanuclear complexes: a new class of metal-organophosphate molecular coolers
journal, January 2015

  • Gupta, Sandeep K.; Dar, Aijaz A.; Rajeshkumar, Thayalan
  • Dalton Transactions, Vol. 44, Issue 13
  • DOI: 10.1039/C4DT03655G

Giant Single-Molecule Magnets: A{Mn84} Torus and Its Supramolecular Nanotubes
journal, April 2004

  • Tasiopoulos, Anastasios J.; Vinslava, Alina; Wernsdorfer, Wolfgang
  • Angewandte Chemie, Vol. 116, Issue 16
  • DOI: 10.1002/ange.200353352

A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
journal, July 2017

  • Guo, Fu-Sheng; Day, Benjamin M.; Chen, Yan-Cong
  • Angewandte Chemie, Vol. 129, Issue 38
  • DOI: 10.1002/ange.201705426

Toward Rapid, “Green”, Predictable Microwave-Assisted Synthesis
journal, November 2005


A Ferromagnetically Coupled Mn19 Aggregate with a RecordS=83/2 Ground Spin State
journal, July 2006

  • Ako, Ayuk M.; Hewitt, Ian J.; Mereacre, Valeriu
  • Angewandte Chemie, Vol. 118, Issue 30
  • DOI: 10.1002/ange.200601467

Single-Molecule Magnets
journal, May 2000

  • Ruiz-molina, Daniel; Christou, George; Hendrickson, David N.
  • Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 343, Issue 1
  • DOI: 10.1080/10587250008023497

Quantum Tunneling of Magnetization in Lanthanide Single-Molecule Magnets: Bis(phthalocyaninato)terbium and Bis(phthalocyaninato)dysprosium Anions
journal, May 2005

  • Ishikawa, Naoto; Sugita, Miki; Wernsdorfer, Wolfgang
  • Angewandte Chemie, Vol. 117, Issue 19
  • DOI: 10.1002/ange.200462638

Quantum Computing in Molecular Magnets
text, January 2000


Spin-enhanced magnetocaloric effect in molecular nanomagnets
text, January 2005


Works referencing / citing this record: