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Title: The remarkable influence of N, O-ligands in the assembly of a bis-calix[4]arene-supported [MnIV2MnIII10MnII8] cluster

Abstract

We report that calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3d, 4f or 3d-4f metal ions. Calixarene-based metal ion fragments act as both bridging and structure capping moieties in these systems, and this behaviour is systematically extended upon moving to bis-calix[4]arene, a relatively new ligand in which two calix[4]arenes are tethered at the methylene bridge position. N,O-Ligands greatly influence cluster formation with bis-calix[4]arene, affording a remarkable mixed-valence [MnIV2MnIII10MnII8] cluster that displays coordination chemistry typical of each ligand type, but also new structure capping behaviour for the latter.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Heriot-Watt Univ., Riccarton, Edinburgh (United Kingdom)
  2. Univ. of Edinburgh, Scotland (United Kingdom)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530277
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 48; 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

Coletta, Marco, Sanz, Sergio, McCormick, Laura J., Teat, Simon J., Brechin, Euan K., and Dalgarno, Scott J. The remarkable influence of N, O-ligands in the assembly of a bis-calix[4]arene-supported [MnIV2MnIII10MnII8] cluster. United States: N. p., 2017. Web. doi:10.1039/c7dt04233g.
Coletta, Marco, Sanz, Sergio, McCormick, Laura J., Teat, Simon J., Brechin, Euan K., & Dalgarno, Scott J. The remarkable influence of N, O-ligands in the assembly of a bis-calix[4]arene-supported [MnIV2MnIII10MnII8] cluster. United States. doi:10.1039/c7dt04233g.
Coletta, Marco, Sanz, Sergio, McCormick, Laura J., Teat, Simon J., Brechin, Euan K., and Dalgarno, Scott J. Fri . "The remarkable influence of N, O-ligands in the assembly of a bis-calix[4]arene-supported [MnIV2MnIII10MnII8] cluster". United States. doi:10.1039/c7dt04233g. https://www.osti.gov/servlets/purl/1530277.
@article{osti_1530277,
title = {The remarkable influence of N, O-ligands in the assembly of a bis-calix[4]arene-supported [MnIV2MnIII10MnII8] cluster},
author = {Coletta, Marco and Sanz, Sergio and McCormick, Laura J. and Teat, Simon J. and Brechin, Euan K. and Dalgarno, Scott J.},
abstractNote = {We report that calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3d, 4f or 3d-4f metal ions. Calixarene-based metal ion fragments act as both bridging and structure capping moieties in these systems, and this behaviour is systematically extended upon moving to bis-calix[4]arene, a relatively new ligand in which two calix[4]arenes are tethered at the methylene bridge position. N,O-Ligands greatly influence cluster formation with bis-calix[4]arene, affording a remarkable mixed-valence [MnIV2MnIII10MnII8] cluster that displays coordination chemistry typical of each ligand type, but also new structure capping behaviour for the latter.},
doi = {10.1039/c7dt04233g},
journal = {Dalton Transactions},
number = 48,
volume = 46,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Single crystal X-ray structures of 1 (A),2a 2 (B),3b H8L1 (C), 14 3 (D),14 4 (E),15 and 5 (F).16 Colour code C – grey, O – red, N – royal blue, MnII – pale blue, MnIII – purple, CuII – light blue, LnIII – green. Hydrogen atoms (exceptmore » those involved in lower-rim H-bonding in C), tBu groups of C[4] and H8L1 / L1 (except those shown in C), ligated solvent molecules in D, E and F, and co-crystallised solvent/anions omitted for clarity. Figures not to scale.« less

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    A new class of single-molecule magnets: mixed-valent [Mn4(O2CMe)2(Hpdm)6][ClO4]2 with an S = 8 ground state
    journal, January 1999

    • Brechin, Euan K.; Huffman, John C.; Christou, George
    • Chemical Communications, Issue 9
    • DOI: 10.1039/a901106d

    Self-assembly and decay of Mn(ii) pivalate–phosphonate complexes
    journal, January 2014

    • Burkovskaya, Nataliya; Aleksandrov, Grigory; Ugolkova, Elena
    • New Journal of Chemistry, Vol. 38, Issue 4
    • DOI: 10.1039/c3nj00899a

    [Mn III 4 Ln III 4 ] Calix[4]arene Clusters as Enhanced Magnetic Coolers and Molecular Magnets
    journal, September 2010

    • Karotsis, Georgios; Kennedy, Stuart; Teat, Simon J.
    • Journal of the American Chemical Society, Vol. 132, Issue 37
    • DOI: 10.1021/ja104848m

    Calixarene supported enneanuclear Cu(ii) clusters
    journal, January 2010

    • Karotsis, Georgios; Kennedy, Stuart; Dalgarno, Scott J.
    • Chemical Communications, Vol. 46, Issue 22
    • DOI: 10.1039/c0cc00011f

    Calix[4]arene-supported FeIII2LnIII2 clusters
    journal, January 2011

    • Sanz, Sergio; Ferreira, Kerry; McIntosh, Ruaraidh D.
    • Chemical Communications, Vol. 47, Issue 32
    • DOI: 10.1039/c1cc13055b

    Self-assembly of two high-nuclearity manganese calixarene-phosphonate clusters: diamond-like Mn 16 and drum-like Mn 14
    journal, January 2015

    • Su, Kongzhao; Jiang, Feilong; Qian, Jinjie
    • RSC Advances, Vol. 5, Issue 42
    • DOI: 10.1039/c5ra02530c

    Metallocalixarene catalysts: α-olefin polymerization and ROP of cyclic esters
    journal, January 2016


    Diol-type ligands as central ‘players’ in the chemistry of high-spin molecules and single-molecule magnets
    journal, January 2008

    • Tasiopoulos, Anastasios J.; Perlepes, Spyros P.
    • Dalton Transactions, Issue 41
    • DOI: 10.1039/b805014g

    Design of magnetic coordination complexes for quantum computing
    journal, January 2012

    • Aromí, Guillem; Aguilà, David; Gamez, Patrick
    • Chem. Soc. Rev., Vol. 41, Issue 2
    • DOI: 10.1039/c1cs15115k

    Complementary ligands direct the formation of a calix[8]arene-supported ferromagnetic MnIVMnIII dimer
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    • McLellan, Ross; Taylor, Stephanie M.; McIntosh, Ruaraidh D.
    • Dalton Transactions, Vol. 42, Issue 19
    • DOI: 10.1039/c3dt50294e

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    Elucidating the Ring Inversion Mechanism(s) for Biscalixarenes
    journal, August 2014

    • Murphy, Paul; Dalgarno, Scott J.; Paterson, Martin J.
    • The Journal of Physical Chemistry A, Vol. 118, Issue 36
    • DOI: 10.1021/jp5070616

    The coordination chemistry of pyridyl oximes
    journal, January 2006

    • Milios, Constantinos J.; Stamatatos, Theocharis C.; Perlepes, Spyros P.
    • Polyhedron, Vol. 25, Issue 1
    • DOI: 10.1016/j.poly.2005.07.022

    Supertetrahedral icosanuclear and ring-like decanuclear mixed valent manganese(ii/iii) triethanolamine clusters
    journal, January 2010

    • Langley, Stuart K.; Moubaraki, Boujemaa; Berry, Kevin J.
    • Dalton Transactions, Vol. 39, Issue 20
    • DOI: 10.1039/b926795f

    Phosphonate Ligands Stabilize Mixed-Valent {MnIII20−xMnIIx} Clusters with Large Spin and Coercivity
    journal, August 2005

    • Maheswaran, Shanmugam; Chastanet, Guillaume; Teat, Simon J.
    • Angewandte Chemie International Edition, Vol. 44, Issue 32
    • DOI: 10.1002/anie.200501265

    A New Family of 3 d -4 f Bis-Calix[4]arene-Supported Clusters
    journal, September 2017

    • Coletta, Marco; McLellan, Ross; Sanz, Sergio
    • Chemistry - A European Journal, Vol. 23, Issue 56
    • DOI: 10.1002/chem.201703197

    A Family of Calix[4]arene-Supported [MnIII2MnII2] Clusters
    journal, May 2011

    • Taylor, Stephanie M.; Karotsis, Georgios; McIntosh, Ruaraidh D.
    • Chemistry - A European Journal, Vol. 17, Issue 27
    • DOI: 10.1002/chem.201003327

    Heterometallic 3d–4f Single-Molecule Magnets: Ligand and Metal Ion Influences on the Magnetic Relaxation
    journal, March 2015


    Synthesis and reactions of a 2-chlorocalix[4]arene and a 2,2′-coupled dicalixarene
    journal, June 2013


    A Mn15 single-molecule magnet consisting of a supertetrahedron incorporated in a loop
    journal, January 2010

    • Moushi, Eleni E.; Masello, Antonio; Wernsdorfer, Wolfgang
    • Dalton Transactions, Vol. 39, Issue 20
    • DOI: 10.1039/b927205d

    Polytopic ligand directed self-assembly—polymetallic [n×n] grids versus non-grid oligomers
    journal, January 2009

    • Dawe, Louise N.; Shuvaev, Konstantin V.; Thompson, Laurence K.
    • Chemical Society Reviews, Vol. 38, Issue 8
    • DOI: 10.1039/b807219c

    Heterometallic Rings: Their Physics and use as Supramolecular Building Blocks
    journal, October 2015

    • McInnes, Eric J. L.; Timco, Grigore A.; Whitehead, George F. S.
    • Angewandte Chemie International Edition, Vol. 54, Issue 48
    • DOI: 10.1002/anie.201502730

    The Use of Calixarenes in Metal-Based Catalysis
    journal, December 2008

    • Homden, Damien M.; Redshaw, Carl
    • Chemical Reviews, Vol. 108, Issue 12
    • DOI: 10.1021/cr8002196

    Facile Interchange of 3d and 4f Ions in Single-Molecule Magnets: Stepwise Assembly of [Mn 4 ], [Mn 3 Ln] and [Mn 2 Ln 2 ] Cages within Calix[4]arene Scaffolds
    journal, June 2015

    • Palacios, Maria A.; McLellan, Ross; Beavers, Christine M.
    • Chemistry - A European Journal, Vol. 21, Issue 31
    • DOI: 10.1002/chem.201500001

    Linked Supramolecular Building Blocks for Enhanced Cluster Formation
    journal, January 2015

    • McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.
    • Chemistry - A European Journal, Vol. 21, Issue 7
    • DOI: 10.1002/chem.201405746

    Syntheses and Properties of Metal-Centered Mixed-Valent [NEt4]{MnII?[MnII3MnIII3Cl6(L)6]} Manganese Wheels
    journal, March 2005

    • Saalfrank, Rolf W.; Nakajima, Takayuki; Mooren, Nicolai
    • European Journal of Inorganic Chemistry, Vol. 2005, Issue 6
    • DOI: 10.1002/ejic.200400773

    Calix[4]arene-supported rare earth octahedra
    journal, January 2012

    • Sanz, Sergio; McIntosh, Ruaraidh D.; Beavers, Christine M.
    • Chem. Commun., Vol. 48, Issue 10
    • DOI: 10.1039/c1cc14603c

    Synthesis and characterization of a series of manganese phosphonate complexes with various valences and nuclearity
    journal, January 2009

    • Wang, Mei; Ma, Chengbing; Wen, Huimin
    • Dalton Trans., Issue 6
    • DOI: 10.1039/b814794a

    Thiacalixarene-based nanoscale polyhedral coordination cages
    journal, September 2014


    Calix[4]arene-Based Single-Molecule Magnets
    journal, September 2009

    • Karotsis, Georgios; Teat, Simon J.; Wernsdorfer, Wolfgang
    • Angewandte Chemie International Edition, Vol. 48, Issue 44
    • DOI: 10.1002/anie.200904094

    A Mixed-Valence Polyoxovanadate(III,IV) Cluster with a Calixarene Cap Exhibiting Ferromagnetic V(III)−V(IV) Interactions
    journal, February 2008

    • Aronica, Christophe; Chastanet, Guillaume; Zueva, Ekaterina
    • Journal of the American Chemical Society, Vol. 130, Issue 7
    • DOI: 10.1021/ja078030q

    Core expansion of bis-calix[4]arene-supported clusters
    journal, January 2016

    • Coletta, Marco; McLellan, Ross; Waddington, Amy
    • Chemical Communications, Vol. 52, Issue 99
    • DOI: 10.1039/c6cc08059f

    Calixarene-supported hexadysprosium cluster showing single molecule magnet behavior
    journal, April 2012


    Synthesis, structure, and properties of a new representative of the family of calix[4]arene-containing [MnII 2MnIII 2]-clusters
    journal, February 2013

    • Aldoshin, S. M.; Antipin, I. S.; Ovcharenko, V. I.
    • Russian Chemical Bulletin, Vol. 62, Issue 2
    • DOI: 10.1007/s11172-013-0074-5

    Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives
    journal, July 2007

    • Kajiwara, Takashi; Iki, Nobuhiko; Yamashita, Masahiro
    • Coordination Chemistry Reviews, Vol. 251, Issue 13-14, p. 1734-1746
    • DOI: 10.1016/j.ccr.2007.01.001

    With complements of the ligands: an unusual S -shaped [Mn 7 ] 2 assembly from tethered calixarenes
    journal, January 2020

    • Coletta, Marco; Sanz, Sergio; Brechin, Euan K.
    • Dalton Transactions, Vol. 49, Issue 28
    • DOI: 10.1039/d0dt01766c

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.