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Title: Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clusters

Journal Article · · Polyhedron
 [1];  [2];  [3];  [4];  [4];  [2];  [5];  [1]
  1. Brock Univ., St. Catharines, ON (Canada). Dept. of Chemistry
  2. Univ. of Cyprus, Nicosia (Cyprus). Dept. of Chemistry
  3. Univ. of Cyprus, Nicosia (Cyprus). Dept. of Chemistry; Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
+ Show Author Affiliations

Here, the employment of cyanato (OCN-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3 in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+ core of representative complex 1 comprises a MnII4MnIII4 double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3 defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/III complexes with structures different than these obtained from the use of the related azides.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Brock Univ., St. Catharines, ON (Canada); Natural Sciences and Engineering Research Council of Canada (NSERC); European Research Area (ERA); Ontario Trillium Foundation; National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231; DMR-1213030
OSTI ID:
1439196
Alternate ID(s):
OSTI ID: 1250199
Journal Information:
Polyhedron, Vol. 108, Issue C; Related Information: © 2015 Elsevier Ltd. All rights reserved.; ISSN 0277-5387
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

References (70)

Architecture of the Photosynthetic Oxygen-Evolving Center journal March 2004
An evaluation of structural models for the photosynthetic water-oxidizing complex derived from spectroscopic and X-ray diffraction signatures journal November 2001
Manganese Cluster in Photosynthesis:  Where Plants Oxidize Water to Dioxygen journal January 1996
Recent advances in the understanding of the biological chemistry of manganese journal April 1999
Single-Molecule Magnets journal November 2000
Single-Molecule Magnets Under Pressure journal January 2006
Molecular magnetism journal January 2007
Quantum Tunneling of Magnetization and Related Phenomena in Molecular Materials journal January 2003
Encapsulation of single-molecule magnets in carbon nanotubes journal July 2011
Electronic read-out of a single nuclear spin using a molecular spin transistor journal August 2012
Design of magnetic coordination complexes for quantum computing journal January 2012
Mn 7 Species with an S = 29 / 2 Ground State: High-Frequency EPR Studies of a Species at the Classical/Quantum Spin Interface journal November 2011
Linking Centered Manganese Triangles into Larger Clusters: A {Mn32} Truncated Cube journal October 2005
Polynuclear NiII and MnII azido bridging complexes. Structural trends and magnetic behavior journal October 1999
Azide as a Bridging Ligand and Magnetic Coupler in Transition Metal Clusters journal November 2006
The bridging azido ligand as a central “player” in high-nuclearity 3d-metal cluster chemistry journal September 2014
Covalently Linked Dimers of Clusters: Loop- and Dumbbell-Shaped Mn 24 and Mn 26 Single-Molecule Magnets journal August 2008
A Ferromagnetically Coupled Mn19 Aggregate with a RecordS=83/2 Ground Spin State journal July 2006
A Mn 17 Octahedron with a Giant Ground-State Spin: Occurrence in Discrete Form and as Multidimensional Coordination Polymers journal June 2009
Single-Molecule Magnets:  A Mn 25 Complex with a Record S = 51/2 Spin for a Molecular Species journal April 2004
Constructing magnetic molecular solids by employing three-atom ligands as bridges journal January 2008
A Nonanuclear Iron(II) Single-Molecule Magnet journal April 2004
Unique Single-Atom Binding of Pseudohalogeno Ligands to Four Metal Ions Induced by Their Trapping into High-Nuclearity Cages journal March 2001
Reactivity in polynuclear transition metal chemistry as a means to obtain high-spin molecules: substitution of µ4-OH– by η1,µ4-N3– increases nine times the ground-state S value of a nonanuclear nickel(ii) cage journal November 2001
Distorted Mn IV Mn III 3 Cubane Complexes as Single-Molecule Magnets journal January 1996
Large Spin-State Changes in Isostructural Cyanate- and Azide-Bridged Mn 3 III Mn 2 II Single-Molecule Magnets journal January 2010
Approaches to Molecular Magnetic Materials from the Use of Cyanate Groups in Higher Oxidation State Metal Cluster Chemistry: Mn 14 and Mn 16 journal March 2013
Heptanuclear and Decanuclear Manganese Complexes with the Anion of 2-Hydroxymethylpyridine journal November 2003
Mn 4 single-molecule magnets with a planar diamond core and S =9 journal July 2003
Single-Molecule Magnets:  A New Family of Mn 12 Clusters of Formula [Mn 12 O 8 X 4 (O 2 CPh) 8 L 6 ] journal April 2002
Slow Relaxation in a One-Dimensional Rational Assembly of Antiferromagnetically Coupled [Mn 4 ] Single-Molecule Magnets journal December 2005
Quantum Tunneling and Quantum Phase Interference in a [Mn II 2 Mn III 2 ] Single-Molecule Magnet journal August 2005
“Spin Tweaking” of a High-Spin Molecule: An Mn25 Single-Molecule Magnet with anS=61/2 Ground State journal January 2007
High-Nuclearity, High-Symmetry, High-Spin Molecules: A Mixed-Valence Mn10 Cage Possessing RareT symmetry and anS=22 Ground State journal June 2006
A tetranuclear manganese carboxylate cluster with bis(2-pyridyl)amine ligation: [Mn4O2(O2CEt)7(bpya)2](ClO4) journal August 2002
Diamagnetic Corrections and Pascal's Constants journal April 2008
SIR2004 : an improved tool for crystal structure determination and refinement journal March 2005
A short history of SHELX journal December 2007
WinGX suite for small-molecule single-crystal crystallography journal August 1999
Single-crystal structure validation with the program PLATON journal January 2003
Azide Groups in Higher Oxidation State Manganese Cluster Chemistry: From Structural Aesthetics to Single-Molecule Magnets journal April 2009
Structural and magnetic variations in tetranuclear Ni II clusters: the effect of the reaction solvent and ligand substitution on product identity journal January 2014
Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination journal October 1980
Cyanato bridged binuclear nickel(II) and copper(II) complexes with pyridylpyrazole ligand: Synthesis, structure and magnetic properties journal September 2011
6-Coordinate tungsten(vi) tris-n-isopropylanilide complexes: products of terminal oxo and nitrido transformations effected by main group electrophiles journal January 2008
Bond valence sum analysis of metal-ligand bond lengths in metalloenzymes and model complexes. 2. Refined distances and other enzymes journal September 1993
Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database journal August 1985
Heterometallic [Mn5-Ln4] Single-Molecule Magnets with High Anisotropy Barriers journal April 2008
Molecular Nanoscale Magnetic Refrigerants: A Ferrimagnetic {Cu II 15 Gd III 7 } Cagelike Cluster from the Use of Pyridine-2,6-dimethanol journal September 2013
Magnetic [ n × n ] ( n = 2−5) Grids by Directed Self-Assembly journal April 2009
A self-assembled hexadecanuclear 4 × [2 × 2] Mn( ii ) 16 square grid from a pyridazine bis(hydrazone) ligand: synthesis, structure and magnetism journal January 2006
Novel 48-Membered Hexadecanuclear and 60-Membered Icosanuclear Manganese Metallamacrocycles journal September 2008
New Structural Motifs in Manganese Single-Molecule Magnetism from the Use of Triethanolamine Ligands journal January 2005
Wheel-Shaped Mn 16 Single-Molecule Magnets journal June 2008
Synthesis, structure and magnetism of a new manganese carboxylate cluster: [Mn16O16(OMe)6(OAc)16(MeOH)3(H2O)3]·6H2O journal March 2002
A Family of Mn 16 Single-Molecule Magnets from a Reductive Aggregation Route journal November 2004
New high-nuclearity manganese clusters containing mixed chelating ligands: Syntheses, crystal structures and magnetochemical characterization journal January 2011
Constructing octa- and hexadecanuclear manganese clusters from tetrahedral MnIII3MnII cores bridged by quinquedentate Schiff base and versatile azide groups journal January 2010
Solvothermal Synthesis and Characterization of Two High-Nuclearity Mixed-Valent Manganese Phosphonate Clusters journal April 2008
Mn 8 and Mn 16 Clusters from the Use of 2-(Hydroxymethyl)pyridine, and Comparison with the Products from Bulkier Chelates: A New High Nuclearity Single-Molecule Magnet journal November 2010
High-Spin Mn Wheels journal August 2007
High symmetry superoctahedron cluster [MnIII18O14]26+ from the use of N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine journal January 2013
High-nuclearity, mixed-valence Mn 17 , Mn 18 and {Mn 62 } n complexes from the use of triethanolamine journal January 2011
Structure and magnetism of decanuclear and octadecanuclear manganese(II/III) triethanolamine clusters journal January 2009
Synthesis and Characterization of Mixed-Valent Manganese Phosphonate Cage Complexes journal November 2006
Quantum Tunneling of Magnetization in a New [Mn 18 ] 2+ Single-Molecule Magnet with S = 13 journal August 2002
Single-Molecule Magnets:  Structure and Properties of [Mn 18 O 14 (O 2 CMe) 18 (hep) 4 (hepH) 2 (H 2 O) 2 ](ClO 4 ) 2 with Spin S = 13 journal February 2005
Nanoscale Cages of Manganese and Nickel with “Rock Salt” Cores journal July 1998
Octadecanuclearity in Manganese Carboxylate Chemistry: K4[Mn18O16(O2CPh)22(phth)2(H2O)4](phthH2= phthalic acid) journal May 1995
On the Paramagnetic Susceptibilities of Some Polynuclear Complex Salts journal January 1950

Cited By (3)

Synthesis, characterization and DFT aspects of some oxovanadium(IV) and manganese(II) complexes involving dehydroacetic acid and β-diketones journal January 2018
Synthesis, characterization and DFT aspects of some oxovanadium(IV) and manganese(II) complexes involving dehydroacetic acid and β-diketones text January 2018
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Manganese
Cyanates
2-(Hydroxymethyl)pyridine
Crystal structures
Magnetism