Professor Stuart Batten

Stuart Batten

Professor
BSc(Hons), PhD, FRACI, C.Chem, GCHE
Address: School of Chemistry, Monash University 3800, Australia.
Phone: (03) 9905 4606
Fax: +61 3 9905 4597
Email: Stuart.Batten@monash.edu
Website: /science/about/schools/chemistry/staff/sbatten/index.html

Chemistry of Small Nitrile Anions

In conjunction with Prof. Keith Murray, we have been studying the structures and magnetism of the coordination polymers of small nitrile anions, such as dicyanamide (dca, N(CN)2-) and tricyanomethanide (tcm, C(CN)3-). We have discovered a new class of magnetically ordering compounds that has sparked a surge in interest in dca coordination polymers. The α-[M(dca)2] compounds all have rutile-like structures in which octahedral metal centres are bridged by three-connecting dca ligands (which coordinate through all three nitrogen atoms). Despite their isomorphous structures, the magnetic properties vary widely: Cr, Mn and Fe are spin-canted antiferromagnets (TN = 47, 16, 19 K), Co, Ni and Cu are ferromagnets (Tc = 9, 21, 1.7 K). The ß-[M(dca)2] phase is formed by tetrahedral metals, and is composed of (4,4) 2D sheets of metals bridged by μ2 ligands (the amide nitrogen does not coordinate). The effect of structure on magnetic properties is illustrated by the fact that both phases can be isolated for M = Co, however while the α phase is a ferromagnet, the ß phase is a spin-canted antiferromagnet (TN = 9 K). The dimensionality of the dicyanamide coordination polymers can also be reduced by the introduction of terminal solvent ligands such as H2O, MeOH, EtOH, DMF and pyridine. An unusual tube-like 1D polymer is formed when 2-aminopyridine is added to the reaction mixture; the topology of the tube is identical to the square channels in the α-[M(dca)2] rutile-like networks.

Mn(dca)2

Polymorphism and pseudo-polymorphism is common in dca coordination polymers. In addition to the α and ß forms of [M(dca)2], α-[Cu(dca)2(pyz)] contains two interpenetrating α-Po-like 3D networks, while the ß form contains 2D (4,4) sheets. Two compounds are isolated from a reaction mixture containing Cu(I), dca and 4,4'-bipyridine whose formulae differ only by the number of solvent molecules in the structure; one contains 1D ladder-like polymers while the other has a thick 2D layer structure. This latter compound displays 2D parallel interpenetration, with each layer interlocked with four others. The mean planes of the layers, however, are parallel but not coincident, and thus the interlocking generates an overall 3D structure rather than the usual formation of 2D layers. Cu(dca)(bpe), bpe = 1,2-bis(4-pyridyl)ethene also has an α phase (twofold parallel interpenetration of (4,4) 2D sheets) and a ß phase (five interpenetrating diamond like nets in which the topology of interpenetration is unprecedented).

More recently we have been studying, in collaboration with Prof. Murray, Prof. Glen Deacon and Dr. David Turner, the chemistry of other related anions, and in particular dicyanonitrosomethanide (dcnm, C(CN)2(NO)-). This anion has been found to undergo nucleophilic addition of water, alcohols, and amines across one or both of the nitrile groups, to generate new families of anions. These anions have been used in a remarkable array of applications, including synthesis of new organic anions and ligands, coordination polymers of interest for long-range magnetic ordering and gas sorption, metal clusters which may act as single molecule magnets, new hydrogen bonded materials, new homoleptic lanthanoid complexes, and as anions for novel ionic liquids (as both the free anion and as anionic [LnL6]3- complexes). We have been investigating the formation and properties of these ionic liquids in collaboration with Prof. Doug MacFarlane (free anions) and Prof. Anja-Verena Mudring (Ln complexes), and have also undertaken theoretical studies on the chemistry of the anions with Dr. Ekaterina Izgorodina.

Selected References

  • "The Chemistry and Complexes of Small Cyano Anions", David R. Turner, Anthony S.R. Chesman, Keith S. Murray, Glen B. Deacon and Stuart R. Batten, Chem. Commun., 2011, 47, 10189-10210.
  • "Structure and Magnetism of Coordination Polymers Containing Dicyanamide and Tricyanomethanide", Stuart R. Batten and Keith S. Murray, Coord. Chem. Rev., 2003, 246, 103-130.
  • "Melting Point Suppression in new Lanthanoid(III) Ionic Liquids by Trapping of Kinetic Polymorphs: an In Situ Synchrotron Powder Diffraction Study", Anthony S.R. Chesman, Mei Yang, Bert Mallick, Tamsyn M. Ross, Ian A. Gass, Glen B. Deacon, Stuart R. Batten, Anja-Verena Mudring, Chem. Commun., 2012, in press.
  • "Theoretical and Experimental Insights into Mechanism of the Nucleophilic Addition of Water and Methanol to Dicyanonitrosomethanide", Ekaterina I. Izgorodina, Anthony S.R. Chesman, David R. Turner, Glen B. Deacon and Stuart R. Batten, J. Phys. Chem. B, 2010, 114, 16517-16527.
  • "New Approaches to 12-coordination: Structural Consequences of Steric Stress, Lanthanoid Contraction and Hydrogen Bonding", Anthony S.R. Chesman, David R. Turner, Glen B. Deacon and Stuart R. Batten, Eur. J. Inorg. Chem., 2010, 2798-2812.
  • "Di- and Triammonium Salts of Carbamoyldicyanomethanide, C(CN)2(CONH2)-: Towards Organic Layered Architectures", David R. Turner and Stuart R. Batten, Cryst. Growth Des., 2010, 10, 2501-2508.
  • "Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d-Block Complexes", Anthony S.R. Chesman, David R. Turner, Boujemaa Moubaraki, Keith S. Murray, Glen B. Deacon, Stuart R. Batten, Eur. J. Inorg. Chem., 2010, 59-73.
  • "Coordination polymers of nitrocyanamide, O2NNCN-: Synthesis, structure and magnetism", Anna M. Kutasi, David R. Turner, Boujemaa Moubaraki, Stuart R. Batten and Keith S. Murray, CrystEngComm, 2009, 11, 2089-2095.
  • "An Octanuclear Iron(III) Cluster Complex Containing the Nitroso Bridging Ligand Carbamoylcyanonitrosomethanide", Anthony S.R. Chesman, David R. Turner, Boujemaa Moubaraki, Keith S. Murray, Glen B. Deacon, and Stuart R. Batten, Aust. J. Chem., 2009, 62, 1137-1141.
  • "Lanthaballs: Chiral, Structurally Layered Polycarbonate Tridecanuclear Lanthanoid Clusters", Anthony S. R. Chesman, David R. Turner, Boujemaa Moubaraki, Keith S. Murray, Glen B. Deacon, and Stuart R. Batten, Chem. Eur. J., 2009, 15, 5203-5207.
  • "Metal-Promoted Nucleophilic Addition and Cyclisation of Diamines with Dicyanonitrisomethanide, [C(CN)2(NO)]-", Anthony S. R. Chesman, David R. Turner, Glen B. Deacon, and Stuart R. Batten, Chem. Asian J., 2009, 4, 761-769.
  • "Ammonium salts of carbamoyldicyanomethanide, C(CN)2(CONH2)-. Effects of hydrogen-bonding cations on anionic networks.", David R. Turner, Rose MacDonald, Wan Teng Lee and Stuart R. Batten, CrystEngComm, 2009, 11, 298-305.
  • "Destabilisation of a dual-synthon hydrogen bonding motif by packing effects and competing hydrogen bond donors", David R. Turner, Sze Nee Pek and Stuart R. Batten, CrystEngComm, 2009, 11, 87-93.
  • "A Sheet of Clusters: Self-Assembly of a (4,4) Network of FeIII10 Clusters", David R. Turner, Sze Nee Pek, John D. Cashion, Boujemaa Moubaraki, Keith S. Murray and Stuart R. Batten, Dalton Trans., 2008, 6877-6879.
  • "Amide-water hydrogen bond motifs in alkali-metal/crown ether complexes of carbamoyldicyanomethanide, C(CONH2)(CN)2-", David R. Turner, Sze Nee Pek and Stuart R. Batten, New J. Chem., 2008, 32, 719-726.
  • "Heterotapes: A Persistent, Dual-Synthon Hydrogen Bonding Motif", David R. Turner, Sze Nee Pek and Stuart R. Batten, Chem. Asian J., 2007, 2, 1534-1539.
  • "Dye-sensitized nanocrystalline solar cells incorporating ethylmethylimidazolium-based ionic liquid electrolytes", Qing Dai, David B. Menzies, Douglas R. MacFarlane, Stuart R. Batten, Stewart Forsyth, Leone Spiccia, Yi-Bing Cheng, Maria Forsyth, C. R. Chimie, 2006, 9, 617-621.
  • "Hybrid Materials Containing Organometallic Cations and 3-D Anionic Metal Dicyanamide Networks of Type [Cp*2M][M'(dca)3]", Patricia van der Werff, Eugenia Martínez-Ferrero, Stuart R Batten, Paul Jensen, Catalina Ruiz-Pérez, Manuel Almeida, Joao C. Waerenborgh, John D. Cashion, Boujemaa Moubaraki, José Ramón Galán-Mascarós, José María Martínez-Agudo, Eugenio Coronado, and Keith S. Murray, Dalton Trans., 2005, 285-290.
  • "Ionic Liquids Based on Imidazolium and Pyrrolidinium Salts of the Tricyanomethanide Anion", Stewart A. Forsyth, Stuart R. Batten, Qing Dai and Douglas R. MacFarlane, Aust. J. Chem., 2004, 57, 121-124.
  • "Structure and magnetism of trinuclear and tetranuclear mixed valent manganese clusters from dicyanonitrosomethanide derived ligands", David J. Price, Stuart R. Batten, Kevin J. Berry, Boujemaa Moubaraki and Keith S. Murray, Polyhedron, 2003, 22,165-176.
  • "Syntheses, crystal structures, and magnetic properties of first row transition metal coordination polymers containing dicyanamide and 4,4'-bipyridine", Paul Jensen, Stuart R. Batten, Boujemaa Moubaraki and Keith S. Murray, J. Chem. Soc., Dalton Trans., 2002, 3712-3722.
  • "New 2D coordination polymers containing both bidentate and tridentate dicyanamide bridges and intercalated phenazine", Anna M. Kutasi, Stuart R. Batten, Boujemaa Moubaraki and Keith S. Murray, J. Chem. Soc., Dalton Trans., 2002, 819-821.
  • "Cation Templation of Anionic Metal Dicyanamide Networks", Patricia M. van der Werff, Stuart R. Batten, Paul Jensen, Boujemaa Moubaraki and Keith S. Murray, Chem. Commun., 2000, 2331-2332.
  • "Anionic metal dicyanamide networks with paramagnetic counter-cations", Stuart R. Batten, Paul Jensen, Boujemaa Moubaraki and Keith S. Murray, Chem. Commun., 2000, 2331-2331.
  • "Infinite molecular tubes: structure and magnetism of M(dca)2(apym), M = Co, Ni, apym = 2-aminopyrimidine, dca = dicyanamide, N(CN)2-", Paul Jensen, Stuart R. Batten, Boujemaa Moubaraki and Keith S. Murray, Inorg. Chem., 2001, 40 1718-1722.
  • "Self-Penetration - a Structural Compromise between Single Networks and Interpenetration: Magnetic Properties and Crystal Structures of [Mn(dca)2(H2O)] and [M(dca)(tcm)], M = Co, Ni, Cu, dca = Dicyanamide, N(CN)2-, tcm = Tricyanomethanide, C(CN)3-", Paul Jensen, David J. Price, Stuart R. Batten, Boujemaa Moubaraki and Keith S. Murray, Chem. Eur. J., 2000, 6, 3186-3195.
  • "Crystal structures and magnetic properties of the interpenetrating rutile-related compounds M(tcm)2 [M = octahedral, divalent metal; tcm- = tricyanomethanide, C(CN)3-] and the sheet structures of [M(tcm)2(EtOH)2] (M = Co or Ni)", Stuart R. Batten, Bernard F. Hoskins, Boujemaa Moubaraki, Keith S. Murray and Richard Robson, J. Chem. Soc., Dalton Trans., 1999, 2977-2986.
  • "Syntheses, Structures and Magnetism of α-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L = pyridine, CH3OH, DMF and dca-= Dicyanamide, N(CN)2-, Stuart R. Batten, Paul Jensen, Cameron J. Kepert, Mohamedally Kurmoo, Boujemaa Moubaraki, Keith S. Murray and David J. Price, J. Chem. Soc., Dalton Trans., 1999, 2987-2997.
  • "Structural isomers of M(dca)2 molecule-based magnets. Crystal structure of tetrahedrally coordinated sheet-like ß-Zn(dca)2 and ß-Co/Zn(dca)2, and the octahedrally coordinated rutile-like α-Co(dca)2, where dca-= dicyanamide, N(CN)2-, and magnetism of ß-Co(dca)2", Paul Jensen, Stuart R. Batten, Gary D. Fallon, Boujemaa Moubaraki, Keith S. Murray and David J. Price, Chem. Commun., 1999, 177-178.
  • "Structure and Molecular Magnetism of the Rutile-Related Compounds M(dca)2, M = CoII, NiII, CuII, dca = dicyanamide, N(CN)2-", Stuart R. Batten, Paul Jensen, Boujemaa Moubaraki, Keith S. Murray and Richard Robson, Chem. Commun., 1998, 439-440.