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Professor
BSc(Hons), PhD, FRACI, C.Chem, GCHE

Address: School of Chemistry,
Monash University,
VIC, 3800, Australia
Phone: (03) 9905 4606
Fax: +61 3 9905 4597

Email: Stuart.Batten@monash.edu

Awards and Medals

  • 2002 Rennie Memorial Medalist
  • 2003 Edgeworth David Medalist
  • 2005 HG Andrewartha Medalist
  • 2006 Faculty of Science Award for Excellence in Research by Early Career Researchers (inaugural award)
  • 2006 Vice Chancellor's Award for Excellence in Research by Early Career Researchers (inaugural award)
  • 2006 Victorian Young Tall Poppy Science Award: The Tall Poppy Campaign
  • 2007 Cosmos Magazine Bright Sparks Award
  • 2008 Le Fèvre Memorial Prize
  • 2008 Thomson Scientific Citation Award
  • 2009 Ollé Prize

Teaching Areas

  • CHM3180 Materials Chemistry
  • CHM4000 Metallosupramolecular Chemistry
  • CHM4000 Instrumental Chemistry

Batten Group Members

Funding for PhD or Postdoctoral positions is available from the following sources:

Current Members

  • Lauren MacReadie (PhD student), with Dr. Anthony Chesman (CSIRO) and Dr. David Turner, 2011-
  • Christin Patzschke (PhD student), with Prof. Alan Chaffee, 2011-
  • Melina Nematirad (PhD student), 2011-
    Variable Length Ligands in Supramolecular Chemistry and Crystal   Engineering (Hons 2010)
  • Hayley Scott (PhD student), with Prof. Keith Murray and Dr. Suzanne Neville, 2010-
  • Greg Hall (PhD student), with Dr. David Turner, 2010-
    Design, Synthesis and Investigation of Supramolecular Nanoballs (Hons 2009)
  • Mohd. Rizal Rizali (PhD student), 2009-
  • Emily Mensforth (PhD student), with Dr. Matthew Hill (CSIRO) and Prof. Robert Lamb (University of Melbourne), 2008-
  • Caspar Schneider (PhD student), with Prof. Keith Murray, 2006-
  • Dr. Aron Urbatsch (Postdoctoral Fellow), with Prof. Glen Deacon, 2011-
  • Dr. Will Gee (Postdoctoral Fellow), 2010-
  • Dr. Hong Xu (Visitor from Zhengzhou U, China), 2011-2012

Past Members

  • Simone d'Agostino (Visiting PhD student, University of Bologna, Italy), 2011
  • Pierre Eckold (Visiting Leipzig student), 2011
    Synthesis and characterisation of coordination polymers based on   2-(pyridin-4-yl)malonaldehyde (2011)
  • Nicholas Chilton, with Prof. Keith Murray, 2011
    Synthesis, Structure and Magnetic Anisotropy of Lanthanoid-Based   Single Ion Magnets (Hons 2011)
  • Thomas Heinze (Visiting Leipzig student), with A/Prof Alan Chaffee, 2008
    Porous coordination polymers for gas storage applications (2008)
  • Dr. Martin Grannas (Postdoctoral Fellow), 2010
  • Benjamin Ho (3990 student), 2010
  • A/Prof. Shi-Yao Yang (Visitor from Xiamen U, China), 2009
  • David Barling (3990 student), 2009
  • Yuniar Ponco Prananto, 2007-2009
    Synthesis and Structure of Metal Complexes and Coordination   Polymers of 3-Pyrazol-1-yl Based Ligands (MSc 2003)
  • Martin Duriska, 2005-2008
    Incorporation of Scorpionate Ligands into Coordination Polymers   and Supramolecules (Hons 2003)
    Introducing Multiple Functions into Discrete Supramolecules and   Coordination Polymers (PhD 2008)
  • Anthony Chesman, with Prof. Glen Deacon, 2007-2010
    Pseudohalide Complexes of Lanthanoid and Transition Metals (Hons 2006)
    Metal Complexes Containing Dicyanonitrosomethanide and its   Derivatives (PhD 2010)
  • Tamsyn Ross, with Prof. Keith Murray, 2007-2010
    Magnetostructural studies of some mono- and polynuclear FeII   spin crossover compounds containing new 2,2'-dipyridylamino-substituted   s-triazine ligands (PhD 2010)
  • Kittipong Chainok (visiting PhD student, Suranaree University of Technology, Thailand), with Prof. Keith Murray, 2006, 2007
    Synthesis and structural studies of hybrid organic-inorganic   nanocomposites (PhD 2008)
  • Dr. Jinzhen Lu (Postdoctoral Fellow), 2004-2006, 2007-2009
  • Sze Nee Pek (vacation student), 2006/7
  • Madleen Busse, 2006
    New Trigonal Ligands for Crystal Engineering and   Metallosupramolecular Chemistry (MSc PtI 2006)
  • Dr. Anna Kutasi, with Prof. Keith Murray, 2001-2006
    Synthesis, Structural and Magnetic Properties of Coordination   Polymers using Dicyanamide and Nitrogen-Donor Heterocyclic Ligands (Hons 2001)
    Synthesis, Structure and Magnetism of Metal Complexes Containing   Organocyano Ligands (PhD 2006)
  • Daniel Tonzing (PhD student), with Prof. Keith Murray, 2005-2006
  • Dr. Paul Jensen (Postdoctoral Fellow), with Prof. Keith Murray, 2004-2006
  • Nic Spiccia (3990 student), 2007
  • Alexis Demetrious (Student Research Scheme), 2006
  • Joshua Strauchn-Hatton (Student Research Scheme), 2007
  • Dr. David Turner (ARC Australian Postdoctoral Fellow), 2006-
  • Nian Miao (MSc(Prelim)), 2004

Other Roles

  • Associate Head (Postgraduate), School of Chemistry
  • Member, School Executive, School of Chemistry
  • Member, Research Degrees Committee, Faculty of Science
  • Victorian representative, Inorganic Division, Royal Australian Chemical Institute
  • Secretary, Society of Crystallographers in Australia and New Zealand (SCANZ)
  • Associate Editor, Australian Journal of Chemistry
  • Editorial Board, Polyhedron
  • Editorial Board, Inorganica Chimica Acta
  • International Advisory Board, ChemPlusChem
  • Member, International Union of Crystallography (IUCr) Commission on Structural Chemistry
  • Member, IUPAC task group on Coordination polymers and metal organic frameworks: terminology and nomenclature guidelines (#2009-012-2-200)
  • Member, IUPAC task group on Terminology and nomenclature of inorganic and coordination polymer (#2011-035-1-800)
  • Member, Powder Diffraction Program Advisory Committee, Australian Synchrotron

Research Areas

Please click on the menus below to read more about the areas I research.

Interepenetration

Table of known examples

Attempts to synthesise polymeric networks with porous structures often result in the formation of interpenetrating networks. These networks have no chemical bonds connecting them and yet cannot be separated without breaking of bonds. They can be considered to be polymeric analogues of rotaxanes and catenanes. The links above are to a comprehensive table of all known examples.

Information of a more general nature is given below.


Definition

Entanglement of polymeric networks such that, although there is no direct connection between the networks, they cannot be separated (in a topological sense) without requiring the breaking of network connections.

This is highlighted by the two examples below which are not interpenetrating. The individual networks could theoretically be separated without breaking bonds.

The chains, although entangled like threads in cloth, can be separated without breaking them.

The sheets are interdigitating not interpenetrating.

The networks must also interpenetrate each other in a mutual fashion - i.e. each network must be penetrated by another. Again, the example below, which shows 1D linear chains within channels created by the stacking of 2D nets, is not interpenetrating because the 1D chains are not penetrated by the 2D
sheets.

This system is not interpenetrating.

Nomenclature

To properly describe a structure with interpenetrating networks, one must describe not only the topology of the individual networks, but also the topology of interpenetration, i.e. the way the networks interpenetrate each other. We have developed a descriptive nomenclature to assist with this.

The first consideration is the dimensionality of the individual nets - 1D, 2D or 3D. If the nets are 1D or 2D, then there are two possibilities. For 1D nets, the mean directions of propogation of the nets can be either parallel or inclined. Similarly, for 2D nets the mean planes of the nets can also be either parallel or inclined.

The next consideration is whether the overall dimension of the entanglement is the same as the constituent nets or higher. For example, parallel interpenetration of 1D nets can lead to overall 1D, 2D or 3D entanglements. In contrast, however, inclined interpenetration of 2D nets can only lead to a 3D entanglement.

These considerations are drawn together in the following notation:

mD → nD parallel/inclined interpenetration

For networks which involve interpenetration between networks of different dimensions (see below), then mD is replaced by mD/pD. For interpenetrating nets which have the same dimensionality but different topology (also see below), mD is replaced by mD/mD. For 2D inclined interpenetration, only a 3D entanglement is possible, so the → 3D is redundant and omitted. Similarly, for 3D interpenetration, everything from the arrow onwards in the nomenclature is redundant and omitted.

Types of Interpenetration

The links below illustrate the different types of interpenetration possible.

Further considerations

The above nomenclature is a useful but often not sufficient description of the topology of interpenetration. For example, the four schematic diagrams below all show 2D → 2D parallel interpenetration of (4,4) nets, however the interpenetration topologies are all different.


Four different topologies of interpenetration.

Similarly, 3D nets can interpenetrate with different topologies. For example, below are two different ways in which two alpha-Po networks can interpenetrate. In the left example, the "normal" mode of interpenetration, each cubic cavity catenates with eight such cavities of the other net. In the example on the right, an "abnormal" mode, a cavity of one net catenates with ten cavities of the other net. Diamond is another 3D topology which commonly shows a normal mode of interpenetration, with a minority of structures which show abnormal modes.


Normal mode of interpenetration.

Abnormal mode of interpenetration.

Selected References

  • "Interpenetration", S.R. Batten, Encyclopedia of Supramolecular Chemistry, Eds. J.L. Atwood and J.W. Steed, Marcel Dekker, New York, USA, 2004, 735-741.
  • "Topology of Interpenetration", S.R. Batten, CrystEngComm, 2001, 3, 67-73.
  • "Catenane and Rotaxane Motifs in Interpenetrating and Self-Penetrating Coordination Polymers", Stuart R. Batten and Richard Robson, in Molecular Catenanes, Rotaxanes and Knots, A Journey Through the World of Molecular Topology, Eds. J.-P. Sauvage and C. Dietrich-Buchecker, Wiley-VCH, Weinheim, 1999, 77-105.
  • "Interpenetrating Nets: Ordered, Periodic Entanglement", S.R. Batten and R. Robson, Angew. Chem. Int. Ed., 1998, 37, 1460-1494; Angew. Chem., 1998, 110, 1558-1595.
  • "Interpenetrating metal-organic and inorganic 3D networks: a computer-aided systematic investigation. Part II. Analysis of the Inorganic Crystal Structure Database (ICSD)", I.A. Baburin, V.A. Blatov, L. Carlucci, G. Ciani and D.M. Proserpio, J. Solid State Chem., 2005, 178, 2471-2493.
  • "Interpenetrating metal-organic and inorganic 3D networks: a computer-aided systematic investigation. Part I. Analysis of the Cambridge structural database", V.A. Blatov, L. Carlucci, G. Ciani and D.M. Proserpio, CrystEngComm, 2004, 6, 377-395.
  • "Borromean links and other non-conventional links in 'polycatenated' coordination polymers: re-examination of some puzzling networks", L. Carlucci, G. Ciani and D.M. Proserpio, CrystEngComm, 2003, 5, 269-279.
  • "Polycatenation, polythreading and polyknotting in coordination network chemistry", L. Carlucci, G. Ciani and D.M. Proserpio, Coord. Chem. Rev., 2003, 246, 247-289.

X-ray Crystallography

The main technique we use to determine the 3D molecular structures of our compounds is X-ray Crystallography, using the two area-detector diffractometers in the School of Chemistry, the MX1 and MX2 beamlines at the Australian Synchrotron, and the Koala beamline at the ANSTO nuclear reactor. By measuring the diffraction patterns formed from an X-ray (or neutron) beam passing through a crystal of our product, we can determine its precise molecular structure.

View some of the results of this analysis.

X-ray Crystallography

Crystal Engineering of Coordination Polymers

The aim of crystal engineering is to control the way molecules assemble in the solid state. Since the properties of any material are largely due to its structure, control over the structure allows us to manipulate these properties. The crystal engineering of coordination polymers is of particular interest to our group. By judicious choice of preferred ligand and metal coordination geometries, control over the topology and geometry of the infinite networks can be gained. Such control allows the deliberate design of materials with a range of useful properties, including electronic properties, magnetic properties (long-range magnetic ordering, spin-crossover materials), microporosity (including the related properties of ion exchange and heterogeneous catalysis), non-linear optical effects and luminescent properties. We are currently developing a number of approaches to such materials. Specific aims include new materials for storage of hydrogen (with applications in e.g. hydrogen fuelled transportation) and the capture of carbon dioxide (for pollution control).

Selected References

  • Coordination Polymers: Design, Analysis and Application, Stuart R. Batten, Suzanne M. Neville and David R. Turner, Royal Society of Chemistry, Cambridge, 2009. 424 pages.
  • "Variable length ligands: a new class of bridging ligands for supramolecular chemistry and coordination polymers", Martin B. Duriska, Suzanne M. Neville and Stuart R. Batten, Chem. Commun., 2009, 5579-5581.
  • "An Exceptional 54-fold Interpenetrated Coordination Polymer with 103-srs Network Topology", Hua Wu, Jin Yang, Zhong-Min Su, Stuart R. Batten and Jian-Fang Ma, J. Am. Chem. Soc., 2011, 133, 11406-11409.
  • "Coordination Polymers of Hexacyanotrimethylenecyclopropanediide and Its Monoanionic Radical: Synthesis, Structure and Magnetic Properties", Anna M. Kutasi, David R. Turner, Paul Jensen, Boujemaa Moubaraki, Stuart R. Batten and Keith S. Murray, Inorg. Chem., 2011, 50, 6673-6684.
  • "Transformation of a 1D to 3D coordination polymer mediated by low temperature lattice solvent loss", Anthony S.R. Chesman, David R. Turner, Glen B. Deacon and Stuart R. Batten, Chem. Commun., 2010, 46, 4899-4901.
  • "Unusual parallel and inclined interlocking modes in polyrotaxane-like metal-organic frameworks", Jin Yang, Jian-Fang Ma, Stuart R. Batten and Zhong-Min Su, Chem. Commun., 2008, 2233-2235.
  • "Solvothermal vs. bench-top reactions: Control over the formation of discrete complexes and coordination polymers", Anthony S.R. Chesman, David R. Turner, David J. Price, Boujemaa Moubaraki, Keith S. Murray, Glen B. Deacon and Stuart R. Batten, Chem. Commun., 2007, 3541-3543.
  • "Temperature-Dependent Synthesis of Metal-Organic Frameworks Based on a Flexible Tetradentate Ligand with Bidirectional Coordination Donors", Yu-Bin Dong, You-Yun Jiang, Jie Li, Jian-Ping Ma, Feng-Ling Liu, Bo Tang, Ru-Qi Huang, and Stuart R. Batten, J. Am. Chem. Soc., 2007, 129, 4520-4521.
  • "An unprecedented eight-connected self-penetrating network based on pentanuclear zinc cluster building blocks", Xin-Long Wang, Chao Qin, En-Bo Wang, Zhong-Min Su, Lin Xu, and Stuart R. Batten, Chem. Commun., 2005, 4789-4791.
  • "Cu2+-Mediated Dehydrogenative Coupling and Hydroxylation of an N-Heterocyclic Ligand: from Generation of a Tetratopic Ligand to the Designed Assembly of Three-Dimensional Copper(I) Coordination Polymers", Sheng Hu, Jing-Cai Chen, Ming-Liang Tong, Bo Wang, Yun-Xin Yan and Stuart R. Batten, Angew. Chem. Int. Ed., 2005, 44, 5471-5475.
  • "Coordination Polymers", Stuart R. Batten, Encyclopedia of Supramolecular Chemistry, Eds. JL Atwood and JW Steed, Marcel Dekker, New York, USA, 2006.
  • "Glorious Uncertainty - Challenges for Network Design", Stuart R. Batten, J. Solid State Chem., 2005, 178, 2475-2479.
  • "New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry", Harry Adams, Stuart R. Batten, Graham M. Davies, Martin B. Duriska, John C. Jeffery, Paul Jensen, Jinzhen Lu, Graham R. Motson, Simon J. Coles, Michael B. Hursthouse and Michael D. Ward, Dalton Trans., 2005, 1910-1923.
  • "A Neutral 3D Copper Coordination Polymer Showing 1D Open Channels and the First Interpenetrating NbO-Type Network", Xian-He Bu, Ming-Liang Tong, Ho-Chol Chang, Susumu Kitagawa and Stuart R. Batten, Angew. Chem. Int. Ed., 2004, 43, 192-195.
  • "A New Self-Penetrating Uniform Net, (8,4) (or 86), Containing Planar 4-Connecting Nodes", Ming-Liang Tong, Xiao-Ming Chen, and Stuart R. Batten, J. Am. Chem. Soc., 2003, 125, 16170-16171.
  • "Malleable Coordination Networks", Stuart R. Batten and Keith S. Murray, Aust. J. Chem., 2001, 54, 605-609.
  • "Coordination Polymers", Stuart R. Batten, Curr. Opin. Solid State Mater. Sci., 2001, 5, 107-114.
  • "Copper(I) dicyanamide coordination polymers: ladders, sheets, layers, diamond-like networks and unusual interpenetration", Stuart R. Batten, Alexander R. Harris, Paul Jensen, Keith S. Murray and Angela Ziebell, J. Chem. Soc., Dalton Trans., 2000,3829-3836.
  • "Ni(tpt)(NO3)2 - A Three-Dimensional Network with the Exceptional (12,3) Topology: A Self-Entangled Single Net", Brendan F. Abrahams, Stuart R. Batten, Martin J. Grannas, Hasan Hamit, Bernard F. Hoskins and Richard Robson, Angew. Chem. Int. Ed., 1999, 38, 1475-1477; Angew. Chem., 1999, 111, 1538-1540.
  • "Interpenetrating Nets: Ordered, Periodic Entanglement", Stuart R. Batten and Richard Robson, Angew. Chem. Int. Ed., 1998, 37, 1460-1494; Angew. Chem., 1998, 110, 1558-1595.
  • "A Cubic 3,4-Connected Net with Large Cavities in Solvated [Cu3(tpt)4](ClO4)3 (tpt = 2, 4, 6-Tri(4-pyridyl)-1, 3, 5-triazine)", Brendan F. Abrahams, Stuart R. Batten, Hasan Hamit, Bernard F. Hoskins and Richard Robson, Angew. Chem. Int. Ed. Engl., 1996, 35, 1690-2; Angew. Chem., 1996, 108, 1794-6.
  • "Two Interpenetrating 3D Networks Which Generate Spacious Sealed-Off Compartments Enclosing of the Order of 20 Solvent Molecules in the Structures of Zn(CN)(NO3)(tpt)2/3.solv (tpt = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, solv = ~3/4C2H2Cl4.3/4CH3OH or ~3/2CHCl3.1/3CH3OH)", Stuart R. Batten, Bernard F. Hoskins and Richard Robson, J. Am. Chem. Soc., 1995, 117, 5385-5386.
    (cf. "Sentencing Molecules to Prison", Robert F. Service, Science, 1995, 268,1698 and Encyclopaedia Britannica, Book of the Year, 1996, 240-241)

Research Outcomes

  • An international reputation in the area of crystal engineering, and world leading expertise on the phenomenon of interpenetration of networks in crystal structures.
  • Batten group funding since 1998 is more than $2.88M, including four ARC Fellowships and five Discovery Grants; CI on grants of more that $12.9M.
  • 228 refereed journal publications, 1 book, 8 book chapters, 89 conference presentations.
  • Lead author of Coordination Polymers: Design, Analysis and Application, Stuart R. Batten, Suzanne M. Neville and David R. Turner, Royal Society of Chemistry, Cambridge, 2009.
  • High citation rates. Total citations (to the Dec. 2011) are 12,237, or over 54 citations per published paper. Twenty-seven papers have over 100 citations each, and 58 have more than 50 citations.H-index = 54, m = 3.6.
  • Publication 14 is one of the most heavily cited papers in its field (over 3000 citations). Publication 42 was the very first 'Highlight' paper written for CrystEngComm, and is the second most highly cited paper to have been published in this journal to date (487 citations). Publication 2 was highlighted in an editorial article in Science, and chosen as one of the highlights of the year for chemistry in the Encyclopaedia Britannica, Book of the Year, 1996. Publication 189 was highlighted as an Editor's Choice in Science. Publications 31, 48, 52, 116, 132 and 170 are highlighted on the covers of their respective journals.
  • Referee for more than 650 papers submitted to 43 different journals since 2000 (including Nature Materials, Nature Chemistry, Chem. Comm., Dalton, New J. Chem., Chem. Soc. Rev., JACS, Inorg. Chem., Angew. Chem., Adv. Mater., Eur. J. Inorg. Chem., Aust. J. Chem.), as well as ARC, NSERC (Canada), SFI (Ireland), Swiss National Science Foundation, Marsden Fund (NZ), Ministry of Education (Singapore), Austrian Science Fund (FWF), Portuguese Foundation for Science and Technology (FCT), KOSK (Norway), NSF (USA) and PRF (USA) funding applications, and beamtime applications for the Bragg Institute and Australian Synchrotron. Examiner for one M.Sc. and five Ph.D. theses.
  • Collaborations with 43 distinct research groups since 2000, based in Australia, China, India, Denmark, New Zealand, Switzerland, Spain, France and the United Kingdom. These include the groups of Keith Murray (Monash), Leone Spiccia (Monash), Bruce West (Monash), Doug MacFarlane (Monash), Glen Deacon (Monash), Alan Chaffee (Monash), Cameron Kepert (Sydney), Christine J. McKenzie and Hans Toftlund (Odense, Denmark), Michael D. Ward (Sheffield, UK), Samiran Mitra (Jadavpur U, Kolkata, India), Partha Sarathi Mukherjee (Bangalore, India), Miao Du and Xiao-Jun Zhao (Tianjin Normal U, Tianjin, China), Xian-He Bu and Jimin Zheng (Nankai U, Tianjin, China), Song Gao and Zheming Wang (Beijing, China), Xian-Ming Zhang (Linfen, China), Yao-Yu Wang (Northwest U, Xi'an, China), Quan-Guo Zhai (Shaanxi Normal U, Xi'an, China), Shi-Yao Yang (Xiamen, China), En-Bo Wang and Jian-Fang Ma (Northeast Normal U, Changchun, China), Xiao-Ming Chen and Ming-Liang Tong (Sun Yat-Sen U, Guangzhou, China), Hong Deng (South China Normal U, Guangzhou, China), Yu-Bin Dong (Jinan, China), Rong Cao and Can-Zhong Lu (Fuzhou, Fujian, China), Fupei Liang (Guangxi Normal U, Guilin, China), Ning-Hai Hu and Hongjie Zhang (Changchun Institute of Applied Chemistry, China), Xiang He (Shanghai U, China), Hegen Zheng (Nanjing U, Nanjing, China), Li-Ya Wang (Luoyang Normal U, China), Chun-Sen Liu (Zhengzhou U of Light Industry, Zhengzhou, China), Zheng-Bo Han (Liaoning U, Shenyang, China), Feng Luo (East China Institute of Technology, Fuzhou, Jiangxi, China), Paul Kruger (U Canterbury, NZ), Ed Constable (Basel, Switzerland), Jean-Franois Létard (ICMCB, Bordeaux, France), and Matthew Hill (Materials Science and Engineering, CSIRO).

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.