Lee BrammerProf. Lee Brammer

Professor of Inorganic and Solid State Chemistry

Room: C95

Tel: +44-(0)114-22-29536

 Fax: +44-(0)114-22-29346

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Biographical Sketch

Prof. Brammer obtained his BSc in Chemistry from the University of Bristol in 1983, which was followed by a PhD in Inorganic Chemistry from the same institution in 1987. After a NATO Postdoctoral Fellowship at the University of New Orleans (1987-88) and a Postdoctoral Fellowship at Brookhaven National Laboratory, New York (1989-90), he became an Assistant Professor and subsequently an Associate Professor at the University of Missouri-St. Louis (1990-2001). Since 2001 he has been in Sheffield, first as Reader, but since 2008 as Professor of Chemistry.

Research Keywords

Supramolecular chemistry, crystal engineering, solid-state chemistry, functional crystalline materials, intermolecular interactions (esp. hydrogen bonding and halogen bonding), reactions in molecular solids, X-ray and neutron diffraction, computational chemistry

Teaching Keywords

Solid State Chemistry; Crystallography

Selected Publications:

Research Interests

Our current research can be divided, broadly speaking, into three areas: (i) inorganic supramolecular chemistry, (ii) porous coordination framework materials, and (iii) reactions in molecular crystals.

Inorganic Supramolecular Chemistry

Work in this area involves the use of transition metals to influence the construction and properties of supramolecular assemblies in the solid state (crystal engineering) and in solution. We have a number of ongoing projects in this area, but the principal focus is on (a) detailed study of intermolecular interactions using various experimental and computational methods, and (b) the application of the knowledge gained to the construction of network solids (infinite assemblies). Specific systems being studied include:

  • recognition of hydrogen bond donors by halometallate ions and use of halometallates as nodes in hydrogen bonded network construction;
  • linking coordination compounds or organometallic compounds into networks using peripherally situated ligand-centred hydrogen bonds;
  • understanding halogen bonding and the use of halogen bonding as a strong directional interaction that is a viable alternative to hydrogen bonding in supramolecular assembly.

Porous Coordination Framework Materials

Framework materials based upon coordination chemistry, often known as metal-organic frameworks (MOFs), provide a highly versatile alternative to well-established porous materials such as zeolites. Their synthesis is based upon molecular chemistry and they are typically constructed as crystalline network solids using metal centres as nodes which are linked via organic bridging ligands. Applications range from sorption and storage of gases (including hydrogen) and volatile pollutants, to host-guest chemistry for chemical separations and even catalysis. Current efforts in our group are focused on flexible, responsive materials and upon functionalised materials tailored to specific applications. Studies involve synthesis, characterisation by diffraction methods (single crystal, powder) and by a range of other techniques including thermal analyses and spectroscopy.

Facilities

Our research is based in excellent modern synthetic laboratories built in 2003, with an accompanying office suite for students and postdocs. The department maintains excellent instrumentation facilities for spectroscopy (NMR, IR, MS) and we have an outstanding X-ray diffraction facility that is crucial in characterisation of the crystalline materials that we study. We also make extensive use of major national and international facilities for diffraction, in particular high flux synchrotron X-ray facilities in the UK (Daresbury SRS and in future Diamond) and at the ESRF in Grenoble, France.

General

My general philosophy is to make use of a variety of approaches and techniques in pursuing research goals. A better overall understanding is developed by such an approach. Thus, students and postdocs have the opportunity to be exposed to many aspects of chemistry, while perhaps developing greater expertise or interests in certain aspects of a project. Many projects involve some synthesis of organic, organometallic and/or coordination compounds, and will involve supramolecular synthesis and/or materials synthesis methods (e.g. solvothermal synthesis). NMR and IR spectroscopy are widely employed and extensive use is made of diffraction methods, particularly single crystal and powder X-ray diffraction, but also neutron diffraction. Materials characterization methods (e.g. DSC, TGA) are also used where needed and computational chemistry is used to support efforts in other areas. Where appropriate the work is conducted within the research group, but collaborative efforts with other research groups have always proven important in our work. We have established collaborations in areas of synthetic and computational chemistry, diffraction and materials characterisation such as gas sorption and magnetic measurements. Such collaborations often provide opportunities for group members to visit and work in other research labs.

Selected Reviews and book chapters

  • “Combining metals with halogen bonds,” L. Brammer, G. Mínguez Espallargas and S. Libri, CrystEngComm, 2008, 10, 1712-1727.
  • “New trends in crystal engineering,” D. Braga, L. Brammer and N. R. Champness, CrystEngComm, 2005, 7, 1-19.
  • “Developments in inorganic crystal engineering,” L. Brammer, Chem. Soc. Rev., 2004, 34, 476-489.
  • “Metals and Hydrogen Bonds,” L. Brammer, Dalton Trans., 2003, 3145-3157. (Perspective article)
  • “Hydrogen Bonds in Inorganic Chemistry: Application to Crystal Design,” L. Brammer, in "Perspectives in Supramolecular Chemistry, Vol 7: Crystal Design – Structure and Function", ed. G. R. Desiraju, Wiley, 2003, pp 1-75.

Teaching Section

Inorganic Chemistry

Undergraduate Courses Taught

  • Introduction to solid state materials (Year 2)
    The course provides an introduction to the structural aspects of solid state chemistry. The description of crystalline solids in terms of lattices, unit cells and space group symmetry is discussed. Long range and short range order is discussed together with defects in crystalline materials. Band structure is introduced in the context of conduction in solids.
  • Diffraction Techniques in Structural Chemistry (Year 3)
    The course provides an introduction to single crystal X-ray diffraction methods. Information that can be derived from this experimental method is identifies and the limitations of the technique are discussed. The course focuses on symmetry and periodicity, diffraction, structure determination, and the interpretation and evaluation of structural information in a chemical context.
  • Supramolecular Chemistry 1 (Year 4)
    The properties of crystalline solids are derived from the collective properties of their molecular components governed by the crystal structure that describes the assembly of these components. Thus, control over crystal structure, namely crystal design and synthesis, offers the prospect of designer materials with designed properties. This course will provide an introduction to different types of intermolecular interactions that are commonly used in the design of crystalline materials composed of molecular building blocks. The strength, directionality and complementarity of these interactions are discussed. Examples are used to illustrate the design process for materials based upon non-covalent interactions (e.g. hydrogen bonds and halogen bonds) and upon coordination networks, the two most common means of designing crystalline materials. The synthesis and characterisation of these solid-state compounds is discussed. Applications of designed materials are presented, including non-linear optics, gas sorption and catalysis. With particular reference to biologically relevant systems, the issue of polymorphism, solvates and co-crystal formation will be discussed in the context of the pharmaceutical industry.

Tutorial & Workshop Support

  • First Year General Tutorials.
  • Second Year Inorganic Chemistry Tutorials.
  • Third Year Workshops (Diffraction Techniques, Inorganic Materials).
  • Third Year Literature Review.
  • Fourth Year Workshops (Supramolecular Chemistry).

Laboratory Teaching

  • Second Year Demonstrating
  • Third Year Laboratory Projects
  • Fourth Year Research Project

Journal articles

Chapters

  • Mínguez Espallargas G & Brammer L (2007) Characterizations and Applications: Diffraction Studies in Crystal Engineering, Making Crystals by Design: Methods, Techniques and Applications (pp. 241-265)..
  • Minguez Espallargas G & Brammer L (2006) Diffraction Studies in Crystal Engineering In Braga D & Grepioni F (Ed.), Making Crystals by Design (pp. 241-265). Wiley.
  • Minguez Espallargas G & Brammer L (2006) Structure and Bonding in Organometallic Compounds: Diffraction Methods In Parkin G (Ed.), Comprehensive Organometallic Chemistry III (pp. 573-604). Elsevier.
  • Brammer L, Zordan F, Minguez Espallargas G, Purver SL, Arroyo Marin L, Adams H & Sherwood P (2004) Complementary features of inorganic and organic halogens: application to crystal engineering, Transactions of the American Crystallographic Association (pp. 114-122). American Crystallographic Association.
  • Brammer L (2003) Hydrogen Bonds in Inorganic Chemistry: Application to Crystal Design In Desiraju GR (Ed.), Crystal Design: Structure and Function (pp. 1-75). Wiley.
  • Brammer L (1999) Direct and indirect roles of metal centres in hydrogen bonding (pp. 197-210)..

Conference proceedings papers

  • Perutz RN, Smith DA, Brammer L & Hunter CA (2014) Halogen bonds to transition metal hydride complexes. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 248
  • Brammer L (2009) Halogen bonds in inorganic chemistry. ABSTR PAP AM CHEM S, Vol. 238
  • Rodger CS, Brammer L, Harburn JJ & Spilling CD (2001) Self-assembly of transition metal coordination polymers and metallapolygons using pyrimidine derivatives.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 222 (pp U599-U599)
  • Lemke FR, Yardy NM, Petersen JL & Brammer L (2001) RuCl2(PPh3)(3) and hydrosilanes: Travels along a very bumpy reaction manifold.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 221 (pp U689-U689)
  • Brammer L, Rivas UCM, Bruton EA & Sherwood P (2000) Design of hydrogen-bonded materials based on perhalometallates.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 219 (pp U824-U824)
  • Brammer L, Bruton EA & Rivas JCM (1998) An assessment of C-H donors and of halogen acceptors in inorganic hydrogen bonding.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 216 (pp U79-U79)
  • Rivas JCM & Brammer L (1998) Exploitation of hydrogen bonds in linking inorganic molecules.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 216 (pp U86-U86)
  • Sherwood P, Barker JJ, Jennings NA, Maunder CM, Orpen AG, Greatbanks SP, Hillier IH, Brammer L, Kwiatowski W, Collins SJ & deVries AH (1996) Modelling inorganic structure and reactivity: Hybrid ab-initio/classical models for complex systems and environmental effects.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 212 (pp 101-COMP)
  • FANG H, ZHAO D, BRAMMER L & BARTON L (1994) CRYSTAL AND MOLECULAR-STRUCTURE OF MU,2'-SNPH2(B5H8)2 AND MU,1'SNPH2(B5H8)2 - THE 1ST STRUCTURALLY CHARACTERIZED EXAMPLES OF 2 PENTABORANE CAGES LINKED BY A SINGLE HETEROATOM. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 208 (pp 13-INOR)
  • BRAMMER L & ZHAO D (1994) X-RAY AND SPECTROSCOPIC STUDIES OF THE SALTS R3NH+CO(CO)3L-(L = CO, PR3) - COMPOUNDS CONTAINING N-H...CO HYDROGEN-BONDS. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 208 (pp 32-INOR)
  • SCHAVERIEN C & BRAMMER L (1994) ASPECTS OF MONOCYCLOPENTADIENYL LANTHANIDE CHEMISTRY - SYNTHESIS, AND REACTIVITY WITH OLEFINS AND DIENES, OF [Y(C5ME5)(OAR)(MU-H)]2. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 207 (pp 215-INOR)
  • BRAMMER L & ZHAO D (1993) TRANSITION-METALS AS HYDROGEN-BOND ACCEPTORS. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 206 (pp 240-INOR)