Prof. Lee Brammer
Professor of Inorganic and Solid State Chemistry
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.
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
Solid State Chemistry; Crystallography
- The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors.
Smith DA, Beweries T, Blasius C, Jasim N, Nazir R, Nazir S, Robertson CC, Whitwood AC, Hunter CA, Brammer L & Perutz RN, J Am Chem Soc, 137(36), 11820-11831, (2015).
- Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: A multi-technique mechanistic study.
Vitõrica-Yrezábal IJ, Libri S, Loader JR, Mínguez Espallargas G, Hippler M, Fletcher AJ, Thompson SP, Warren JE, Musumeci D, Ward MD & Brammer L, Chemistry, 21(24), 8799-8811, (2015).
- A solvent-resistant halogen bond.
Robertson CC, Perutz RN, Brammer L & Hunter CA, Chem. Sci., 5(11), 4179-4183, (2014).
- Metal hydrides form halogen bonds: Measurement of energetics of binding.
Smith DA, Brammer L, Hunter CA & Perutz RN, J Am Chem Soc, 136(4), 1288-1291, (2014).
- Zipping and unzipping of a paddlewheel metal-organic framework to enable two-step synthetic and structural transformation.
Smart P, Mason CA, Loader JR, Meijer AJ, Florence AJ, Shankland K, Fletcher AJ, Thompson SP, Brunelli M, Hill AH & Brammer L, Chemistry, 19(11), 3552-3557, (2013).
- Chemical transformations of a crystalline coordination polymer: A multi-stage solid-vapour reaction manifold.
Vitórica-Yrezábal IJ, Mínguez Espallargas G, Soleimannejad J, Florence AJ, Fletcher AJ & Brammer L, Chemical Science, 4(2), 696-708, (2013).
- Energetics of halogen bonding of group 10 metal fluoride complexes.
Beweries T, Brammer L, Jasim NA, McGrady JE, Perutz RN & Whitwood AC, J Am Chem Soc, 133(36), 14338-14348, (2011).
- Mechanistic insights into a gas-solid reaction in molecular crystals: the role of hydrogen bonding.
Mínguez Espallargas G, van de Streek J, Fernandes P, Florence AJ, Brunelli M, Shankland K & Brammer L, Angew Chem Int Ed Engl, 49(47), 8892-8896, (2010).
- Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds.
Mínguez Espallargas G, Zordan F, Arroyo Marín L, Adams H, Shankland K, van de Streek J & Brammer L, Chemistry, 15(31), 7554-7568, (2009).
- Noncovalent interactions under extreme conditions: high-pressure and low-temperature diffraction studies of the isostructural metal-organic networks (4-chloropyridinium)2(CoX4) (X = Cl, Br).
Mínguez Espallargas G, Brammer L, Allan DR, Pulham CR, Robertson N & Warren JE, J Am Chem Soc, 130(28), 9058-9071, (2008).
- Metal fluorides form strong hydrogen bonds and halogen bonds: measuring interaction enthalpies and entropies in solution.
Libri S, Jasim NA, Perutz RN & Brammer L, J Am Chem Soc, 130(25), 7842-7844, (2008).
- Ligand Substitution within nonporous crystals of a coordination polymer: elimination from and insertion into Ag-O bonds by alcohol molecules in a solid-vapor reaction.
Libri S, Mahler M, Mínguez Espallargas G, Singh DC, Soleimannejad J, Adams H, Burgard MD, Rath NP, Brunelli M & Brammer L, Angew Chem Int Ed Engl, 47(9), 1693-1697, (2008).
- Reversible gas uptake by a nonporous crystalline solid involving multiple changes in covalent bonding.
Espallargas GM, Hippler M, Florence AJ, Fernandes P, van de Streek J, Brunelli M, David WI, Shankland K & Brammer L, J Am Chem Soc, 129(50), 15606-15614, (2007).
- Ligand flexibility and framework rearrangement in a new family of porous metal-organic frameworks.
Hawxwell SM, Espallargas GM, Bradshaw D, Rosseinsky MJ, Prior TJ, Florence AJ, van de Streek J & Brammer L, Chem Commun (Camb)(15), 1532-1534, (2007).
- Supramolecular chemistry of halogens: Complementary features of inorganic (M-X) and organic (C-X ') halogens applied to M-X center dot center dot center dot X '-C halogen bond formation.
Zordan F, Brammer L & Sherwood P, J Am Chem Soc, 127(16), 5979-5989, (2005).
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.
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.
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.
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).
- Second Year Demonstrating
- Third Year Laboratory Projects
- Fourth Year Research Project
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