SNIC-RSC Joint Symposium on Inorganic Chemistry 7-8 January 2013 Institute of Materials Research and Engineering, A*STAR, Singapore www.rsc.org SNIC-RSC Joint Symposium on Inorganic Chemistry Welcome addresses The Republic of Singapore became an independent and sovereign republic in 1965 The Singapore National Institute of Chemistry (SNIC) was established in March 1970 as a national body to develop the interest of chemistry and chemical scientists in Singapore In its earlier years, it was closely linked to the Royal Institute of Chemistry (RIC) in London through the RIC Malaya Section and later the RIC Singapore Section After four decades of nation building, it became clear that chemical science and engineering is central to the educational, social and economic development in Singapore The R&D manpower shot up 71% from Year 2000 (25,220) to 2012 (43,164) whilst the national 5-year Science & Technology budget rose from S$6 bn in 2001-2005 to S$16.1bn in 2011-2015 More than 20% of the national GDP came from the manufacturing sector, which is anchored by two major industries viz chemicals and electronics that are well served by the chemistry and engineering professionals The biomedical science, which also provides attractive career opportunities for many chemists, added another 10% to the manufacturing account The World Economic Forum in its Global Competitiveness Report 2012-2013 ranked Singapore the 2nd most competitive country/economy in the world There are 12 pillars in the ranking framework which include the likes of higher education and training, innovation, and technological readiness All of these are key drivers in the numerous conferences, symposia, workshops and seminars that SNIC run regularly We are delighted to have this opportunity to jointly organise this symposium with the Royal Society of Chemistry (RSC) of UK with which we have had four decades of fruitful relationship and partnership in different forms, tracing back to the days of the RIC We have chosen the theme “Inorganic Chemistry” for this meeting not only because of its central role in chemistry and traditional research strength in Singapore, but also of its value to the modern science and technology in areas such as catalysis for pharmaceutical manufacturing and biomass conversion, solidstate fuel-cell and photovoltaic materials, metal composites and functional engineering materials, metal oxides and semi-conducting materials, photo-emissive complexes, covalent porous solids, etc etc This symposium creates an ideal platform for Singapore academics and researchers to foster new collaborative links with our UK counterparts It also provides an opportunity for our young scientists and students to experience the wonders of inorganic chemistry and share our enthusiasm in this traditional science in contemporary context We wish to take this opportunity to invite more people to enter and advance this field through interdisciplinary collaboration and bilateral cooperation On behalf of SNIC, I wish everyone a pleasant and productive meeting Professor Andy Hor D.Sc.(Lond), D.Phil(Oxon), FSNAS, FSNIC, FRSC President, Singapore National Institute of Chemistry, http://www.snic.org.sg/ President-Elect, Federation of Asian Chemical Societies, http://www.facs-as.org/ Executive Director, Institute of Materials Research & Engineering, A*Star, http://www.imre.a-star.edu.sg/ Professor, National University of Singapore, http://www.chemistry.nus.edu.sg/ SNIC-RSC Joint Symposium on Inorganic Chemistry Dear Colleagues The Royal Society of Chemistry (RSC) is delighted to be co-organizing this “SNIC-RSC Joint Symposium on Inorganic Chemistry” with the Singapore National Institute of Chemistry (SNIC) and the Institute of Materials Research (IMRE) which is part of the Agency for Science, Technology & Research We very much appreciate the commitment of SNIC and IMRE in hosting this one and a half day meeting and we thank Professor Andy Hor and his team for all their help and support We hope that it will be another successful and memorable SNIC-RSC activity that will facilitate and foster future collaborations between the societies and scientists in each country As part of the symposium, the RSC will renew its 5-year Collaboration Agreement with SNIC and we look forward to continuing our collaboration which benefits those in the chemical sciences communities in both Singapore and the United Kingdom The RSC is a learned society, concerned with advancing chemistry as a science, developing its applications, and disseminating chemical knowledge, and a professional body that maintains professional qualifications and sets high standards of competence and conduct for professional chemists We have 47,500 members worldwide drawn from all areas of the chemical sciences We are active in industry, academia and education and play an important role in shaping science policy both in the UK and internationally In addition the RSC is a major publisher of research journals, magazines, databases and books that cover all areas of the chemical sciences The RSC’s Dalton Division looks after the interests of inorganic chemists across the world, frequently running meetings jointly with other chemical societies across the globe The breadth and importance of inorganic chemistry and its applications has been recognized by the RSC’s Roadmap activities (www.rsc.org/roadmap) directed at identifying where the big challenges and opportunities lie for the chemical sciences This symposium tackles some of these challenges under the headings: Catalysis, Energy and Scarce Resources The speakers are international experts in the areas of inorganic chemistry which underpin the development of new products and processes in these important areas This symposium will also highlight some of the achievements of women in science, including contributions from world-leading researchers on the Roadmap challenges We hope that the presentations will stimulate the exchange of ideas and experiences between all participants, setting a good platform for discussions We are also very thankful to Johnson Matthey, UK and the British High Commission of Singapore, Southeast Asia Science and Innovation for their support of the event We thank all of the speakers, poster presenters and participants in advance for their contributions Once again a very warm welcome to what promises to be an exciting and unique scientific event We hope that the symposium will provide a springboard for future activities and that it will foster new research collaborations Professor Lesley Yellowlees President Royal Society of Chemistry Professor Peter Tasker President RSC Dalton Division SNIC-RSC Joint Symposium on Inorganic Chemistry SNIC-RSC Joint Symposium on Inorganic Chemistry Monday 7th January, 2013 Time Event 9:00 am Ms Judith Slater, Deputy High Commissioner in Singapore, Director of Trade & Investment Professor Andy Hor, SNIC President, IMRE, Singapore Professor Lesley Yellowlees, RSC President, University of Edinburgh, UK Introduction and welcome 9:30 am Signing of International Cooperation Agreement between the Royal Society of Chemistry (RSC) and the Singapore National Institute of Chemistry (SNIC) 9:45 am Tea/coffee break 10:15 am Professor Nicola Armaroli, National Research Council, Italy Energy for the 21st century: Challenges and opportunities for chemistry 11:00 am Professor Xiaogang Liu, National University of Singapore/IMRE, Singapore Rare-earth nanocrystals: A new class of luminescent bioprobes 11:30 am Professor Christian Nijhuis, National University of Singapore, Singapore Turning around a diode at the molecular level 12:00 pm Professor Jishan Wu, National University of Singapore/IMRE, Singapore Open-shell polycyclic hydrocarbons 12:30 pm Lunch 1:30 pm Professor Peter Tasker, RSC Dalton Division President, University of Edinburgh, UK “Resources that don’t cost the earth” – GreenER extractive metallurgy 2:15 pm Professor Tomislav Friščić, McGill University, Canada New low-energy and low-solvent approaches to chemical and materials synthesis 3:00 pm Tea/coffee break and poster session sponsored by Johnson Matthey, UK 4:30 pm Dr Stephen Poulston, Johnson Matthey, UK New commercial applications for inorganic chemistry 5:15 pm Professor Pak-Hing Leung, Nanyang Technological University, Singapore Palladacycle-catalysed asymmetric hydrophosphination: direct and efficient synthesis of functionalised chiral tertiary phosphines 5:45 pm Dr He-Kuan Luo, IMRE, Singapore Highly active catalysts for ethylene polymerisation 6:15 pm Close of day Chair Dr Kathleen Too Royal Society of Chemistry, UK Professor Andy Hor SNIC President, IMRE, Singapore Professor Nicola Armaroli National Research Council, Italy Professor Polly Arnold University of Edinburgh, UK SNIC-RSC Joint Symposium on Inorganic Chemistry SNIC-RSC Joint Symposium on Inorganic Chemistry Tuesday 8th January, 2013 Time Event 8:30 am Professor Lesley Yellowlees, RSC President, University of Edinburgh, UK Women in Science: What has chemistry ever done for me? 9:00 am Professor Vivian Yam, The University of Hong Kong, Hong Kong Versatile metal-ligand chromophoric building blocks – From design to assembly and functions 9:45 am Professor Bin Liu, National University of Singapore/IMRE, Singapore Solid state dye-sensitised solar cells 10:15 am Tea/coffee break 10:45 am Professor Rong Xu, Nanyang Technological University, Singapore Development of low-cost & efficient photocatalyst systems for production of solar fuels 11:15 am Dr Jia Min Chin, IMRE, Singapore Mixing work and play – Liquid marble formation, control and encapsulation 11:45 am Professor Polly Arnold, University of Edinburgh, UK Carbon-carbon and carbon-element bond forming reactions with organometallic f-block complexes 12:30 pm Professors Andy Hor, SNIC President, and Peter Tasker, RSC Dalton Division President Poster prize awards and closing remarks 12:45 pm End of conference Chair Dr Kathleen Too Royal Society of Chemistry, UK Professor Lesley Yellowlees RSC President University of Edinburgh, UK SNIC-RSC Joint Symposium on Inorganic Chemistry Speaker biographies Professor Nicola Armaroli National Research Council, Italy Email: nicola.armaroli@isof.cnr.it Nicola Armaroli got the PhD in chemical sciences in 1994 from the University of Bologna, Italy After postdoc periods in USA and Italy, in 1997 he joined the Italian National Research Council (CNR) where he became Senior Research Scientist in 2002 and Research Director in 2007 His scientific activity is concerned with the photochemistry and photophysics of coordination compounds, carbon nanostructures and supramolecular materials, with focus on luminescence, light harvesting, and photoinduced energy- and electrontransfer This basic research is related to technological applications such as solar energy conversion and novel materials for efficient lighting Nicola Armaroli has given invited lectures at international conferences, universities and research centres worldwide To date he has published books on the subject of energy and over 150 papers and review articles on international journals Since 2010, he has served as chairman of the Working Party on Chemistry and Energy of EUCheMS the European Association for Chemical and Molecular Sciences Nicola Armaroli is also an active consultant and science communicator for the public at large on the issues of energy, natural resources and environment, also through interviews and contributions on mass media He was awarded the 2001 Grammaticakis-Neumann International Prize in Photochemistry and the Italian Galileo Prize 2009 for science communication Updated list of publication and citation profile: http://www.researcherid.com/rid/B-9094-2009 SNIC-RSC Joint Symposium on Inorganic Chemistry Professor Polly Arnold University of Edinburgh, UK Email: Polly.Arnold@ed.ac.uk Polly obtained a BA from Oxford in 1994 and DPhil in 1997 from Sussex She was awarded a Fulbright Scholarship for postdoctoral research at MIT, and returned to the UK to a lectureship at the University of Nottingham in 1999 She moved to the University of Edinburgh in 2007, and was promoted to Chair in 2009 She is also currently an EPSRC Leadership Research Fellow Other recent research awards include the Bessel Prize from the Humboldt Foundation, the Chancellor’s prize of the University of Edinburgh, and the Hans Fischer Senior Fellowship from the Institute of Advanced Study in Munich In the last year, she has been awarded the Rosalind Franklin medal by the Royal Society, the Corday-Morgan prize by the Royal Society of Chemistry, and elected a Fellow of the Royal Society of Edinburgh and a Fellow of the Royal Society of Chemistry Polly’s research is focused on exploratory synthetic chemistry that challenges preconceived ideas of reactivity and bonding, particularly in f-block metal systems The group is working towards innovative catalytic transformations and in the activation of small, unreactive molecules such as carbon oxides and hydrocarbons New knowledge about uranium and its neighbours is necessary for the reduction of worldwide nuclear waste legacies and for future fuel design; new catalytic conversions of hydrocarbons and simple carbon oxides will be key enablers for the future renewables-based chemical industry SNIC-RSC Joint Symposium on Inorganic Chemistry Dr Jia Min Chin Institute of Materials Research and Engineering, Singapore Email: chinjm@imre.a-star.edu.sg Dr Jia Min Chin was awarded the prestigious I I Rabi Fellowship from Columbia University (New York) as well the National Science Scholarship from A*STAR to pursue her undergraduate studies in Columbia College, Columbia University, where she graduated magna cum laude with a B.A in Biochemistry within three years During her years at Columbia, she worked in the lab of Professor Jack R Norton, studying organometallic chromium hydride complexes Subsequently, she pursued her PhD in the lab of Professor Richard R Schrock at MIT on dinitrogen activation by molybdenum and tungsten complexes, receiving a PhD in Inorganic Chemistry in 2010 She started working at the Institute of Materials Research and Engineering (IMRE) in Singapore towards the end of 2010, and is currently studying Metal-Organic Frameworks, as well as superhydrophobic materials and their applications She is a strong believer in utilising simple chemical techniques for materials synthesis and tailoring She is also active in engaging students, having mentored more than ten students in the time she has been at IMRE Her research has led to publications in various journals including Chem Commun., J Am Chem Soc., Inorg Chem., CrystEngComm etc Professor Tomislav Friščić McGill University, Canada Email: tomislav.friscic@mcgill.ca Tomislav Friščić is an Assistant Professor in the area of Green Chemistry at McGill University, Canada, since August 2011, and a member of the FRQNT Centre for Green Chemistry and Catalysis (CCVC) and the FRQNT Centre for Self-Assembled Structures (CSACS) He is an experienced researcher in solid-state chemistry, in particular in the mechanochemistry and solvent-free transformations of metal oxides and the design of molecular co-crystals for pharmaceutical applications He has co-authored 100 papers and 10 book chapters with over 1900 citations and an h-index of 30 Following a B.Sc degree in chemical crystallography at the University of Zagreb (Croatia) in 2001, he conducted doctoral studies with Len MacGillivray at the University of Iowa (USA) on using solid-state co-crystals to direct organic photosynthesis In 2006 he took up postdoctoral research with William Jones at the University of Cambridge (UK) in the area of mechanochemistry and pharmaceutical materials science From 2008 to 2011, he has been a Herchel Smith Research Fellow at the University of Cambridge, investigating the dynamic nature of solids and using principles of supramolecular chemistry to develop new, cleaner and energy-efficient methods to convert inorganic substances into functional materials His work on solid-state self-assembly processes was awarded with a RSC Harrison-Meldola Medal and lectureship in 2011 SNIC-RSC Joint Symposium on Inorganic Chemistry Professor Andy Hor President, Singapore National Institute of Chemistry President-Elect, Federation of Asian Chemical Societies Executive Director, Institute of Materials Research & Engineering, A*Star Professor, National University of Singapore Institute of Materials Research and Engineering, Singapore Email: andyhor@imre.a-star.edu.sg Andy Hor was a graduate of Imperial College (B.Sc.(Hon)) and Oxford University (D.Phil.) Born in Hong Kong, he came to Singapore (and subsequently naturalised as Singaporean) after postdoctoral associateship at Yale University, rose to the rank of Professor of Chemistry at the National University of Singapore (NUS) in 2000, became Fellow of the Teaching Academy of NUS in 2009, and took up numerous management roles including Vice-Dean (Academic) of Science and Head of Chemistry He is the President of the Singapore National Institute of Chemistry, President-Elect of the Federation of Asian Chemical Societies, and Fellow of the Singapore National Academy of Science (SNAS) He is currently seconded to the Institute of Materials Research & Engineering (IMRE) under Agency for Science, Technology & Research (A*STAR) as its Executive Director, and appointed as Advisor to the Early-Career Researchers of A*Star He chairs the A*Star Scientific Conference (Oct 2012), 15th Asian Chemical Congress (Aug 2013) and 41st International Coordination Chemistry Conference (July 2014) in Singapore He chairs the SNAS & A*Star Young Scientist Award of Singapore He is the Jury President for L’Oréal Singapore for Women in Science National Fellowships 2012 He also chairs the Advisory Committee for Hazardous Substances & Toxic Wastes of the National Environment Agency For three decades, his academic thrusts have been delicately balanced among research, education, management & services To date, he has published ~300 ISI papers with ~570 citations in 2011 in the area of organometallic materials & catalysis as well as supramolecular assembly and heterometallic syntheses He is a member of the Advisory Board of Dalton Transactions, Inorganica Chimica Acta, Chemistry – An Asian Journal and the A*Star Scientific Publication He is also the Associate Editor of the Australian Journal of Chemistry and Editor of the Journal of Molecular & Engineering Materials His awards include NSTB Young Scientist & Engineer Award (1991), ASEAN Achievement Award (Science) (1994), NUS Outstanding Educator Award (2002), GIST-SNIC Award in Chemistry Education (2010), Outstanding Chemist Award (2011), among others SNIC-RSC Joint Symposium on Inorganic Chemistry Professor Pak-Hing Leung Nanyang Technological University, Singapore Email: pakhing@ntu.edu.sg Pak-Hing Leung, born in Hong Kong (1956) Education Polytechnic of North London (BSc Hons 1982, supervised by Peter A Tasker) Australian National University (PhD 1986, supervised by S Bruce Wild) University of Toronto & University of Chicago (posdoc fellow, 1987-1989, supervised by Brice Bosnich) Career Lecturer - Professor at National University of Singapore (NUS) (1989-2005) Vice Dean and Head of Department at the Nanyang Technology University (NTU) (2005-2011) Currently Professor and Associate Chair at NTU Awards University Researcher Award (NUS, 1998) 14 University Teaching Awards (since 1993, both from NUS and NTU) SNIC-RSC Joint Symposium on Inorganic Chemistry Abstracts Energy for the 21st century: Challenges and opportunities for chemistry Nicola Armaroli Istituto per la Sintesi Organica e la Fotoreattività, CNR - Consiglio Nazionale delle Ricerche Via Gobetti 101, 40129 Bologna, Italy During the 20th century, world primary energy consumption has increased over ten times, leading to an unprecedented improvement of the quality of life in some regions of the world This was made possible thanks to a massive exploitation of fossil fuels (coal, oil, natural gas) that, in the decades to come, has to be significantly moderated due to environmental constraints In particular, anthropogenic climate forcing caused by the dumping of CO2 and other greenhouse gases in the atmosphere.1 Solar energy, in its multifaceted forms, is the most abundant, reliable, sustainable, and safe primary energy source that can profitably replace fossil fuels.2,3 The transition to a solar-powered world will be a long and difficult process4 in which some key trends can be already envisaged: (1) growing share of electricity in energy end use;5 (2) increase of efficiency in energy production and consumption;2,3 (3) establishment of technologies for the manufacturing of “solar fuels”;6,7 (4) recycling the equipment used for converting renewable energy flows, that is often made of materials available in very limited supply (eg precious metals).8 The solutions to the tremendous challenge of energy transition require the mobilisation of huge human and economic resources in all scientific and technological fields In this context chemistry, and particularly inorganic chemistry, will play a prominent role, as it will be discussed in selected examples, related to materials for solar energy conversion9 and efficient lighting technologies.10 N Armaroli and V Balzani, The legacy of fossil fuels, Chem.-Asian J., 2011, 6, 768-784 2 N Armaroli and V Balzani, Energy for a sustainable world From the oil age to a sun powered future, Wiley-VCH, Weinheim, 2011 3 N Armaroli, V Balzani and N Serpone, Powering planet earth - energy solutions for the future, Wiley-VCH, Weinheim, 2013 4 N Armaroli and V Balzani, The future of energy supply: Challenges and opportunities, Angew Chem Int Ed., 2007, 46, 52-66 5 N Armaroli and V Balzani, Towards an electricity-powered world, Energ Environ Sci., 2011, 4, 3193-3222 J Barber, Photosynthetic energy conversion: Natural and artificial, Chem Soc Rev., 2009, 38, 185-196 7 RSC - Royal Society of Chemistry, Solar fuels and artificial photosynthesis: Science and innovation to change our future energy options, 2012, http://www.rsc.org/ScienceAndTechnology/Policy/Documents/solar-fuels.asp BK Reck and TE Graedel, Challenges in metal recycling, Science, 2012, 337, 690-695 9 J Iehl, M Vartanian, M Holler, JF Nierengarten, B Delavaux-Nicot, JM Strub, A Van Dorsselaer, YL.Wu, J Mohanraj, K Yoosaf and N Armaroli, Photoinduced electron transfer in a clicked fullerene-porphyrin conjugate, J Mater Chem., 2011, 21, 1562-1573 10 RD Costa, E Orti, HJ Bolink, F Monti, G Accorsi and N Armaroli, Luminescent ionic transition-metal complexes for light-emitting electrochemical cells, Angew Chem Int Ed., 2012, 51, 8178-8211 17 SNIC-RSC Joint Symposium on Inorganic Chemistry Carbon-carbon and carbon-element bond forming reactions with organometallic f-block complexes Polly L Arnold,*a Stephen M Mansell, Rebecca C White, Isobel Marr,a Anne I Germeroth,a Zoe R Turner,a Ronan Bellabarbab and Robert P Toozeb a EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, The King’s Buildings, Edinburgh, EH9 3JJ, UK b Sasol Technology (UK) Ltd., Purdie Building, St Andrews, KY16 9ST, UK Organometallic compounds of the lanthanides and actinides have shown many interesting small molecule activation reactions, including hydrocarbon C-H bond cleavage, over the last 25 years We will show new f-block complexes of polydentate tethered N-heterocyclic carbenes which can activate small molecules such as CO and CO2 They can also add polar substrates across the metal-NHC bond (c.f Frustrated Lewis Pair, FLP behaviour) The reversibility of this addition reaction provides an alternative to OA/RE reactions in d-block chemistry and catalysis, and allows a variety of heteroatom reagents to functionalise the metal-bound group Reactions that form C-C, C-Si, and other C-element bonds will be presented We will also show how, in the absence of the NHC as small molecule directing group, even the simplest UIII complexes, normally regarded as starting materials, are also capable of the reductive activation and functionalisation of CO, CO2, N2, and arenes References PL Arnold and IJ Casely, Chem Rev., 2009, 109, 3599 ZR Turner, R Bellabarba, RP Tooze, PL Arnold, J Am Chem Soc., 2010, 132, 4050 PL Arnold, ZR Turner, R Bellabarba, RB Tooze, Chem Sci., 2011, 2, 77 SM Mansell, N Kaltsoyannis and PL Arnold, J Am Chem Soc., 2011, 133, 9036 PL Arnold, SM Mansell, D McKay, and L Maron, Nature Chem., 2012, 4, 668 18 SNIC-RSC Joint Symposium on Inorganic Chemistry Mixing work and play – Liquid marble formation, control and encapsulation Jia Min Chin Institute of Materials Research and Engineering, 3, Research Link, Singapore, 117602 Since the seminal discovery of liquid marbles by Quéré and co-workers, tremendous interest has been incited in this material Essentially, liquid marbles are non-stick droplets (usually of water) with a hydrophobic coating and possess the ability to roll on various surfaces (and even on the surface of water) without wetting them As such, they are objects of fascination for many people In this talk, the synthesis and tailoring of highly hydrophobic nano- and microparticles based on metal-organic frameworks, as well as metal oxides, will be discussed Through the use of various types of particles, liquid marbles with specific functionalities (eg magnetic, gas-sensing, pH-sensing and light-responsive liquid marbles) may be formed These liquid marbles present a new method of manipulating liquid droplets and have been demonstrated by various groups to be useful as micro-reactors, and even for remotely-controlled release of chemicals I will also talk about the various methods of liquid marble encapsulation that have been attempted thus far, as well as our own efforts in this area In particular, I will mention “supergluing” of liquid marbles, whereby chemical vapor deposition of ethyl-2-cyanoacrylate on a liquid marble followed by moisture-initiated polymerisation leads to a water-containing capsule 19 SNIC-RSC Joint Symposium on Inorganic Chemistry New low-energy and low-solvent approaches to chemical and materials synthesis Tomislav Friščić Department of Chemistry and FRQNT Centre for Green Chemistry and Catalysis, McGill University, Canada The development of new, highly efficient and environmentally-friendly methodologies for the synthesis of molecules and materials is one of the central missions of modern chemical synthesis In the past ten years, reactions initiated and/or sustained by mechanical force have evolved from a laboratory curiosity into a powerful alternative to conventional synthesis.1 This presentation will illustrate how such mechanochemical reactions can transform the solvent- and energy-intensive syntheses of porous metal-organic frameworks (MOFs) and metallodrugs2 into processes akin to molecular self-assembly under mild conditions.1 A recently emerged “accelerated aging” technique3 for low-energy and scalable synthesis of functional solids directly from raw metal oxide and sulfide precursors will be presented Finally, the use of mechanochemistry in establishing a working model of a “solvent-free” research laboratory will be illustrated in the context of coordination polymers and organic synthesis,4 together with the first methodology for in situ monitoring of mechanochemical reactions Topologically selective mechanosynthesis of MOFs from ZnO (top), and the results of real-time monitoring of the synthesis of porous ZIF-8 by mechanochemical milling (bottom) References T Friščić Chem Soc Rev 2012, 41, 3493 V André et al Angew Chem Int Ed 2011, 50, 7858 MJ Cliffe et al Chem Sci 2012, 3, 2495 4 Štrukil et al Green Chem 2012, 14, 2462 20 SNIC-RSC Joint Symposium on Inorganic Chemistry Palladacycle-catalysed asymmetric hydrophosphination: Direct and efficient synthesis of functionalised chiral tertiary phosphines Pak-Hing Leung Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Over the past few decades, enantiomerically pure tertiary phosphines have attracted considerable interest by virtue of the fact that they have proven themselves as important ligands in asymmetric synthesis and catalysts In spite of the continuing progress in the development of analogus ligand systems such as carbenes, chiral phosphines have maintained their role as the most frequently employed class of ligands in asymmetric catalysis However, due to the lack of a natural chiral pool, high reactivity and, in particular, the configurational instability of phosphorus stereocenters, the synthesis of tertiary phosphines has posted considered challenges to synthetic chemists Furthermore these asymmetric ligands could NOT be prepared in the catalytic manner, due to the inherent challenges in the product elimination process In this talk, the development of a range of chiral Aryl-Pd complexes as chiral templates (stoichoimetry amount) and chiral catalysts for the direct synthesis of functionalised tertiary phosphines via hydrophosphination reaction will be presented 21 SNIC-RSC Joint Symposium on Inorganic Chemistry Solid state dye-sensitised solar cells Bin Liu*, Xizhe Liu, Long Wang, Zhaosheng Xue Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117576 Institute of Materials Research & Engineering, Research Link, Singapore, 117602 Dye sensitised solar cells (DSSCs) have attracted intense research interest due to their high efficiency and low fabrication cost The high power efficiencies (>11% for liquid electrolyte based DSSCs) are attributed to the ultrafast charge transfer from the dye to the TiO2, the high surface area of the TiO2 film, the broad absorption of the dye, and the efficient separation of opposite charges into different materials However, these DSSCs possess the problem of low stability since a volatile liquid electrolyte is used In addition, the iodine/iodide redox couple also leads to grid corrosion In order to eliminate difficulties associated with liquid electrolyte, considerable research is devoted to the development of solid state dye sensitised solar cells Different hole conductors, such as p-type semiconductors, ionic liquid electrolytes and polymer electrolytes have been used As compared to the liquid electrolyte based DSSCs, the conversion efficiency of most solid state DSSCs employed p-type semiconductors is relatively low, which is due to the low intrinsic conductivity of organic hole transporting materials (HTMs), the high frequencies of charge recombination from TiO2 to HTMs, and the poor electronic contact between dye molecules and HTMs In this talk, we present our recent progress in solid state dye sensitised solar cells, which include dye engineering and interfacial engineering1 and in-situ polymerisation of polymer hole transporting materials to yield an average efficiency of 6.1%,2 which represents a remarkable improvement for polymer HTM based DSSCs References R Zhu, C Jiang, B Liu* and S Ramakrishna Adv Mater 2009, 21(9), 994-1000 X Liu, W Zhang, S Uchida, L Cai, B Liu* and S Ramakrishna Adv Mater 2010, 22, E150–E155 Rare-earth nanocrystals: A new class of luminescent bioprobes Xiaogang Liu Department of Chemistry, National University of Singapore, Singapore 117543 Institute of Materials Research and Engineering A*STAR, Research Link, Singapore 117602 Lanthanide-doped inorganic nanocrystals typically comprise an insulating host material and lanthanide dopant ions embedded in the host lattice The luminescence of lanthanide-doped nanocrystals primarily originates from intra-configurational 4f electron transitions within the localised dopant ions In stark contrast to quantum dots, quantum confinement effects are typically not expected in lanthanide-doped nanocrystals due to small Bohr radius of the exciton in the host, as well as weak interaction between the 4f electrons of the dopant ions and the host material As a result, the luminescence properties of lanthanide-doped nanocrystals closely resemble those of the bulk counterparts The emission profiles of lanthanide-doped nanocrystals are usually manipulated by varying dopant compositions and concentrations in the host lattice In this talk, I will present a doping principle that is capable of altering nanocrystal growth processes with simultaneous control over crystallographic phase and size of the nanocrystals I will also discuss our recent efforts in developing novel photon upconversion schemes based on energy migration processes and utilising upconversion nanocrystals as novel luminescent labels for biological applications 22 SNIC-RSC Joint Symposium on Inorganic Chemistry Highly active catalysts for ethylene polymerisation He-Kuan Luo Institute of Materials Research and Engineering A*STAR, Research Link, Singapore 117602 Driven by catalyst innovation, polyolefins has grown into one of the largest synthetic resins in modern chemical industry The key challenge is to develop practically high performance catalysts that have high activity, good stability and produce high MW polymers In this seminar, a brief overview will be given on silica-supported classical Ziegler-Natte catalysts, bi-nuclear and multi-nuclear late transition metal catalysts and self-assembled multi-nuclear catalysts for ethylene polymerisation These catalysts are capable of producing useful materials including copolymers of ethylene with alpha-olefins and UltraHigh-Molecular-Weight Polyethylene (UHMWPE) Turning around a diode at the molecular level Christian A Nijhuis Department of Chemistry, National University of Singapore, Science Drive 3, Singapore 117543 Understanding the mechanisms of charge transport across molecules, or self-assembled monolayers, is important in organic based photovoltaics, OLEDs, energy storage, bio-electronic devices, etc Issues regarding how molecular orbitals couple to the electrodes, or the influence of subtle changes of the intermolecular interactions between the molecules in the SAMs, on the performance of molecular electronic devices has rarely experimentally been addressed We identified a molecular diode: junctions with SAMs of S(CH2)11Fc, ie, SAMs with ferrocene at the top, on Ag bottom-electrodes contacted with EGaIn (an eutectic alloy of Ga and In) top-electrodes rectified currents with a rectification ratio of 100, while those junctions with SAMs of S(CH2)10CH3, ie, SAMs without Fc units, did not rectify To study the influence of subtle changes in the intermolecular interactions between the molecules in the SAMs, and the coupling of the molecular orbitals with the electrodes, we fabricated devices with a series molecules of the type S(CH2)nFc (with n = 3, 4, …, 15) and SCnFcCn-13 (with n = 1, 2, 3, …, 15), respectively We found that devices with n is odd are ten times better diodes than those devices with n = even This so-called odd-even effect originates from small changes in the structures of the SAMs, which, in turn, depends on the van der Waals interactions between the molecules in the SAM By controlling the coupling of the molecular orbitals with the electrodes, we succeeded at “turning” around a diode at the molecular level 23 SNIC-RSC Joint Symposium on Inorganic Chemistry New commercial applications for inorganic chemistry Stephen Poulson Johnson Matthey, JMTC, Blount’s Court, Sonning Common, Reading, RG4 9NH, UK Though there can be significant barriers to the introduction of new commercial applications involving high value, advanced materials it is possible if substantial benefits can be demonstrated Two examples are given, one commercialised one still in the development stage, which illustrate new opportunities for inorganic chemistry in the areas of sustainability and energy Though food packaging is often regarded as contributing to waste it can in fact substantially reduce waste JM has developed an ethylene scavenger technology (e+) which can significantly increase shelf life and reduce food wastage for fresh produce such as fruit Ethylene is a fruit hormone that promotes fruit ripening and so has a major impact on the post-harvest lifetime of fresh produce This represents a significant new opportunity in active packaging Efficient cleaning and conditioning of biomass derived syngas for use in fuel synthesis continues to be a significant technical barrier to commercialising biofuels/chemicals derived from biomass gasification These fuels/chemicals are regarded as a sustainable alternative to their petrochemical alternatives The process relies on high temperature hydrocarbon steam reforming which is traditionally carried out with Ni based catalysts Rh based catalysts are also known to be effective, though are considerably more expensive per kilo We have assessed the relative effectiveness of a range of nickel and rhodium containing catalysts for the conversion of model tar compounds (benzene, toluene and naphthalene) in a simulated bio-syngas stream containing up to 100 ppm H2S and up to % CH4 at temperatures from 700-900 °C Selected catalysts were also evaluated using oak modeled syngas from a NREL pilot scale gasification unit The best Ni and Rh catalyst was then selected for testing under real conditions using oak derived syngas Rh based catalysts gave significantly better hydrocarbon conversion than Ni catalysts at comparable conditions Though H2S was found to significantly reduce hydrocarbon conversion near complete conversion of methane and tar could be achieved on a Rh based catalyst at 850 °C with a GHSV of 5,000 h-1 Furthermore, the H2S deactivation was fully reversible and could be attributed to a transient site-blocking mechanism The best catalyst demonstrated 200 hr on stream durability with little apparent loss of activity Initial estimates indicate that the additional cost of Rh over Ni based catalysts can be justified from the improved efficiency that results 24 SNIC-RSC Joint Symposium on Inorganic Chemistry “Resources that don’t cost the earth” – GreenER extractive metallurgy Peter A Tasker University of Edinburgh, Edinburgh, UK, EH9 3JJ The Royal Society of Chemistry has been working with others on the Roadmap Project (www.rsc.org/roadmap) to define the challenges and opportunities which chemists face in the next decade The report “Resources that Don’t Cost the Earth” (http://rsc.li/metals-2012) deals with a topic which is particularly relevant to this conference How are we going to maintain supplies of materials which will be essential for products and processes to improve our environment the quality of life of future genertaions? In this talk I propose to focus on the recovery and recyling of metals Whilst in the context of total systems it is very unlikely that we can ever make these processes genuinely sustainable, there is great potential for making huge improvements to the materials and energy balances involved An example is the introduction of hydrometallurgical flow sheets to replace pyrometallurgical (smelting-type) processes An apropriate combination of reactions for leaching/solvent extraction-stripping/electrolytic reduction allows all the reagents to be recycled and, for recovery of copper from oxidic ores (see below), results in splitting the oxide into its component elements Such an achievemment requires highly selective complexing agents1 which function as solvent extractants, transporting the desired metal (copper) into a water-immiscible solvent such as kerosene The simple phenolic oximes shown perform this function in processes which now account for approximately 25% of the world’s copper production Ligand design is one of the key factors in achieving high strength and selectivity of metal solvent extraction In this talk we will focus on exploiting both inner and outer sphere coordination chemistry.2,3 References 1 Turkington JR, Bailey PJ, Love JB, Wilson AM, et al., Chem Commun Feature Article in press Forgan RS; Roach BD; Wood PA; et al., Inorg, Chem 2010, 4515-22 Ellis RJ, Chartres J, Henderson DK, Cabot R, Richardson PR et al.; Chem Eur J., 2012, 18, 7715-28 25 SNIC-RSC Joint Symposium on Inorganic Chemistry Open-shell polycyclic hydrocarbons Jishan Wu Department of Chemistry, National University of Singapore, Science Drive 3, Singapore 117543 Institute of Materials Research and Engineering, 3, Research Link, Singapore, 117602 I will discuss two types of open-shell polycyclic hydrocarbons:1 Z-shaped zethrenes and2 extended p-quinodimethanes The discussion will include:1 their challenging synthesis and stabilisation strategy,2 their characterisations of the ground-state electronic and geometric structure by steady-state and transient absorption, VT NMR, ESR, SQUID, FT-Raman, crystallographic analysis assisted by DFT calculations; and3 their unique optical, electronic and magnetic properties References Sun, Z et al., Chem Soc Rev 2012, 41, 7857 Li, Y et al J Am Chem Soc 2012, 134, 14913 Zeng, Z et al J Am Chem Soc 2012, 134, 14513 Sun, Z et al J Am Chem Soc 2011, 133, 11896 Li, J et al Chem Sci 2012, 3, 846 26 SNIC-RSC Joint Symposium on Inorganic Chemistry Development of low-cost & efficient photocatalyst systems for production of solar fuels Rong XU School of Chemical & Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459 Finding long-term solutions to meet the growing energy demands of human society is one of the greatest challenges we face today The widespread use of the free and sustainable solar energy is unavoidable in the long run However, only less than 1.0% of current world energy is derived from sunlight mainly by solar photovoltaic and solar heat Due to the intermittent nature of solar energy, a mix of solutions will be required to compensate the output variability and limitation of the individual technologies The research in our group focuses on the development of nano-engineered particulate semiconductor photocatalysts and molecular systems for efficient conversion of solar energy to chemical energy via two types of photocatalytic reactions: water splitting for hydrogen production and carbon dioxide reduction to hydrocarbons and oxygenates So far, we have tried to 1) tailor the morphological properties and band structures of semiconductor materials for efficient light absorption, and charge separation and transportation; 2) develop earth abundant co-catalysts nanoparticles; and 3) design fine-tuned homogeneous molecular systems including photosensitizers and metal-complex catalysts to achieve usable light extension to longer wavelengths Versatile metal-ligand chromophoric building blocks – From design to assembly and functions Vivian Wing-Wah Yam Institute of Molecular Functional Materials† and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, PR China Recent works in our laboratory have shown that novel photofunctional metal complexes could be assembled through the use of various metal-ligand chromophoric building blocks In this presentation, various design and synthetic strategies together with the successful isolation of new classes of photofunctional complexes of selected metals will be described A number of these complexes have been shown to display rich luminescence behaviour The luminescence properties have been studied and their emissive origins elucidated Correlations of the luminescence behaviour with the electronic and structural effects of the metal complexes have also been made By understanding the spectroscopic origin and the structure-property relationships, the characteristics of these complexes could be finetuned for specific applications and functions through rational design and assembly strategies based on various coordination motifs or weak non-covalent metallophilic and π-π interactions These metalcontaining molecular materials may find potential applications and functions as efficient triplet emitters and in chemosensing and luminescence signalling † Areas of Excellence Scheme, University Grants Committee (Hong Kong) 27 SNIC-RSC Joint Symposium on Inorganic Chemistry Women in Science: What has chemistry ever done for me? Lesley Yellowlees, RSC President University of Edinburgh, UK As the first woman president of the Royal Society of Chemistry in its 171 year history I am passionate about inspiring and increasing the numbers of women studying and working in the sciences It is of great concern that the majority of women with qualifications in science, technology, engineering and mathematics (STEM) subjects not work in STEM areas in Scotland This is in contrast to men The consequence is a serious loss to the economy and to the subject area The ‘leaky pipeline’ as it has been christened has significant implications for skills shortages in STEM areas This is not a problem unique to Scotland but what can be done to fix the leak? So why so many female scientists opt not to have a career in STEM? If there was only one reason then it would be easier to tackle Instead there are many, such as long working hours, lack of support, unconscious bias, macho culture, family considerate working conditions, inflexible funding structures, isolation Some of these reasons are real and some are perceptions but the distinction between these two doesn’t really matter In contrast I have had a very positive experience in Chemistry and try and make it a priority to remember the help and support I was given and to give back Statistics, observations and recollections will all feature in the presentation 28 SNIC-RSC Joint Symposium on Inorganic Chemistry NEW for 2013 Journal of Materials Chemistry becomes THREE! From issue 2013 Journal of Materials Chemistry will continue in the form of three journals, each focusing on an area of materials chemistry, divided by the nature of the intended applications of the materials studied The journals will all publish high impact research with a more interdisciplinary nature Journal of Materials Chemistry A – Materials for Energy and Sustainability Journal of Materials Chemistry B – Materials for Biology and Medicine Journal of Materials Chemistry C – Materials for Optical and Electronic Devices www.rsc.org/materialsA www.rsc.org/materialsB www.rsc.org/materialsC www.rsc.org Registered charity number 207890 SNIC-RSC Joint Symposium on Inorganic Chemistry 11th International Conference on Materials Chemistry (MC11) – 11 July 2013 University of Warwick, UK In the 20th year of this international Materials Chemistry conference series, MC11 will bring together researchers from across this exciting field to discuss four key areas of application of materials chemistry Conference Themes l Biomaterials l Electronic, Optical & Magnetic Materials l Energy Materials l Environmental Materials Scientific Committee Dr Andrew Dove (co-chair) University of Warwick Professor Richard Walton (co-chair) University of Warwick Professor Ian Hamley University of Reading Plenary Speakers Professor Robert Cava Princeton University Professor Andy Cooper University of Liverpool Professor Clare Grey FRS University of Cambridge Professor Alan Heeger University of California, Santa Barbara (Chemistry Nobel Laureate 2000) Professor Allan Hoffman University of Washington Professor Samuel Stupp Northwestern University Professor Neil McKeown University of Cardiff Dr Neil Robertson University of Edinburgh Dr Stephen Skinner Imperial College London Key dates Oral abstract deadline – November 2012 Early bird and poster abstract deadline – 10 May 2013 Standard registration deadline – June 2013 www.rsc.org/MC11 Registered Charity Number 207890 Front cover image courtesy of Science Photo library/Shutterstock Royal Society of Chemistry Email: international@rsc.org Registered charity number 207890 © Royal Society of Chemistry 2012 Thomas Graham House Science Park, Milton Road Cambridge, CB4 0WF, UK Tel: +44 (0)1223 420066 Burlington House Piccadilly, London W1J 0BA, UK Tel: +44 (0)20 7437 8656 RSC International Offices São Paulo, Brazil Bangalore, India Beijing, China Tokyo, Japan Shanghai, China Philadelphia, USA [...]... of Regional Symposium on Chemical Engineering since 2005 She is also a member of Editorial Board for Energy Focus and ISRN Nanotechnology 15 SNIC-RSC Joint Symposium on Inorganic Chemistry Professor Vivian W W Yam The University of Hong Kong, Hong Kong Email: wwyam@hku.hk Vivian WW Yam obtained her BSc(Hons) and PhD from The University of Hong Kong, and is currently the Philip Wong Wilson Wong Professor... electron transfer in a clicked fullerene-porphyrin conjugate, J Mater Chem., 2011, 21, 1562-1573 10 RD Costa, E Orti, HJ Bolink, F Monti, G Accorsi and N Armaroli, Luminescent ionic transition-metal complexes for light-emitting electrochemical cells, Angew Chem Int Ed., 2012, 51, 8178-8211 17 SNIC-RSC Joint Symposium on Inorganic Chemistry Carbon-carbon and carbon-element bond forming reactions with... turn, depends on the van der Waals interactions between the molecules in the SAM By controlling the coupling of the molecular orbitals with the electrodes, we succeeded at “turning” around a diode at the molecular level 23 SNIC-RSC Joint Symposium on Inorganic Chemistry New commercial applications for inorganic chemistry Stephen Poulson Johnson Matthey, JMTC, Blount’s Court, Sonning Common, Reading,... photon upconversion schemes based on energy migration processes and utilising upconversion nanocrystals as novel luminescent labels for biological applications 22 SNIC-RSC Joint Symposium on Inorganic Chemistry Highly active catalysts for ethylene polymerisation He-Kuan Luo Institute of Materials Research and Engineering A*STAR, 3 Research Link, Singapore 117602 Driven by catalyst innovation, polyolefins... coordination chemistry. 2,3 References 1 Turkington JR, Bailey PJ, Love JB, Wilson AM, et al., Chem Commun Feature Article in press 2 Forgan RS; Roach BD; Wood PA; et al., Inorg, Chem 2010, 4515-22 3 Ellis RJ, Chartres J, Henderson DK, Cabot R, Richardson PR et al.; Chem Eur J., 2012, 18, 7715-28 25 SNIC-RSC Joint Symposium on Inorganic Chemistry Open-shell polycyclic hydrocarbons Jishan Wu Department of Chemistry, ... career in STEM? If there was only one reason then it would be easier to tackle Instead there are many, such as long working hours, lack of support, unconscious bias, macho culture, family considerate working conditions, inflexible funding structures, isolation Some of these reasons are real and some are perceptions but the distinction between these two doesn’t really matter In contrast I have had a very... Materials for Optical and Electronic Devices www.rsc.org/materialsA www.rsc.org/materialsB www.rsc.org/materialsC www.rsc.org Registered charity number 207890 SNIC-RSC Joint Symposium on Inorganic Chemistry 11th International Conference on Materials Chemistry (MC11) 8 – 11 July 2013 University of Warwick, UK In the 20th year of this international Materials Chemistry conference series, MC11 will bring... mention “supergluing” of liquid marbles, whereby chemical vapor deposition of ethyl-2-cyanoacrylate on a liquid marble followed by moisture-initiated polymerisation leads to a water-containing capsule 19 SNIC-RSC Joint Symposium on Inorganic Chemistry New low-energy and low-solvent approaches to chemical and materials synthesis Tomislav Friščić Department of Chemistry and FRQNT Centre for Green Chemistry. .. very positive experience in Chemistry and try and make it a priority to remember the help and support I was given and to give back Statistics, observations and recollections will all feature in the presentation 28 SNIC-RSC Joint Symposium on Inorganic Chemistry NEW for 2013 Journal of Materials Chemistry becomes THREE! From issue 1 2013 Journal of Materials Chemistry will continue in the form of three... Committee (Hong Kong) 27 SNIC-RSC Joint Symposium on Inorganic Chemistry Women in Science: What has chemistry ever done for me? Lesley Yellowlees, RSC President University of Edinburgh, UK As the first woman president of the Royal Society of Chemistry in its 171 year history I am passionate about inspiring and increasing the numbers of women studying and working in the sciences It is of great concern that