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I recently co-organised the RSC Dalton Regional conference for Inorganic Chemistry (with Dr L.J. Gillie) hosted at the University of Huddersfield.
Re-Programmable Molecular Systems
The aim of this research is to control the assembly of supramolecular species via allosteric interactions. For example, a system has been designed and synthesized whose coordination mode changes in the presence of Ba2+. Thus a dinuclear double helicate complex is formed with Hg(II) (i.e. [Hg2(L)2]4+) but in the presence of Ba2+ a mononuclear complex is formed (i.e. [Hg(L)Ba]4+). This is a very significant advance in the area of supramolecular chemistry, with implications in many areas, from increasing the fundamental understanding of biological processes to materials chemistry. Preliminary communications on this work have been published (see Angew. Chem. 2004; Chem. Commun. 2005). This novel area of reprogrammable systems and use in areas such as optical sensors, metal specific ligands and controlling metal-metal communication are showing great promise (see Angew. Chem. 2005).
Ditopic Cryptate-Containing Sensors
A series of cryptates, containing N- and O- donor exo-binding binding domains, has been synthesized to produce sensors capable of sensing s- and d-block metal ions. For example, a europium cryptate derivative has been prepared which contains an exo-crown ether unit. It is hoped that upon coordination of s-block metal ions to the crown ether will significantly modulate the emission properties of the f-block metal ion (in collaboration with Dr S. Faulkner, Univ. Manchester). Furthermore, progress has been made in the preparation of a similar system which contains a [Ru(bipy)2]2+ fragment bound to a cryptate; such a system will allow detection and measurement of Na+ ions in aqueous media. The stability of these systems makes them attractive for in vitro measurement of biologically important metal ions.
Member of Materials and Catalysis Research Centre
Bullock, S., Davidson, F., Faulkner, R., Parkes, G., Rice, C. and Towns-Andrews, E. (2017) ‘Control of metallo-supramolecular assemblies via steric, hydrogen bonding and argentophilic interactions; formation of a 3-dimensional polymer of circular helicates’ CrystEngComm , 19 (9), pp. 1273-1278. ISSN 1466-8033
Abdulla, O., Clayton, A., Faulkner, R., Gill, D., Rice, C., Walton, S. and Sweeney, J. (2017) ‘Catalytic sp3 -sp3 Functionalisation of Sulfonamides: Late-Stage Modification of Drug-Like Molecules’ Chemistry - A European Journal , 23 (7), pp. 1494-1497. ISSN 0947-6539
Adams, K., Ball, A., Birkett, J., Brown, L., Chappell, B., Gill, D., Lo, P., Patmore, N., Rice, C., Ryan, J., Raubo, P. and Sweeney, J. (2016) ‘An iron-catalysed CC bond-forming spirocyclization cascade providing sustainable access to new 3D heterocyclic frameworks’ Nature Chemistry , 9 (4), pp. 396-401. ISSN 1755-4330
Scattergood, P., Ross, D., Rice, C. and Elliott, P. (2016) ‘Labilizing the Photoinert: Extraordinarily Facile Photochemical Ligand Ejection in an [Os(N^N)3]2+Complex’ Angewandte Chemie International Edition , 55 (36), pp. 10697-10701. ISSN 1433-7851
Scattergood, P., Khushnood, U., Tariq, A., Cooke, D., Rice, C. and Elliott, P. (2016) ‘Photochemistry of [Ru(pytz)(btz)2]2+and Characterization of a ?1-btz Ligand-Loss Intermediate’ Inorganic Chemistry , 55 (15), pp. 7787-7796. ISSN 0020-1669
Hemming, K., Blackburn, J., Molyneux, G., Pitard, A., Rice, C., Page, M., Afshinjavid, S., Javid, F., Coles, S. and Horton, P. (2016) ‘Synthesis, Conformation and Antiproliferative Activity of Isothiazoloisoxazole 1,1-dioxides’ Organic and Biomolecular Chemistry , 14, pp. 2134-2144. ISSN 1477-0539
Faulkner, R., Harding, L., Higginson, J., Rice, C. and Slater, C. (2014) ‘Formation of a Dimer of Trinuclear Helicates which Encapsulates an Array of Six Hydrogen-Bonded Anions’ Angewandte Chemie International Edition . ISSN 14337851
Aiken, S., Booth, K., Gabbutt, C., Heron, B., Rice, C., Charaf-Eddin, A. and Jacquemin, D. (2014) ‘The first structural and spectroscopic characterisation of a ring-opened form of a 2H-naphtho[1,2-b]pyran: a novel photomerocyanine’ Chemical Communications , 50 (58), pp. 7900-7903. ISSN 1359-7345
Welby, C., Armitage, G., Bartley, H., Wilkinson, A., Sinopoli, A., Uppal, B., Rice, C. and Elliott, P. (2014) ‘Photochemistry of RuII4,4?-Bi-1,2,3-triazolyl (btz) Complexes: Crystallographic Characterization of the Photoreactive Ligand-Loss Intermediatetrans-[Ru(bpy)(?2-btz)(?1-btz)(NCMe)]2+’ Chemistry - A European Journal . ISSN 0947-6539
Aiken, S., Gabbutt, C., Gillie, L., Heywood, J., Jacquemin, D., Rice, C. and Heron, B. (2013) ‘The Remarkable Hyperchromicity of Ketohydrazone Dyes and Pigment Lakes Derived from 4-Morpholino-2-naphthol’ European Journal of Organic Chemistry , 2013 (36), pp. 8097-8107. ISSN 1434-193X
Clegg, O., Harding, L., Miller, J. and Rice, C. (2013) ‘Tricarbonylchlorido(6'7'-dihydro-5H-spiro[cyclopentane-1,6'-dipyrido-[3,2-d:2',3'-f][1,3]diazepine]-?2N1,N11)-rhenium(I)’ Acta Crystallographica Section E , 69 (10), p. m526. ISSN 1600-5368
Welby, C., Rice, C. and Elliott, P. (2013) ‘Unambiguous Characterization of a Photoreactive Ligand-Loss Intermediate’ Angewandte Chemie International Edition , 52 (41), pp. 10826-10829. ISSN 1433-7851
Clegg, O., Harding, L., Miller, J. and Rice, C. (2013) ‘Tricarbonylchlorido(6,7-dihydro-5H-spiro[cyclohexane-1,6-dipyrido[3,2-d :2,3-f][1,3]diazepine]-?2N1,N11)rhenium(I)’ Acta Crystallographica Section E , 69, p. m527. ISSN 1600-5368
Cooke, D., Cross, J., Fennessy, R., Harding, L., Rice, C. and Slater, C. (2013) ‘Steric control of the formation of dinuclear double helicate and dinuclear meso-helicate assemblies’ Chemical Communications , 49 (71), pp. 7785-7787. ISSN 1359-7345
Elliott, P., Welby, C., Rice, C., Gibson, E., Gilmartin, L., Marriott, R. and Zahid, A. (2013) ‘Luminescent biscyclometalated arylpyridine iridium(III) complexes with 4,4-bi-1,2,3-triazolyl ancillary ligands’ Dalton Transactions , 42 (37), pp. 13527-13536. ISSN 14779226
Bullock, S., Harding, L., Moore, M., Mills, A., Piela, S., Rice, C., Towns-Andrews, E. and Whitehead, M. (2013) ‘Synthesis of Ligands Containing N-oxide Donor Atoms and Their Assembly into Metallosupramolecular Structures.’ Dalton Transactions . ISSN 1477-9226
Welby, C., Grkinic, S., Zahid, A., Uppal, B., Gibson, E., Rice, C. and Elliott, P. (2012) ‘Synthesis, characterisation and theoretical study of ruthenium 4,4?-bi-1,2,3-triazolyl complexes: fundamental switching of the nature of S1 and T1 states from MLCT to MC’ Dalton Transactions , 41 (25), pp. 7637-7646. ISSN 1477-9226
Cox, N., Harding, L., Jones, J., Pope, S., Rice, C. and Adams, H. (2012) ‘Probing solution behaviour of metallosupramolecular complexes using pyrene fluorescence’ Dalton Transactions , 41 (5), pp. 1568-1573. ISSN 14779226
Sutton, C., Harding, L., Hardie, M., Riis-Johannessen, T. and Rice, C. (2012) ‘Allosteric Effects in a Ditopic Ligand Containing Bipyridine and Tetra-aza-crown Donor Units’ Chemistry - A European Journal , 18 (12), pp. 3464-3467. ISSN 0947-6539
Hemming, K., Khan, M., Kondakal, V., Rice, C., Pitard, A. and Qamar, M. (2012) ‘Pyridines from azabicyclo[3.2.0]hept-2-en-4-ones through a proposed azacyclopentadienone’ Organic Letters , 14 (1), pp. 126-129. ISSN 15237060
Clegg, O., Fennessy, R., Harding, L., Rice, C., Riis-Johannessen, T. and Fletcher, N. (2011) ‘Diastereoselective assembly of pentanuclear circular helicates’ Dalton Transactions , 40 (45), pp. 12381-12387. ISSN 1477-9226
Uppal, B., Booth, R., Ali, N., Lockwood, C., Rice, C. and Elliott, P. (2011) ‘Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands’ Dalton Transactions , 40 (29), pp. 7610-7616. ISSN 1477-9226
Allen, K., Faulkner, R., Harding, L., Rice, C., Riis-Johannessen, T., Voss, M. and Whitehead, M. (2010) ‘Head-To-Tail and Heteroleptic Pentanuclear Circular Helicates’ Angewandte Chemie International Edition , 49 (37), pp. 6655-6658. ISSN 1433-7851
Bain, L., Bullock, S., Harding, L., Riis-Johannessen, T., Midgley, G., Rice, C. and Whitehead, M. (2010) ‘Controlling the formation of metallosupramolecular assemblies by metal ionic radii’ Chemical Communications , 46 (20), pp. 3496-3498. ISSN 1359-7345
Bullock, S., Felton, C., Fennessy, R., Harding, L., Andrews, M., Pope, S., Rice, C. and Riis-Johannessen, T. (2009) ‘Coumarin-based luminescent ligand that forms helicates with dicationic metal ions’ Dalton Transactions , 47, pp. 10570-10573. ISSN 14779226
Bullock, S., Gillie, L., Harding, L., Rice, C., Riis-Johannessen, T. and Whitehead, M. (2009) ‘Isomeric pyridyl-thiazole donor units for metal ion recognition in bi- and tri-metallic helicates’ Chemical Communications , 2009 (32), pp. 4856-4858. ISSN 1359-7345
Felton, C., Harding, L., Jones, J., Kariuki, B., Pope, S. and Rice, C. (2008) ‘A wavelength and lifetime responsive cryptate-containing fluorescent probe for zinc ions in water’ Chemical Communications (46), pp. 6185-6187. ISSN 1359-7345
Clayton, H., Harding, L., Irvine, J., Jeffery, J., Riis-Johannessen, T., Laws, A., Rice, C. and Whitehead, M. (2008) ‘Metal-specific allosteric activation and deactivation of a diamine’ Chemical Communications (1), p. 108. ISSN 1364-548X
Bokolinis, G., Riis-Johannessen, T., Jeffery, J. and Rice, C. (2008) ‘Synthesis and X-ray structures of cadmium-containing dinuclear double helicates derived from ligands containing N-oxide units’ New Journal of Chemistry , 32 (1), pp. 115-119. ISSN 11440546
Riis-Johannessen, T., Harding, L., Jeffery, J., Moon, R. and Rice, C. (2007) ‘Allosteric deprogramming of a trinuclear heterometallic helicate’ Dalton Transactions (16), pp. 1577-1587. ISSN 14779226
Baylies, C., Harding, L., Jeffery, J., Moon, R., Rice, C. and Riis-Johannessen, T. (2007) ‘Electrostatic control of the formation of heteroleptic transition metal helicates’ New Journal of Chemistry , 31 (8), pp. 1525-1529. ISSN 11440546
Jeffery, J., Riis-Johannessen, T., Anderson, C., Adams, C., Robinson, A., Argent, S., Ward, M. and Rice, C. (2007) ‘Localization and Delocalization in a Mixed-Valence Dicopper Helicate’ Inorganic Chemistry , 46 (7), pp. 2417-2426. ISSN 00201669
Jeffery, J., Rice, C., Harding, L., Baylies, C. and Riis-Johannessen, T. (2007) ‘Ligand Reprogramming in Dinuclear Helicate Complexes: A Consequence of Allosteric or Electrostatic Effects?’ Chemistry - A European Journal , 13 (18), pp. 5256-5271. ISSN 09476539
Rice, C (2006) ‘Metal-assembled anion receptors’ Coordination Chemistry Reviews , 250 (23-24), pp. 3190-3199. ISSN 0010-8545
Bokolinis, G., Riis-Johannessen, T., Harding, L., Jeffery, J., McLay, N. and Rice, C. (2006) ‘This facile interconversion of dinuclear double helicates and side-by-side species: a reprogrammable ligand with potential sensor applications’ Chemical Communications , pp. 1980-1982. ISSN 1364-548X
Coldwell, J., Felton, C., Harding, L., Moon, R., Pope, S. and Rice, C. (2006) ‘Barium induced modulation of NIR emission in a neodymium cryptate complex’ Chemical Communications , 2006, pp. 5048-5050. ISSN 1364-548X
Riis-Johannessen, T., Jeffery, J., Robson, A., Rice, C. and Harding, L. (2005) ‘Solution and solid-state complexes of the potentially tetradentate pyridyl-thiazole ligand 6,6?-bis(4-methylthiazol-2-yl)-2,2?-bipyridine with Co, Ni, Cu, Cd, Hg, Cu and Ag’ Inorganica Chimica Acta , 358 (9), pp. 2781-2798. ISSN 0020-1693
Baylies, C., Riis-Johannessen, T., Harding, L., Jeffery, J., Moon, R., Rice, C. and Whitehead, M. (2005) ‘Allosteric-Controlled Metal Specificity of a Ditopic Ligand’ Angewandte Chemie International Edition , 44 (42), pp. 6909-6912. ISSN 1433-7851
Baylies, C., Jeffery, J., Miller, T., Moon, R., Rice, C. and Riis-Johannessen, T. (2005) ‘Allosteric pitch length tuning of a dinuclear double helicate’ Chemical Communications , pp. 4158-4160. ISSN 1364-548X
Baylies, C., Harding, L., Jeffery, J., Riis-Johannessen, T. and Rice, C. (2004) ‘Allosteric and electrostatic reprogramming of a ditopic ligand’ Angewandte Chemie International Edition , 43 (34), pp. 4515-4518. ISSN 14337851
Harding, L., Jeffery, J., Riis-Johannessen, T., Rice, C. and Zeng, Z. (2004) ‘Anion control of the formation of geometric isomers in a triple helical array’ Dalton Transactions (16), pp. 2396-2397. ISSN 14779226
Harding, L., Jeffery, J., Riis-Johannessen, T., Rice, C. and Zeng, Z. (2004) ‘Anion control of ligand self-recognition in a triple helical array’ Chemical Communications (6), pp. 654-655. ISSN 1364-548X
Rice, C., Baylies, C., Harding, L., Jeffery, J., Paul, R. and Ward`, M. (2003) ‘Cadmium-containing pyridylthiazole complexes: crystal structures and solution behaviour of mononuclear, dinuclear double helicate and dinuclear triple helicate complexes’ Polyhedron , 22 (5), pp. 755-762. ISSN 02775387
Rice, C., Baylies, C., Clayton, H., Jeffery, J., Paul, R. and Ward, M. (2003) ‘Novel multidentate pyridyl/thiazolyl ligands containing terpyridine units: formation of dinuclear and trinuclear double helicate complexes.’ Inorganica Chimica Acta , 351, pp. 207-216. ISSN 00201693
Rice, C., Onions, S., Vidal, N., Wallis, J., Senna, M., Pilkington, M. and Stoeckli-Evans, H. (2002) ‘The Coordination Chemistry of 3,3?-Diamino-2,2?-bipyridine and Its Dication: Exploring the Role of the Amino Groups by X-ray Crystallography’ European Journal of Inorganic Chemistry , 2002 (8), pp. 1985-1997. ISSN 1434-1948
Rice, C., Baylies, C., Harding, L., Jeffery, J. and Paul, R. (2001) ‘Pyridyl-thiazole multidentate ligands: metal-specific recognition of a combination of ligands from a mixture’ Journal of the Chemical Society Dalton Transactions (20), pp. 3039-3044. ISSN 1472-7773
Rice, C., Guerrero, A., Bell, Z., Paul, R., Motson, G., Jeffery, J. and Ward, M. (2001) ‘New hybrid ditopic ligands containing fused phenanthroline and crown ether units’ New Journal of Chemistry , 25 (2), pp. 185-187. ISSN 11440546
Rice, C., Worl, S., Jeffery, J., Paul, R. and Ward, M. (2001) ‘New multidentate ligands for supramolecular coordination chemistry: double and triple helical complexes of ligands containing pyridyl and thiazolyl donor units’ Journal of the Chemical Society Dalton Transactions (5), pp. 550-559. ISSN 14727773
Pope, S., Rice, C., Ward, M., Morales, A., Accorsi, G., Armaroli, N. and Barigelletti, F. (2001) ‘Folding of a poly(oxyethylene) chain as probed by photoinduced energy transfer between Ru and Ospolypyridine termini’ Journal of the Chemical Society Dalton Transactions (15), pp. 2228-2231. ISSN 14727773
Rice, C., Worl, S., Jeffery, J., Paul, R. and Ward, M. (2000) ‘Pyridyl-thiazoles as a new class of ligand for metallosupramolecular chemistry: formation of double and triple helicates with Cu(ii)’ Chemical Communications (16), pp. 1529-1530. ISSN 1364-548X
Norman, N., Orpen, A., Quayle, M. and Rice, C. (2000) ‘Diborane(4) compounds incorporating thio- and seleno-carboranyl groups’ New Journal of Chemistry , 24 (11), pp. 837-839. ISSN 11440546
Rice, C., Ward, M., Nazeeruddin, M. and Gratzel, M. (2000) ‘Catechol as an efficient anchoring group for attachment of rutheniumpolypyridine photosensitisers to solar cells based on nanocrystalline TiO2 films’ New Journal of Chemistry , 24 (9), pp. 651-652. ISSN 11440546
This proposal is concerned with the synthesis and characterisation of a number of Re(I)-containing species capable of specific detection of amino acids in biological media. Although amino acids are present within the human body large excesses of these compounds can have deleterious affects (e.g. increased levels of phenylalanine is caused by the metabolic disorder phenylketonuria (PKU)). Early detection of this disease is essential so that treatment can be established. As early diagnosis is required for successful treatment every newborn in both Western Europe and North America is tested for this disorder. Although there are tests, current detection methods are either lengthy (such as the Guthrie test which uses bacterial growth) or use expensive and delicate machinery (tandem mass spectrometry).
This PhD programme involves the synthesis of Re(I)-containing complexes which will bind amino acids (via a tritopic coreceptor) and in doing so the luminescent properties will be modulated. Luminescent species are relatively easy to detect and can be detected even at very low concentrations. Furthermore the instrumentation required to this can be made small, portable and robust. This work will hopefully advance the detection of amino acids and go some way to the construction of portable, inexpensive and easy to use detectors for amino acids.
Lithium is important for the management of treatment resistant depression. However, the body is particularly sensitive to high serum levels of lithium and lithium intoxication occurs at approximately 1.3 mmol/l and is characterised by vomiting, diarrhoea, tremor, cognitive impairment and agitation. At higher levels (2-3 mmol/l) severe confusion, convulsions, coma and death can occur quickly and at these levels lithium intoxication is a medical emergency and is easily confused with alcohol (ethanol) intoxication and missed. Current tests for lithium require large and complicated equipment which are expensive and time consuming to use and dont meet the needs of patients in a modern NHS. What is needed is a quick and accurate test for this drug, which can be used either in the patients homes or in emergency settings such as A&E departments. This project involves the synthesis of transition metal complexes that are able to detect lithium ions at low concentrations in aqueous media.
The ability of some multidenate ligands, upon reaction with transition metals, to self-assemble into double and triple stranded helicates has been known for some time. This project exploits the ability of pyridyl-thiazole ligands to form dinuclear triple helicates upon complexation to suitable transition metal ions. Incorporation of substituents onto these ligands will produce, upon complexation, specific cavities. These cavities can be tailored to form receptors for specific molecules such as anions, cations and electron-poor/electron-rich compounds and the selectivity of the host-guest interaction measured.
Synthesis of cavities is an important area of chemistry due to their ability to be host specific; this has important implications especially in the area of sensors
The detection of "s block" metals (e.g. sodium, potassium, calcium, magnesium etc) in the environment, chemical processes and the human body is of great importance. The usual methods for detection of these chemicals are often difficult and require both lengthy procedures and expensive equipment.
This PhD programme is concerned with the synthesis and characterisation of transition metal complexes that are capable of sensing biologically, industrially and environmentally important metals. These complexes will "sense" by colorimetry i.e. in the presence of the required metal the compounds will change colour dramatically and thus they can be detected by the naked eye.