Pryce, Mary T.
Pryce, Mary T.
Pryce, Mary T.
Now showing 1 - 3 of 3
- PublicationPhotoinduced rearrangements in transition metal compounds(Elsevier, 2010-11)
;In this contribution a range of photo induced ligand rearrangements observed for first and second row transition metal and organometallic compounds are discussed. The processes discussed include photoinduced ligand exchange, linkage isomerisation and changes occurring within the coordination sphere of the compounds such as cis-trans and fac-mer isomerisations. The relevance of these processes for photocatalytic cycles or their application as synthetic tools is discussed where appropriate. 819Scopus© Citations 46
- PublicationSynthesis, Photo-, and Electrochemistry of Ruthenium Bis(bipyridine) Complexes Comprising a N-heterocyclic Carbene Ligand(American Chemical Society, 2013-05-06)
; ; ; ; ;Analogues of [Ru(bpy)3]2+ were prepared in which one pyridine ligand site is substituted by a N-heterocyclic carbene (NHC) ligand, that is, either by an imidazolylidene with a variable wingtip group R (R = Me, 3a; R = Et, 3b; R = iPr, 3c), or by a benzimidazolylidene (Me wingtip group, 3d), or by a 1,2,3-triazolylidene (Me wingtip group, 3e). All complexes were characterized spectroscopically, photophysically, and electrochemically. An increase of the size of the wingtip groups from Me to Et or iPr groups distorts the octahedral geometry (NMR spectroscopy) and curtails the reversibility of the ruthenium oxidation. NHC ligands with methyl wingtip groups display reversible ruthenium oxidation at a potential that reflects the donor properties of the NHC ligand (triazolylidene > imidazolylidene > benzimidazolylidene). The most attractive properties were measured for the triazolylidene ruthenium complex 3e, featuring the smallest gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the series (2.41 eV), a slightly red-shifted absorption profile, and reasonable excited-state lifetime (188 ns) when compared to [Ru(bpy)3]2+. These features demonstrate the potential utility of triazolylidene ruthenium complexes as photosensitizers for solar energy conversion. 372Scopus© Citations 95
- PublicationDye sensitised solar cells with nickel oxide photocathodes prepared via scalable microwave sintering(RSC Publishing, 2012-12-06)
; ; ; ; ; ; ;Photoactive NiO electrodes for cathodic dye-sensitised solar cells (p-DSCs) have been prepared with thicknesses ranging between 0.4 and 3.0 mm by spray-depositing pre-formed NiO nanoparticles on fluorine-doped tin oxide (FTO) coated glass substrates. The larger thicknesses were obtained in sequential sintering steps using a conventional furnace (CS) and a newly developed rapid discharge sintering (RDS) method. The latter procedure is employed for the first time for the preparation of p-DSCs. In particular, RDS represents a scalable procedure that is based on microwave-assisted plasma formation that allows the production in series of mesoporous NiO electrodes with large surface areas for p-type cell photocathodes. RDS possesses the unique feature of transmitting heat from the bulk of the system towards its outer interfaces with controlled confinement of the heating zone. The use of RDS results in a drastic reduction of processing times with respect to other deposition methods that involve heating/calcination steps with associated reduced costs in terms of energy. P1-dye sensitized NiO electrodes obtained via the RDS procedure have been tested in DSC devices and their performances have been analysed and compared with those of cathodic DSCs derived from CS-deposited samples. The largest conversion eﬃciencies (0.12%) and incident photon-to-current conversion eﬃciencies, IPCEs (50%), were obtained with sintered NiO electrodes having thicknesses of B1.5–2.0 mm. In all the devices, the photogenerated holes in NiO live significantly longer (th B 1 s) than have previously been reported for P1-sensitized NiO photocathodes. In addition, P1-sensitised sintered electrodes give rise to relatively high photovoltages (up to 135 mV) when the triiodide–iodide redox couple is used. 2202Scopus© Citations 66