The reaction of Cerium Ammonium Nitrate (CAN) with varying amounts of KO(t)Bu produced homometallic Ce(O(t)Bu)4(NC5H5)2 (1) and the heterometallic derivative KCe2(O(t)Bu)10 (3) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce3O(O(t)Bu)9 (2) was obtained from a solution of cerium(IV) tetrakis(tert-butoxide) in n-heptane under stringent precautions to avoid any adventitious hydrolysis. Lewis acid-base reactions of in situ generated Ce(O(t)Bu)4(THF)2 (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [M(O(t)Bu)x]n (M = Ge, Sn; x = 2; n = 2; M = Pb, x = 2; n = 3; M = Al, Fe; x = 3; n = 2) resulted in volatile products of the general formula MCe(O(t)Bu)(4+x) (M = Al (4), Fe (5); x = 3; M = Ge (8), Sn (9), Pb (10); x = 2) in high yields. By dissolving 4 and 5 in pyridine the solvent adducts MCe(O(t)Bu)7(NC5H5) (M = Al (6), Fe (7)) were formed, whereas 8 and 9 reacted with Mo(CO)6 in boiling toluene to yield the termetallic complexes (CO)5MoM(μ2-O(t)Bu)3Ce(O(t)Bu)3 (M = Ge (11), Sn (12)). The new compounds were characterized by comprehensive spectral studies, mass spectroscopy, and single crystal X-ray diffraction analysis.

Luminescent Solar Concentrators (LSCs) have drawn huge interest recently as a technology to pave the way towards the seamless integration of photovoltaics to a range of high-value industries; from architecture and sports to leisure and consumer electronics. Additional device flexibility comes with the inherent ability to attain freeform shapes, expanding the possible fabrication methods, applications and retro-fitting techniques. Unfortunately, flexible LSCs suffer from curvature induced losses which can severely reduce their efficiency, inhibiting the potential of large-scale devices. In this work, we experimentally demonstrate an all-silicone based flexible LSC and Distributed Bragg Reflector (DBR) combination diminishing curvature induced losses. The DBRs, fabricated using scalable solution-based processes, exhibit optical properties precisely engineered to partner our LSCs, as well as high uniformity, resistance to temperature and curvature. Comprehensive modelling shows that for large-scale devices (1m 2) we can essentially decouple the performance of the LSC from curvature, steering the technology towards commercial viability.

An advanced synthesis for the homometallic derivative [Ce2(O(t)Bu)8] (1) starting from [Ce(O(t)Bu)2{N(SiMe3)2}2] was developed. Structural characterization of a cerium(IV) complex and its decomposition products confirmed the coexistence of both ether elimination and Ce-O bond cleavage processes, which lead to the formation of [Ce3O(O(t)Bu)10] and [Ce3(O(t)Bu)11] (2) derivatives, respectively. Variable-temperature NMR spectroscopy under strict exclusion of moisture enabled insight into the decomposition processes in noncoordinating solvents and at elevated temperature. In addition, structural analysis of the heterovalent 2 and of two new complexes of the general formula [Ce2(O(t)Bu)8(L)] [L = HO(t)Bu (3), OCPh2 (4)] is described.

Single phase rare earth pyrochlores, Ln2M2O7, were produced as nanofibers and thin films by electrospinning and spin-coating of chemical sols obtained from bimetallic metal-organic precursors, Ln III M II (O t Bu)5Py (Ln III = La, Pr, Nd, Sm, Er, Yb; M II = Ge, Sn, Pb; Py = pyridine). Compatibility of the metal ratio in the single-source compounds was confirmed by single crystal X-ray diffraction analyses and the ratio was preserved during the processing as the crystalline pyrochlore materials originated from an amorphous preceramic aggregate as confirmed by powder XRD and TEM studies. The photocatalytic activity of the Nd2Sn2O7 nanofibers was found to be significantly higher than that of TiO2. Nd2Sn2O7 thin films deposited on F:SnO2 as bilayered Nd2Sn2O7//Fe2O3 photoanodes showed superior photoelectrochemical (PEC) efficiency 2 for water splitting reaction with an over threefold higher photocurrent density than bare Fe2O3 photoanodes.