Individual ultrasmall CdSe nanocrystals have recently been found to emit white light, but the ultimate origin of the phenomenon has remained elusive. Here we use a combination of state-of-the-art experiment and theory to show that excitation sets the ultrasmall nanocrystals into a fluxional state. Their energy gaps vary continuously on a femtosecond time scale, so that even an individual nanocr...

Pentacoordinated iridium(i) complexes of formula IrCl(SiNP)(tfbb) (1) and IrCl(HNP)2(tfbb) (2) (SiNP = SiMe2{N(4-C6H4CH3)PPh2}2; HNP = NH(4-C6H4CH3)PPh2) have been prepared and fully characterised. Both feature a distorted square pyramidal coordination polyhedron at the metal centre in the solid state and are fluxional in solution. Their reaction with trimethyl phosphite yields the derivatives ...

Tri(1-cyclohepta-2,4,6-trienyl)phosphane, P(C7H7)3 (1), serves as a bidentate chelating ligand [P] in platinum(II) and palladium(II) complexes. Here the synthesis of the four dichalcogenolene complexes [P]M[E2C2(CO2Me)2] (4) (M = Pt) and 5 (M = Pd) with E = S (a) and Se (b) from the reaction of the respective dicyclopentadienyltitanium dichalcogenolenes, Cp2Ti[E2C2(CO2Me)2], and [P]MCl2 with M ...

The first observation of fluxional covalent Si⋯F interactions in functionalised T8-F cage silsesquioxanes containing an encapsulated fluoride is reported.

This paper provides a first-principles theoretical investigation of the polytopal rearrangements and fluxional behavior of five-coordinate d-transition metal complexes. Our work is primarily based on a potential energy surface analysis of the iron tetracarbonyl hydride radical HFec(CO)4. We demonstrate the existence of distorted coordination geometries in this prototypical system and, for the f...

The dioxomolybdenum(vi) complex ((t)BuClipH2)MoO2 ((t)BuClipH4 = 4,4'-di-tert-butyl-N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-2,2'-diaminobiphenyl) reacts with 3,5-di-tert-butylcatechol to form oxo-free ((t)BuClip)Mo(3,5-(t)Bu2Cat). The bis(amidophenoxide)-monocatecholate complex is monomeric and exhibits a cis-β geometry in the solid state. Variable-temperature NMR data are consistent with t...

The coordination of a bis(methyliminophosphoranyl)pyridine ligand (L) to copper centres was studied. The use of copper(I) bromide precursors gave access to [LCuBr] (2) in which only one iminophosphorane arm is coordinated to the metal, as observed by X-ray crystallography and MAS (31)P NMR. Its fluxional behaviour in solution was demonstrated by VT-(31)P NMR, and investigated by DFT calculation...

Neutral, cationic and anionic allyl compounds of scandium contain highly fluxional allyl ligands in solution, whilst in the solid state both η(1)- and η(3)-binding modes are detected.