We found that gallium mediates ferromagnetic coupling between ligand spins, creating a ferromagnetic kagomé lattice. By modulation of the interlayer spacing via post-synthetic cation metathesis of 1 to (NMe4)3.5Ga2(C6O4Cl2)3 (2) and (NEt4)2(NMe4)1.5Ga2(C6O4Cl2)3 (3), we determined the nature of the magnetic coupling between neighboring planes is antiferromagnetic. Additionally, we determined the role of the metal in mediating this magnetic coupling by comparison of 2 with the In3+ analogue, (NMe4)3.5In2(C6O4Cl2)3 (4), and we found that Ga3+ supports stronger superexchange coupling between ligand-based spins than In3+. The combination of intraplanar ferromagnetic coupling and interplanar antiferromagnetic coupling exchange interactions suggests these are promising materials to host topological phenomena.We describe an example of a two-electron metal- and ligand-based reduction of Me3SiN3 using uranium(iv) complexes with varying steric properties. Reaction of (C5Me5)2U(CH3)[P(SiMe3)(Ph)] with Me3SiN3 produces the imidophosphorane complex, (C5Me5)2U(CH3)[N[double bond, length as m-dash]P(SiMe3)2(Ph)] through oxidation of phosphorus. However, a similar reaction with a more sterically encumbering phosphido ligand, (C5Me5)2U(CH3)[P(SiMe3)(Mes)] forms the U(iv) complex, (C5Me5)2U[κ 2-(N,N)-N(SiMe3)P(Mes)N(SiMe3)]. In probing the mechanism of this reaction, a U(vi) bis(imido) complex, (C5Me5)2U([double bond, length as m-dash]NSiMe3)[double bond, length as m-dash]N[P(SiMe3)(Mes)] was isolated. DFT calculations show an intramolecular reductive cycloaddition reaction leads to the formation of the U(iv) bis(amido)phosphane from the U(vi) bis(imido) complex. This is a rare example of the isolation of a reaction intermediate in f element chemistry.Gold nanoparticles (AuNPs) are widely used in various applications such as cancer imaging and drug delivery. The functionalisation of AuNPs has been shown to affect their cellular internalisation, accumulation and targeting efficiency. The mechanism of cellular uptake of functionalised AuNPs by different cancer cells is not well understood. Therefore, a detailed understanding of the molecular processes is necessary to improve AuNPs for their selective uptake and fate in specific cellular systems. This knowledge can greatly help in designing nanotags with higher cellular uptake for more selective and specific targeting capabilities with less off-target effects. Here, we demonstrate for the first time a straightforward and non-destructive 3D surface enhanced Raman spectroscopy (SERS) imaging approach to track the cellular uptake and localisation of AuNPs functionalised with an anti-ERα (estrogen receptor alpha) antibody in MCF-7 ERα-positive human breast cancer cells under different conditions including temperature and dynamin inhibition. 3D SERS enabled information rich monitoring of the intracellular internalisation of the SERS nanotags. It was found that ERα-AuNPs were internalised by MCF-7 cells in a temperature-dependent manner suggesting an active endocytosis-dependent mechanism. 3D SERS cell mapping also indicated that the nanotags entered MCF-7 cells using dynamin dependent endocytosis, since dynamin inhibition resulted in the SERS signal being obtained from, or close to, the cell surface rather than inside the cells. NS 105 molecular weight Finally, ERα-AuNPs were found to enter MCF-7 cells using an ERα receptor-mediated endocytosis process. This study addresses the role of functionalisation of SERS nanotags in biological environments and highlights the benefits of using 3D SERS for the investigation of cellular uptake processes.We report the excited-state behavior of a structurally simple bis-sulfoxide complex, cis-S,S-[Ru(bpy)2(dmso)2]2+, as investigated by femtosecond pump-probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis-S,O-[Ru(bpy)2(dmso)2]2+ and cis-O,O-[Ru(bpy)2(dmso)2]2+. The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis-O,O-[Ru(bpy)2(dmso)2]2+. Transient absorption measurements on cis-O,O-[Ru(bpy)2(dmso)2]2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump-repump-probe transient absorption spectroscopy of cis-S,S-[Ru(bpy)2(dmso)2]2+ shows that a pump-repump time delay of 3 ps dramatically alters the S,O  O,O product ratio; pump-repump-probe transient absorption spectroscopy of cis-O,O-[Ru(bpy)2(dmso)2]2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction.Combined computational and experimental studies elucidated the distinctive mechanistic features of electrochemical cobalt-catalyzed C-H oxygenation. A sequential electrochemical-chemical (EC) process was identified for the formation of an amidylcobalt(iii) intermediate. The synthesis, characterization, cyclic voltammetry studies, and stoichiometric reactions of the related amidylcobalt(iii) intermediate suggested that a second on-cycle electro-oxidation occurs on the amidylcobalt(iii) species, which leads to a formal Co(iv) intermediate. This amidylcobalt(iv) intermediate is essentially a cobalt(iii) complex with one additional single electron distributed on the coordinating heteroatoms. The radical nature of the coordinating pivalate allows the formal Co(iv) intermediate to undergo a novel carboxylate-assisted HAT mechanism to cleave the arene C-H bond, and a CMD mechanism could be excluded for a Co(iii/i) catalytic scenario. The mechanistic understanding of electrochemical cobalt-catalyzed C-H bond activation highlights the multi-tasking electro-oxidation and the underexplored reaction channels in electrochemical transition metal catalysis.