The phenomenon of spin crossover involves coordination complexes with switchable spin states. This spin state change is accompanied by significant geometric changes such that low and high spin forms of a complex are distinct isomers that exist in equilibrium with one another. Typically, spin-state isomers interconvert rapidly and are similar enough in polarity to prevent their independent separation and isolation.
View Article and Find Full Text PDFN-Heterocyclic carbene (NHC) ligands support gold(I) sulfide complexes of varying nuclearity and charge. For sterically undemanding ligands, gold(I) chlorides react with sulfide to form trigold μ-sulfido cations as the first observed products. The ligand IMes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] supports a monomeric cation, whereas the ICy-(1,3-dicyclohexylimidazol-2-ylidene-) supported cation crystallises as a dimer linked through an aurophilic interaction.
View Article and Find Full Text PDFControl of equilibrium and non-equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (T ), both T and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MW of flexible linear segments but increases with increasing MW of stiff segments.
View Article and Find Full Text PDFThis study examines the reactivity of a series of copper(I) sulfide complexes stabilized by the expanded-ring N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene (7Dipp) toward the nitrosonium ion (NO). 7Dipp is shown to support neutral sulfide- and disulfide-bridged dicopper(I) complexes, as well as mononuclear copper(I) hydrosulfide. The addition of NO to each of these results in the formation of NHC-supported copper(I) cations and elemental sulfur.
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