59 Search Results

The multiexciton quintet state, ⁵ TT, generated as a singlet fission intermediate in pairs of molecular chromophores, is a promising candidate as a qubit or qudit in future quantum information science schemes.

Manifesting chemical differences in individual rare earth (RE) element complexes is challenging due to the similar sizes of the tripositive cations and the corelike 4f shell. In this work, we disclose a new strategy for differentiating between similarly sized Dy³⁺ and Y³⁺ ions through a tailored photochemical reaction of their isostructural complexes in which the f-electron states of Dy³⁺ act as an energy sink. Complexes RE(hfac)₃(NMMO)₂ (RE = Dy (2-Dy) and Y (2-Y), hfac = hexafluoroacetylacetonate, and NMMO = N-methylmorpholine-N-oxide) showed variable rates of oxygen atom transfer (OAT) to triphenylphosphine under ultraviolet (UV) irradiation, as monitored by ¹H and ¹⁹Fmore » NMR spectroscopies. Ultrafast transient absorption spectroscopy (TAS) identified the excited state(s) responsible for the photochemical OAT reaction or lack thereof. Competing sensitization pathways leading to excited-state deactivation in 2-Dy through energy transfer to the 4f electron manifold ultimately slows the OAT reaction at this metal cation. The measured rate differences between the open-shell Dy³⁺ and closed-shell Y³⁺ complexes demonstrate that using established principles of 4f ion sensitization may deliver new, selective modalities for differentiating the RE elements that do not depend on cation size.« less