Quantum Point Defects for Solid-State Laser Refrigeration.

Herein, the role that point defects have played over the last two decades in realizing solid-state laser refrigeration is discussed. A brief introduction to the field of solid-state laser refrigeration is given with an emphasis on the fundamental physical phenomena and quantized electronic transitions that have made solid-state laser-cooling possible. Lanthanide-based point defects, such as trivalent ytterbium ions (Yb3+ ), have played a central role in the first demonstrations and subsequent development of advanced materials for solid-state laser refrigeration. Significant discussion is devoted to the quantum mechanical description of optical transitions in lanthanide ions, and their influence on laser cooling. Transition-metal point defects have been shown to generate substantial background absorption in ceramic materials, decreasing the overall efficiency of a particular laser refrigeration material. Other potential color centers based on fluoride vacancies with multiple potential charge states are also considered. In conclusion, novel materials for solid-state laser refrigeration, including color centers in diamond that have recently been proposed to realize the solid-state laser refrigeration of semiconducting materials, are discussed.

Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [FeIII(S2Me2N3(Pr,Pr))]+ (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H2O2) to afford a rare example of a singly oxygenated sulfenate, [FeIII(η2-SMe2O)(SMe2)N3(Pr,Pr)]+ (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O)Cys114 proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [FeIIIS2Me2NMeN2amide(Pr,Pr)]- (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N3-) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.