Oxygen quenching of structurally characterized [5,10,15,20-tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrinato]platinum(II).

The compound [5,10,15,20-tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrinato]platinum(II), [Pt(C52H40F4N4)] or Pt(II)TFP, has been synthesized and structurally characterized by single-crystal X-ray crystallography. The Pt porphyrin exhibits a long-lived phosphorescent excited state (τ0 = 66 µs), which has been characterized by transient absorption and emission spectroscopy. The phosphorescence is extremely sensitive to oxygen, as reflected by a quenching rate constant of 5.0 × 108 M-1 s-1, and as measured by Stern-Volmer quenching analysis.

High zT and Its Origin in Sb-doped GeTe Single Crystals.

A record high zT of 2.2 at 740 K is reported in Ge0.92Sb0.08Te single crystals, with an optimal hole carrier concentration ≈4 × 1020 cm-3 that simultaneously maximizes the power factor (PF) ≈56 µW cm-1 K-2 and minimizes the thermal conductivity ≈1.9 Wm-1 K-1. In addition to the presence of herringbone domains and stacking faults, the Ge0.92Sb0.08Te exhibits significant modification to phonon dispersion with an extra phonon excitation around ≈5-6 meV at Γ point of the Brillouin zone as confirmed through inelastic neutron scattering (INS) measurements. Density functional theory (DFT) confirmed this phonon excitation, and predicted another higher energy phonon excitation ≈12-13 meV at W point. These phonon excitations collectively increase the number of phonon decay channels leading to softening of phonon frequencies such that a three-phonon process is dominant in Ge0.92Sb0.08Te, in contrast to a dominant four-phonon process in pristine GeTe, highlighting the importance of phonon engineering approaches to improving thermoelectric (TE) performance.