We describe the inorganic polymer K4P8Te4 which is soluble, giving solutions that exhibit white emission upon 355 nm laser irradiation. An indirect band gap semiconductor (Eg ≈ 1.4 eV), K4P8Te4 crystallizes in the space group P2 1/m, with a = 6.946(1) Å, b = 6.555(1) A, c = 9.955(2) Å, and β = 90.420(3)° at 173(2) K. The compound features infinite chains of [P8Te44-] with covalent P-Te bonding and exhibits reversible crystal-glass phase-change behavior. When deposited from solution, the material forms highly crystalline K4P 8Te4 nanospheres. The thermal analysis, FT-IR, UV-vis diffuse reflectance, 31P magic angle spinning solid-state NMR spectroscopy, and pair distribution function (PDF) analysis for the crystal and glass forms and ab initio electronic structure calculations by the screened-exchange local density function approximation are also reported. Speciation of K4P8Te4 in solution studied with 31P solutionstate NMR spectroscopy, electrospray ionization mass spectrometry, and PDF analysis indicate exfoliation of [P8Te 44-] chains followed by rearrangement into molecular species.
ASJC Scopus subject areas
- Colloid and Surface Chemistry