高价分子
化学
结晶学
镧系元素
多硫化物
晶体工程
化学物理
配体(生物化学)
离子
硫族元素
硫系化合物
晶体结构
超分子化学
物理化学
电解质
有机化学
受体
生物化学
试剂
电极
标识
DOI:10.1002/zaac.201200241
摘要
Abstract The structures and ligand binding modes of polychalcogenide anions are reviewed in this article. Participation in hypervalent 3 c ‐4 e bonds and/or weaker secondary np 2 → nσ * bonds leads to a strikingly more diverse homopolytaomic anion chemistry for selenium and tellurium in comparison to sulfur, for which only unbranched chain anions S n 2– with n = 2–9 have been reported. Trapped S 2 · – and S 3 · – radicals are responsible for the characteristic colours of the ultramarine pigments and S 3 · – is the dominant sulfur species at the high temperatures and pressures of deep metamorphic settings. Hypervalent linear TeTe 2 4– , T‐shaped TeTe 3 4– and square‐planar TeTe 4 6– units generate a remarkable variety of structural motifs and connectivity patterns for 1 to 3D polytelluride anions. Electron‐deficient polytelluride sheets are, however, prone to periodic spatial modifications of their charge density (CDWs) with a lower total free energy, whose formation is driven by nesting effects in the electronic band structure causing Fermi surface instabilities. Polychalcogenide ligands augment the typical terminal and bridging coordination modes of monoatomic chalcogenide anions through their ability to participate in chelation, side‐on and combination binding modes. In addition to the electrical conductivity and thermoelectric energy conversion properties of the polytellurides, potential applications of the polychalcogenides range from the manufacture of synthetic zeolite pigments and ion‐exchangeable polysulfide aerogels to NIR‐emissive lanthanide polyselenides with high quantum efficiency.
科研通智能强力驱动
Strongly Powered by AbleSci AI