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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Stereochemistry controlled by an asymmetric sulfur atom, and a rare example of a kryptoracemate
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Stereochemistry controlled by an asymmetric sulfur atom, and a rare example of a kryptoracemate

机译：由不对称硫原子控制的立体化学，以及一种稀有的race酮酸酯

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The ligands 4-methylthio-6-phenyl-2,2′-bipyridine (1) and the corresponding sulfoxide (2) and sulfone (3) have been synthesized and characterized in solution, and in the solid state by single crystal X-ray diffraction. Compounds 2 and 3 crystallize in the same space group (C2/c) with similar unit cell parameters; a small increase in the unit cell volume allows for the presence of the extra oxygen atom in 3. The sulfoxide and sulfone groups adopt conformations that permit intramolecular O?HC _(aryl) hydrogen bonds. The complexes [Ir(ppy) _2L][PF _6] with L = 1, 2 or 3 have been prepared and characterized. The asymmetric sulfur atom in ligand 2 gives rise to pairs of diastereoisomers of the complex which can be distinguished in the ~1H and ~(13)C NMR spectra. In solution, exchange of [PF _6] ~- by [Δ-TRISPHAT] ~- gives rise to four diastereoisomers and we observed good dispersion of ~1H NMR resonances, especially for those assigned to protons close to the asymmetric sulfur atom. A single crystal X-ray diffraction study of 2{[Ir(ppy) _2(3)][PF _6]}·CHCl _3·3H _2O reveals that the complex crystallizes in the chiral space group P2 _12 _12 _1, the asymmetric unit containing crystallographically independent Δ- and Λ-[Ir(ppy) _2(3)] ~+ cations. This provides a rare example of a so-called kryptoracemate in the solid state. In MeCN solution, [Ir(ppy) _2(1)][PF _6], [Ir(ppy) _2(2)][PF _6] and [Ir(ppy) _2(3)][PF _6] are weakly emissive (λ _(em) = 600, 647 and 672 nm, respectively) and preliminary studies of the electroluminescent properties of [Ir(ppy) _2(2)][PF _6] indicate that the complexes are not suitable candidates for LECs.
机译：配位体4-甲硫基-6-苯基-2,2'-联吡啶（1）和相应的亚砜（2）和砜（3）已在溶液中合成，并通过单晶X射线表征为固态衍射。化合物2和3在相同的空间群（C2 / c）中具有相似的晶胞参数结晶;晶胞体积的少量增加允许在3中存在额外的氧原子。亚砜和砜基团采用的构象允许分子内O？HC_（芳基）氢键。已经制备并表征了具有L ＝ 1、2或3的配合物[Ir（ppy）_2L] [PF _6]。配体2中的不对称硫原子产生了复合物的非对映异构体对，可以在〜1H和〜（13）C NMR光谱中区分出来。在溶液中，通过[Δ-TRISPHAT]〜-交换[PF _6]〜-产生了四个非对映异构体，我们观察到〜1H NMR共振的良好分散，尤其是对于那些分配给质子的非对称硫原子。对2 {[Ir（ppy）_2（3）] [PF _6]}·CHCl _3·3H _2O的单晶X射线衍射研究表明，该络合物在不对称单元P2 _12 _12 _1的手性空间群中结晶含有晶体学上独立的Δ-和Λ-[Ir（ppy）_2（3）]〜+阳离子。这提供了固态中所谓的色氨酸的罕见例子。在MeCN解决方案中，[Ir（ppy）_2（1）] [PF _6]，[Ir（ppy）_2（2）] [PF _6]和[Ir（ppy）_2（3）] [PF _6]较弱发射（分别为λ_（em）= 600、647和672 nm）和对[Ir（ppy）_2（2）] [PF _6]的电致发光性质的初步研究表明，该络合物不适合用作LEC的候选物。

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