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首页> 外文期刊>Chemistry: A European journal >DPP dyes as Ligands in transition-metal complexes
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DPP dyes as Ligands in transition-metal complexes

机译：DPP染料在过渡金属配合物中的配体

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The DPP dyes (=diketopyrrolopyrrole) 1 are deprotonated to give the corresponding dianions 2. These are treated with two moles of the transition-metal complexes [LnMX] = [(Ph3P)(2)MX] (M = Cu, Ag; X = Cl, NO3), [(Ph3P)AuCl], [(Et3P)AuCl], [(tBuNC)AuCl], [(Ph3P)(2)PdCl2], and [(Ph3P)(2)PtCl2] to give the novel bismetalated DPP dyes [LnM-N{C3R1(O)}(2)-N-MLn] (4-10). In comparison with the starting materials, these compounds show better solubilities, high fluorescence quantum yields (Phi greater than or equal to 80%), and bathochromic absorptions. The compounds 4c, 5a, 6b, 6c, 6e, 7c, and 8c were characterized by X-ray crystallography. The copper and silver atoms in 4 c and 5a are trigonal planar and are surrounded by the P atoms of the phosphane ligands and the N atom of the DPP dianion 2. Both metals are somewhat forced out-of-plane, and the P2M plane and the phenyl planes of R-1 are twisted by >70degrees and <25degrees, respectively, towards the chromophore plane. The gold atoms in 6-8 are linearly coordinated to one N and one P (6b, c, e, 7c) or one C atom (8c), respectively. The gold atoms are only slightly pressed out-of-plane, and the P substituents are staggered so that there is enough space for the planarization of R-1 into the plane of the chromophore. Compound 8c shows intermolecular d(10)-d(10) interactions between Au-I centers of different molecules, and these interactions lead to infinite chains of parallel orientated molecules in a gauche conformation of neighbors (torsion angle = 150degrees) in the crystal. [References: 24]
机译：将DPP染料（=二酮吡咯并吡咯）1去质子化，得到相应的二价阴离子。将它们用两摩尔过渡金属配合物[LnMX] = [（Ph3P）（2）MX]（M = Cu，Ag; X = Cl，NO3），[（Ph3P）AuCl]，[（Et3P）AuCl]，[（tBuNC）AuCl]，[（Ph3P）（2）PdCl2]和[（Ph3P）（2）PtCl2]给出新型双金属DPP染料[LnM-N {C3R1（O）}（2）-N-MLn]（4-10）。与起始原料相比，这些化合物具有更好的溶解度，较高的荧光量子产率（Phi大于或等于80％）和红移吸收。通过X射线晶体学表征化合物4c，5a，6b，6c，6e，7c和8c。 4 c和5a中的铜和银原子是三角形平面，并被膦配体的P原子和DPP二价阴离子2的N原子包围。这两种金属都在某种程度上被迫离开平面，P2M平面和R-1的苯基平面分别向生色团平面扭曲> 70度和<25度。 6-8中的金原子分别与一个N和一个P（6b，c，e，7c）或一个C原子（8c）线性配位。金原子仅被轻微地压出平面，并且P取代基错开排列，以便有足够的空间将R-1平面化到发色团平面中。化合物8c显示了不同分子的Au-1中心之间的分子间d（10）-d（10​​）相互作用，这些相互作用导致晶体中邻居的gauche构型（扭转角= 150度）中平行取向的分子的无限链。 [参考：24]

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