A series of sulfonate anions paired aromatic triangular palladium clusters 3–7, abbreviated as [Pd3]+[ArSO3]−, were synthesized using a simple “one pot” method, and gave excellent isolated yields (90–95%). Their structures and properties have been fully characterized and further investigated by fluorescence, single crystal X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). In varying
使用简单的“一锅法”合成了一系列磺酸根阴离子配对的芳香三角钯簇3–7,缩写为 [Pd 3 ] + [ArSO 3 ] - ,并获得了优异的分离收率(90–95%)。它们的结构和性质已通过荧光、单晶 X 射线衍射 (XRD) 和 X 射线光电子能谱 (XPS) 进行了充分表征和进一步研究。在不同的有机溶剂中,在氢键和极性的共同相互作用的驱动下,它们在甲醇中表现出明显更强的吸收和发射。晶体学数据表明,甲基橙离子稳定的配合物7具有D 3h对称金属核,该金属核仍然共面且几乎等边,共同受到磺酸盐的巨大位阻和较温和的供体效应的影响。通过XPS测量的Pd n + 3d 5/2和Pd n + 3d 3/2的结合能分别为336.55和342.00 eV。这些数据远低于普通Pd 2+ 3d 的数据,显着高于Pd 0物种的数据,进一步证明了三钯核心中统一的钯价态(+4/3)及其芳香性。循环电子离域。
Synthesis of Phenylbutadiynylpyridinium Derivatives for Nonlinear Optics
作者:Shin-ya Kan-no、Shuji Okada
DOI:10.1080/15421400701548993
日期:2007.9.4
1- Methyl- 4-[ 4-( dimethylamino) phenyl] butadiynyl} pyridinium ( PBP) derivatives with iodide or benzenesulfonate anion were synthesized as potential compounds for both second- and third- order NLO applications. PBP shows peculiar absorption spectrum in methanol, in which molar extinction coefficient at absorption maximum ( lambda(max)) decrease irrespective of bathochromic shift of lambda(max) compared with the corresponding compound with one triple bond between two aromatic rings. From semiempirical MO calculations, it was explained by aromatic- ring rotation of PBP in methanol. Activity on second- harmonic generation ( SHG) was found in four out of thirteen compounds synthesized. Although most of PBP derivatives were found to show exothermic reaction before melting, pure solid- state polymerization was not confirmed in these compounds.
Aminostilbazolium Derivatives Substituted by Hydroxyethyl Groups for Second-Order Nonlinear Optics
As DAST (1-methyl-4-2-[4-(dimethylamino)phenyl]ethenyl}pyridinium p-toluenesulfonate) derivatives for improved crystal stability and inhibition of crystal water inclusion, 1-(2-hydroxyethyl)-4-(2-4-[bis(2-hydroxyethyl)amino]phenyl}ethenyl)pyridinium salts 2 (2a-2l) and 1-(2-hydroxyethyl)-4-2-[4-(diethylamino)phenyl]ethenyl}pyridinium salts 3 (3a-3l) were synthesized and their properties were investigated. Salts 3 were found to have no crystal water, and the cation with one hydroxyethyl group was effective to eliminate water inclusion in the crystals. Although the melting points of 2 were lower than those of the corresponding 3, decomposition temperatures of these chromophores were above 250 degrees C indicating their good thermal stability. Crystals of m-nitrobenzenesulfonate salt 3f was obtained without crystal water and showed SHG activity.