Role of Anions and Mixtures of Anions on the Thermochromism, Vapochromism and Polymorph Formation of Luminescent Crystals of a Single Cation, [(C6H11NC)2Au]+,Journal of the American Chemical Society

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Role of Anions and Mixtures of Anions on the Thermochromism, Vapochromism and Polymorph Formation of Luminescent Crystals of a Single Cation, [(C6H11NC)2Au]+
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-02-28 , DOI: 10.1021/jacs.9b13168
Lucy M C Luong ₁ , Mark A Malwitz ₁ , Venoos Moshayedi ₁ , Marilyn M Olmstead ₁ , Alan L Balch ₁

Affiliation

Non-coordinating anions, which generally play a subordinate role in coordination chemistry, alter the structure, lumines-cence, as well as the thermochromic and vapochromic behaviors of salts of the two-coordinate cation, [(C6H11NC)2AuI]+. Thus, while the yellow polymorphs of [(C6H11NC)2AuI](PF6) and [(C6H11NC)2AuI](AsF6) contain single chains of cations and are vapochromic, yellow [(C6H11NC)2AuI](SbF6) does not form the same polymorph, is not vapochromic, but contains two distinct chains of cations connected through aurophilic interactions. Mixed crystals such as [(C6H11NC)2AuI](PF6)0.50(AsF6)0.50 have been prepared by adding diethyl ether to a dichloromethane solution containing equimolar amounts of [(C6H11NC)2AuI](PF6) and [(C6H11NC)2AuI](AsF6). The initial (kinetic) product for the three combina-tion of anions ((PF6)-/(AsF6)-; (PF6)-/(SbF6)-; and (AsF6)-/(SbF6)-) was a precipitate of fine yellow needles with a green emis-sion, which were gradually transformed at rates that depended upon the anions present, into colorless crystals with a blue emission. While neither polymorph of [(C6H11NC)2AuI](PF6) nor [(C6H11NC)2AuI](SbF6) is thermochromic, the colorless mixed crystal [(C6H11NC)2AuI](PF6)0.50(SbF6)0.50 is thermochromic and converts from blue-emitting to green-emitting at 87-95 °C. The temperature required to transform a crystal of the type [(C6H11NC)2Au](PF6)n(AsF6)1-n from colorless (blue-emitting) to yellow (green-emitting) increases as the fraction of hexafluorophosphate ion in the crystal increases. The yellow crystals of [(C6H11NC)2AuI](PF6)0.75(AsF6)0.25, [(C6H11NC)2AuI](PF6)0.50(AsF6)0.50, and [(C6H11NC)2AuI](PF6)0.25(AsF6)0.75 are vapochromic, whereas the yellow crystals of [(C6H11NC)2AuI](PF6)0.50(SbF6)0.50 and [(C6H11NC)2AuI](AsF6)0.50(SbF6)0.50 are not.

中文翻译：

阴离子和阴离子混合物对单阳离子 [(C6H11NC)2Au]+ 发光晶体的热致变色、蒸汽变色和多晶型形成的作用

非配位阴离子通常在配位化学中起次要作用，可改变双配位阳离子 [(C6H11NC)2AuI]+ 盐的结构、发光度以及热致变色和气相变色行为。因此，虽然 [(C6H11NC)2AuI](PF6) 和 [(C6H11NC)2AuI](AsF6) 的黄色多晶型物包含单链阳离子并且是蒸汽变色的，但黄色的 [(C6H11NC)2AuI](SbF6) 不形成相同的多晶型物，不是蒸汽变色的，但包含通过亲热相互作用连接的两条不同的阳离子链。混合晶体如 [(C6H11NC)2AuI](PF6)0.50(AsF6)0.50 已通过将乙醚添加到含有等摩尔量 [(C6H11NC)2AuI](PF6) 和 [(C6H11NC)2AuI]( AsF6）。三种阴离子组合的初始（动力学）产物 ((PF6)-/(AsF6)-；(PF6)-/(SbF6)-；(AsF6)-/(SbF6)-) 是带有绿色发射光的黄色细针状沉淀物，其以取决于存在的阴离子的速率逐渐转变为具有蓝色发射光的无色晶体。虽然 [(C6H11NC)2AuI](PF6) 和 [(C6H11NC)2AuI](SbF6) 的多晶型物都不是热致变色的，但无色混晶 [(C6H11NC)2AuI](PF6)0.50(SbF6)0.50 是热致变色的并由蓝色转变- 在 87-95 °C 下发射到绿色发光。将 [(C6H11NC)2Au](PF6)n(AsF6)1-n 类型的晶体从无色（发蓝光）转变为黄色（发绿光）所需的温度随着晶体中六氟磷酸根离子的含量增加而增加增加。[(C6H11NC)2AuI](PF6)0.75(AsF6)0.25、[(C6H11NC)2AuI](PF6)0.50(AsF6)0.50和[(C6H11NC)2AuI](PF6)0.25.7AsF6的黄色晶体为蒸汽变色，

更新日期：2020-02-28

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