Vaidya Shefali, Veselska Oleksandra, Zhadan Antonii, Diaz-Lopez Maria, Joly Yves, Bordet Pierre, Guillou Nathalie, Dujardin Christophe, Ledoux Gilles, Toche François, Chiriac Rodica, Fateeva Alexandra, Horike Satoshi, Demessence Aude
Univ Lyon , Université Claude Bernard Lyon 1 , CNRS , Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON) , Villeurbanne , France . Email:
Institute of Experimental and Applied Physics , Czech Technical University in Prague , CZ-11000 Prague , Czech Republic.
Chem Sci. 2020 Jun 9;11(26):6815-6823. doi: 10.1039/d0sc02258f. eCollection 2020 Jul 14.
Obtaining transparent glasses made of functional coordination polymers (CPs) represents a tremendous opportunity for optical applications. In this context, the first transparent and red-emissive glasses of gold thiolate CPs have been obtained by simply applying mechanical pressure to amorphous powders of CPs. The three gold-based CP glasses are composed of either thiophenolate [Au(SPh)] , phenylmethanethiolate [Au(SMePh)] or phenylethanethiolate [Au(SEtPh)] . The presence of a longer alkyl chain between the thiolate and the phenyl ring led to the formation of glass with higher transparency. The glass transitions, measured by thermomechanical analysis (TMA), occurred at lower temperature for CPs with longer alkyl chains. In addition, all three gold thiolate glasses exhibit red emission at 93 K and one of them, [Au(SMePh)] , remains luminescent even at room temperature. An in-depth structural study of the amorphous gold thiolates by XRD, PDF and EXAFS analysis showed that they are formed of disordered doubly interpenetrated helical chains. These d metal-based compounds represent the first examples of transparent and luminescent CP glasses.
获得由功能配位聚合物(CPs)制成的透明玻璃为光学应用带来了巨大机遇。在此背景下,通过简单地对CPs的无定形粉末施加机械压力,首次获得了硫醇金CPs的透明且发红光的玻璃。这三种金基CP玻璃分别由苯硫酚盐[Au(SPh)]、苯甲硫醇盐[Au(SMePh)]或苯乙硫醇盐[Au(SEtPh)]组成。硫醇盐与苯环之间存在较长的烷基链导致形成具有更高透明度的玻璃。通过热机械分析(TMA)测量,对于具有较长烷基链的CPs,玻璃化转变发生在较低温度。此外,所有三种硫醇金玻璃在93 K时均呈现红色发射,其中一种[Au(SMePh)]即使在室温下也保持发光。通过XRD、PDF和EXAFS分析对无定形硫醇金进行的深入结构研究表明,它们由无序的双互穿螺旋链组成。这些基于d金属的化合物代表了透明且发光的CP玻璃的首个实例。