Development of Coordination Polymer Glass as a Luminescent Solar Concentrator Materials

多孔玻璃在分离、能源和催化方面的应用备受追捧。然而，对于现有的材料，精细控制孔隙结构和性能是非常困难的。配位聚合物（CPs）是一种无机杂化框架材料，广泛应用于气体储存/分离、催化、磁性、离子等领域。在文献中普遍存在结晶性CPs的同时，非晶态的玻璃态CPs因其缺陷丰富的动态结构和优异的可成形性而备受关注。通过对CPs玻璃态和液态领域的仔细审查，我们确定了需要立即关注的关键挑战。将晶体CPs的多孔性质控制地转移到玻璃态CPs是一个重要的挑战。合成了新型多孔CP Cu(dpp)TFSI (dpp=1,3- di（4-吡啶）丙烷；TFSI = (trifluoromethanesulfonyl)酰亚胺)。在熔融淬火过程中，CP形成玻璃状结构，但孔隙度完全消失，玻璃结构与结晶结构相同。然后我们利用机械铣削诱导玻璃形成。CP表现出玻璃性质，吸附能力优于晶体。利用铣削时间作为工具引入CP玻璃中不同数量的缺陷，使我们能够精确控制CP玻璃的多孔性。CP玻璃（以颗粒形式）的成型能力被发现优于结晶CP，这要归功于玻璃中悬垂和高动态键。在磨玻璃中，可逆晶体-玻璃晶体的形成是罕见的，有待进一步研究。

Porous glasses are highly sought for separation, energy and catalytic applications. However, for the existing materials fine control of pore structure and hence properties are very difficult. Coordination polymers(CPs) are designer inorganic hybrid framework materials widely studied for gas storage/separation, catalysis, magnetic, ionics applications. While crystalline CPs are prevalent in the literature the amorphous glassy states of CPs have attracted much attention due to defect rich dynamic structure and excellent formability. With careful review in the area of glassy and liquid states of CPs, we identified the key challenges need immediate attention. Controlled transfer of porous properties of crystalline CPs to glassy CPs is one of the important challenges. We have synthesized new porous CP Cu(dpp)TFSI (dpp=1,3-Di(4-pyridy)propane; TFSI=(trifluoromethanesulfonyl)imide). The CP formed a glass on melt quenching but the porosity was lost completely although the glass structure was found to be same as the crystalline one. We then utilized mechanical milling induced glass formation. The CP showed glassy behavior with sorption capacity better than the crystals. Milling time is used as tool to introduce different amounts of defects in CP glass which allowed us to precisely control the porous properties of CP glass. The shaping ability of CP glass(in the form of pellets) is found to be superior than the crystalline CP thanks to dangling and highly dynamic bonds in glasses. Reversible crystal-glass-crystal formation in milled glass is rare and is to be further investigated.