Development of Coordination Polymer Glass as a Luminescent Solar Concentrator Materials

多孔玻璃在分离、能源和催化等方面的应用受到高度重视。然而，对于现有的材料来说，很难对孔结构进行精细控制，从而很难获得性能。配位聚合物(CP)是一种新型无机杂化骨架材料，广泛应用于气体储存/分离、催化、磁性、离子等领域。虽然晶态CP在文献中普遍存在，但非晶态CP由于其缺陷、丰富的动态结构和优良的成形性而备受关注。通过对CPS的玻璃态和液态的仔细审查，我们确定了需要立即关注的关键挑战。将晶态CPS的孔道性质控制转移到玻璃态CPS是一个重要的挑战。我们合成了新型多孔Cp-Cu(DPP)TFSI(DPP=1，3-二(4-吡啶)丙烷；TFSI=(三氟甲磺酰亚胺))。CP在熔体淬火时形成玻璃，但孔隙率完全消失，玻璃结构与晶态结构相同。然后，我们利用机械球磨诱导玻璃形成。CP呈玻璃态，吸附能力好于晶体。以球磨时间为工具，在CP玻璃中引入不同数量的缺陷，可以精确地控制CP玻璃的多孔性。由于玻璃中的悬垂和高度动态的键，CP玻璃(以颗粒形式)的成形能力被发现优于晶态CP。在研磨玻璃中形成可逆的晶体-玻璃-晶体是罕见的，有待于进一步的研究。

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.