电喷雾质谱在线监测3d配位分子簇的组装过程及其机理研究

Rational design of 3d coordination cluster to realize anticipated structure and functions is an important multidisciplinary challenge. Real-time on-line monitoring of the assembly process of 3d coordination cluster and combination with other characterization techniques are the important solutions to solve the above problem, and the related research was just beginning. This project intends to select the cage-like and disc-like 3d coordination cluster as research object, utilize a new type of self-designed sampling system and soft ESI source to explore the controllable on-line MS monitoring technology. By using the on-line MS monitoring of 3d coordination cluster to avoid the problems of untimely monitoring and the reaction intermediates changed during the sampling process by off-line MS, to realize the tracking of time-dependent dynamic assembly process of intermediates under different pressure and temperature. Aimed at the above multiphase coexisting system, based on the crystallography and spectroscopy technology, this project intends to reveal the change of different components including solution, sediment and crystal with the change of reaction conditions and time, and their structure relevance. And then speculate the reasonable step-by-step assembly process and possible reaction mechanism of 3d coordination cluster. Through the capture of structure information of different intermediates, this implementation will provide some examples and basis for rational construction and controllable synthesis of complex functional 3d coordination clusters.

定向设计3d配位分子簇，实现预设结构和预期功能，是一个多学科交叉的重要挑战。实时在线监测研究3d配位分子簇组装过程，结合其它表征技术解析其机理是解决上述问题的必由途径之一，目前此类研究才刚刚萌芽。本项目拟选定典型的盘状和笼状3d分子簇作为研究对象，为避免离线监测中存在的反应监测不及时、反应中间体在取样过程中发生变化等问题，依托自设计的新型实时反应和联机进样系统与软电离ESI技术联用，摸索可控式在线质谱监测技术；实现在不同反应温度和压力条件下，跟踪3d配位分子簇随时间依赖的各种中间片段信息。针对以上多相共存的变化体系的在线监测，结合晶体学、谱学等表征手段，揭示溶液、沉淀和晶体等成分随反应条件、时间的变化和结构相关性，进而推测出合理的逐级组装过程和可能的反应机理。通过捕获典型的盘状和笼状簇的各种中间片段结构信息，为典型3d分子簇的定向构筑和可控合成提供实例和依据。

传统的离线监测3d分子簇组装过程虽然有一些成功的例子，但是离线监测通常存在反应监测不及时、反应过程中生成的一些亚稳定的中间体可能在降温过程中发生改变而无法被捕获等问题。本项目建立了简单、直接的在线质谱监测方法用于分子簇的逐级组装过程的原位实时跟踪，采用设计的新型实时反应和联机进样系统与软电离ESI技术联用，摸索可控式在线质谱监测技术，最终实现了在不同反应温度和压力条件下，跟踪3d配位分子簇随时间依赖的各种中间片段信息。项目中还利用合成的3d配位分子簇丰富的官能团可作为吸附位点，大的比表面积可以提高吸附速率和吸附容量等优势，将合成的3d配位分子簇用作萃取材料，为3d分子簇在样本前处理方面的应用提供了实例。