【摘要】 采用电喷雾电离质谱通过直接进样方式对合成的3个含硫的三联吡啶配体及2个钌配合物进行分析,详细研究了其在电喷雾条件下的质谱行为。结果表明,含有芳硫基和苄硫基的三联吡啶配体在电喷雾过程中采取了不同的断裂方式,前者首先从与芳硫键相连的碳硫键断裂失去不含硫的部分碎片离子,而后者则从苄基碳硫键断裂失去含硫的部分碎片离子。两类配体与钌形成的配合物均具有较稳定的结构,不易发生多级质谱断裂。通过对配合物分子离子峰和同位素峰的分析讨论,确定了含硫的三联吡啶合钌配合物的结构。这一研究结果表明电喷雾多级串联质谱适合于含硫三联吡啶类配体及其钌配合物的结构研究,方法简便高效、准确可靠,为该类化合物的结构研究提供了参考。更多还原

【Abstract】 In this study,several sulfur-terpyridines and ruthenium complexes designed for development of new reusable ECL sensor were characterized by electrospray multi-stage tandem mass spectrometry(ESI-MSn)with direct injection,and their cleavage fragments and fragmentation pathways under ESI conditions were analyzed.The results showed that the sulfur-terpyridine derivatives are readily protonated by positive-ion ESI-MS and the carbon-sulfur bonds of sulfur-terpyridine derivatives are easy to break during the process of positive mode of ESI-MS.Also,the cleavage ways of carbon-sulfur bonds are different.The terpyridyl ligands containing arylthio firstly decomposed from the carbon-sulfur bond attached to the aromatic carbon-sulfur bond and lost some non-sulfur fragments while the terpyridyl ligands containing benzylthio broke from the benzylic carbon-sulfur bond and lost some fragments containing sulfur.The complexes of sulfur-terpyridyl ruthenium are easy to be detected by ESI-MS in positive mode.These complexes are stable and not easy to decompose in multi-stage mass fracture.Through identification of molecular ion peaks and further comparison of isotope mass peaks with the simulation value,the structures of complexes were identified.This research not only shows that ESI-MS is simple and accurate,and is suitable to study the structures of sulfur-terpyridine ligands and corresponding ruthenium complexes,but also provides a reference for study on the structures of this kind of compounds.更多还原