水溶性金属有机配合物的自聚集

具有大共轭体系的炔类化合物，由于它们在非线性光学，液晶，电致发光，
导电和电子/能量转移等方面有潜在的应用前景而受到越来越多的关注。 一价金
配合物丰富的光谱学性质，其自旋轨道耦合常数很大，因而有助于通过系间窜
跃进入低位发射三重态。 一价金配合物由于可能产生具有特定形态的超分子聚
集体，且具有可调节的发光性能，其研究领域正在迅速扩大。目前，关于金(I)
芳香炔金属有机配合物的研究比较少。本课题着眼于调控金(I)芳香炔金属有机
配合物的溶解性以研究其自聚集行为和磷光性质，并探索其在光活化磷光方面
的应用。
基于此，本课题选择不同溶解性的膦配体作为外围基团， 将用于合成磷光
金属有机配合物的经典的芳香炔作为内核骨架，并且与 d10电子构型的线形 Au(I)
配位，设计并合成了一系列金(I)芳香炔模型配合物。 通过 1H NMR、 13C NMR、
31P NMR、 HR-MS 等进行确证和表征。一方面， 基于目标配合物的两亲性结构，
其在 H2O 中发生自聚集，并随着时间延长有红光发射的现象。另一方面，通过
对比这一系列的不同内核和外围基团的 Au(I)芳香炔金属有机配合物在不同溶
剂中的光谱性质，发现浓度依赖的荧光向转换磷光的现象有以下特点： 1. 与配
合物有关，无论是改变外围基团还是内核配体，在分子级的溶液中，都仅有 Au1
出现浓度依赖的荧光向磷光的转换； 2. 与溶剂有关，在 Au1 可以溶解的几种
溶剂中，都仅有在 DMSO 和 MeOH 中才会出现浓度依赖的荧光向磷光的转换。
因此，我们猜想，可能是由于 Au1 在 DMSO 和 MeOH 溶液中出现了与浓度相
关的自聚集。 另外，还研究了 Au(I)芳香炔金属有机配合物在 DMSO 溶液里的
的光活化磷光行为， 并证明其在 PVP/DMSO 流体和 PVP/DMF 流体可以发生光
活化磷光行为，同时能实现光刻，并在流体的立体化光刻方面做了初步探索。
 

Alkyne compounds with large conjugated systems have received increasing
attention due to their potential applications in nonlinear optics, liquid crystals,
electroluminescence, conduction. The rich spectral properties of monovalent gold
complexes have a large spin coupling constant, which helps to enter the
low-emitting triplet state through intersystem crossing. Research field of Au(I)
complexes are rapidly expanding due to the possibility of producing supramolecular
aggregates with specific morphology and tunable luminescence properties. At
present, there are few studies on metal complexes of Au(I) arylethynyl. This project
focuses on the regulation of the solubility of Au(I) aromatic alkyne metal
complexes to study their self-aggregation behavior and phosphorescence properties
and explore its application in photoactivated phosphorescence.
Therefore, we chose different phosphine ligands with variable solubility as
peripheral groups, classical arylethynyl used to synthesize phosphorescent metal
organic complexes as a core skeleton, to coordinate with the linear Au(I) of the d10
electronic configuration. A series of Au(I) arylethynyl model complexes were
designed and synthesized. Confirmation and characterization by 1H NMR, 13C NMR,
31P NMR, HR-MS and the like. Based on the amphiphilic structure of the target
complex, it self-aggregates in H2O. By comparing the spectral properties of the
Au(I) arylethynyl metal organic complexes of different core and peripheral groups
in different solvents, it is found that the phenomenon of concentration-dependent
fluorescence-to-phosphorescence switching has the following characteristics:1.
Complex-related, whether changing the peripheral group or the core backbone, only
the concentration-dependent fluorescence-to-phosphorescence switching of Au1
occurs in the molecular-scale solution. 2. Solvent-related, in several solvents that
Au1 can be dissolved in, concentration-dependent fluorescence-to-phosphorescence
switching occurs only in DMSO and MeOH solution. Therefore, we suspect that it
may be due to the concentration-dependent self-aggregation of Au1 in DMSO and
MeOH solutions. In addition, the photoactivated phosphorescence behavior of Au(I)
arylethynyl metal complexes in DMSO solution was also studied, and it was proved
that photoactivated phosphorescence behavior can be achieved in PVP/DMSO fluid
and PVP/DMF fluid, can be utilizedfor photo-writing. Besides, a preliminary
exploration in the three-dimensional photo-writng of fluids also demonstrated.
 

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