A Suite of Tetraphenylethylene-Based Discrete Organoplatinum(II) Metallacycles: Controllable Structure and Stoichiometry, Aggregation-Induced Emission, and Nitroaromatics Sensing

被引:268
作者
Yan, Xuzhou [1 ]
Wang, Haoze [1 ,2 ]
Hauke, Cory E. [3 ]
Cook, Timothy R. [3 ]
Wang, Ming [4 ,5 ]
Saha, Manik Lal [1 ]
Zhou, Zhixuan [1 ]
Zhang, Mingming [1 ]
Li, Xiaopeng [4 ,5 ]
Huang, Feihe [2 ]
Stang, Peter J. [1 ]
机构
[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
[2] Zhejiang Univ, Dept Chem, State Key Lab Chem Engn, Ctr Chem High Performance & Novel Mat, Hangzhou 310027, Zhejiang, Peoples R China
[3] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA
[4] Texas State Univ, Dept Chem & Biochem, San Marcos, TX 78666 USA
[5] Texas State Univ, Mat Sci Engn & Commercializat Program, San Marcos, TX 78666 USA
基金
美国国家科学基金会;
关键词
METAL-ORGANIC FRAMEWORK; TURN-ON FLUORESCENCE; HIGHLY SELECTIVE DETECTION; LIGHT-EMITTING-DIODES; HOST-GUEST COMPLEXES; SUPRAMOLECULAR POLYMERS; RATIONAL DESIGN; ORGANOMETALLIC BACKBONE; LUMINESCENT PROBES; COORDINATION;
D O I
10.1021/jacs.5b10130
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Materials that organize multiple functionally active sites, especially those with aggregation-induced emission (ALE) properties, are of growing interest due to their widespread applications. Despite promising early architectures, the fabrication and preparation of multiple AIEgens, such as multiple tetraphenylethylene (multi-TPE) units, in a single entity remain a big challenge due to the tedious covalent synthetic procedures often accompanying such preparations. Coordination-driven self-assembly is an alternative synthetic methodology with the potential to deliver multi-TPE architectures with light-emitting characteristics. Herein, we report the preparation of a new family of discrete multi-TPE metallacycles in which two pendant phenyl rings of the TPE units remain unused as a structural element, representing novel ATE-active metal organic materials based on supramolecular coordination complex platforms. These metallacycles possess relatively high molar absorption coefficients but weak fluorescent emission under dilute conditions because of the ability of the untethered phenyl rings to undergo torsional motion as a non-radiative decay pathway. Upon molecular aggregation, the multi-TPE metallacycles show ATE-activity with markedly enhanced quantum yields. Moreover, on account of their ATE characteristics in the condensed state and ability to interact with electron-deficient substrates, the photophysics of these metallacydes is sensitive to the presence of nitroaromatics, motivating their use as sensors. This work represents a unification of themes including molecular self-assembly, AIE, and fluorescence sensing and establishes structure-property-application relationships of multi-TPE scaffolds. The fundamental knowledge obtained from the current research facilitates progress in the field of metal- organic materials, metal-coordination-induced emission, and fluorescent sensing.
引用
收藏
页码:15276 / 15286
页数:11
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