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含酰胺官能化三联吡啶的炔基铂(II)配合物的阴离子结合性质:主客体相互作用及氟离子诱导的去质子化

Anion Binding Properties of Alkynylplatinum(II) Complexes with Amide-Functionalized Terpyridine: Host-Guest Interactions and Fluoride Ion-Induced Deprotonation.

作者信息

Yeung Margaret Ching-Lam, Chu Ben Wai-Kin, Yam Vivian Wing-Wah

机构信息

Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee) and Department of Chemistry, The University of Hong Kong Pokfulam Road, Hong Kong (P. R. China) E-mail:

出版信息

ChemistryOpen. 2014 Oct;3(5):172-6. doi: 10.1002/open.201402019. Epub 2014 Sep 4.

DOI:10.1002/open.201402019
PMID:25478312
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4234213/
Abstract

Molecular sensors able to detect ions are of interest due to their potential application in areas such as pollutant sequestration. Alkynylplatinum(II) terpyridine complexes with an amide-based receptor moiety have been synthesized and characterized. Their anion binding properties based on host-guest interactions have been examined with the use of UV-vis absorption and emission spectral titration studies. Spectral changes were observed for both complexes upon the addition of spherical and nonspherical anions. Their titration profiles were shown to be in good agreement with theoretical results predicting a 1:1 binding model, and the binding constants were determined from the experimental data. Drastic color changes from yellow to orange-red were observed for one of the complexes upon titration with fluoride (F(-)) ion in acetone. These changes were ascribed to the deprotonation of the amide functionalities induced by F(-) ion, and this was confirmed by the restoration of spectral changes upon addition of trifluoroacetic acid to the F(-) ion-complex mixture as well as by electrospray ionization mass spectrometry (ESI-MS) data.

摘要

能够检测离子的分子传感器因其在污染物螯合等领域的潜在应用而备受关注。已合成并表征了带有酰胺基受体部分的炔基铂(II)三联吡啶配合物。通过紫外可见吸收和发射光谱滴定研究,考察了它们基于主客体相互作用的阴离子结合特性。加入球形和非球形阴离子后,两种配合物均观察到光谱变化。其滴定曲线与预测1:1结合模型的理论结果吻合良好,并根据实验数据确定了结合常数。在用氟离子(F(-))在丙酮中滴定其中一种配合物时,观察到从黄色到橙红色的剧烈颜色变化。这些变化归因于F(-)离子诱导的酰胺官能团的去质子化,这通过向F(-)离子 - 配合物混合物中加入三氟乙酸后光谱变化的恢复以及电喷雾电离质谱(ESI-MS)数据得到证实。

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