N^C^N型Pt(II)配合物与大环主体葫芦[10]脲的识别及发光性质研究

doi:10.6023/A22020078

摘要/Abstract

由于过渡金属配合物具有独特的光物理化学性质而被广泛研究. 其中Pt(Ⅱ)配合物发生组装时会因Pt(Ⅱ)-Pt(Ⅱ)之间的距离不同而显示不同的荧光特性, 而主客体相互作用可以影响发光小分子的排列及组装. 为进一步探究主客体相互作用对Pt(Ⅱ)配合物发光性能的影响, 设计合成了不同取代的N^C^N型Pt(Ⅱ)配合物, 研究了大环主体葫芦[10]脲(CB[10])对这类配合物的识别作用及包合物的光谱性质. 核磁共振氢谱和质谱证明CB[10]可与配合物以1∶2的比例结合. 紫外-可见吸收光谱和荧光发射光谱分析表明主客体作用对该类金属配合物光谱性质有较大影响, 所形成的主客体包合物的磷光寿命及量子产率都有不同程度的变化. 研究结果表明, CB[10]可通过包结两个Pt(Ⅱ)配合物分子, 拉近铂原子之间的距离, 增强该类配合物在水相中的Pt(II)…Pt(II)相互作用和π-π相互作用, 实现水相中的长寿命磷光发射. 同时, 主客体作用对这类金属配合物的力致变色性质也有一定的影响.

关键词: 金属配合物, N^C^N配体, Pt(Ⅱ)-Pt(Ⅱ)相互作用, 主客体相互作用, 葫芦[10]脲

Transition metal complexes have been widely studied due to their unique photophysical and chemical properties. In order to further explore the influence of host-guest interaction on luminescent property of Pt complexes, three different substituted water-soluble Pt complexes were designed and synthesized. Cucurbit[10]uril (CB[10]), with the largest cavity among the cucurbit[n]uril family, was selected as the host molecule. The ¹H NMR titration experiments proved CB[10] binded three guests with 1∶2 stoichiometry, and the 1,3-di(2-pyridyl)benzene (N^C^N) ligand part on the guest molecule was encapsulated antiparallelly in the cavity of CB[10] in a head-to-tail manner. Mass spectrometry characterization further proved the binding between host and guest with 1∶2 stoichiometry. The low-energy absorption peaks of N^C^N Pt(II) complexes at >400 nm attributed to metal-metal-to-ligand charge transfer (MMLCT) were enhanced upon binding with CB[10]. Compared to free [2,6-di(2-pyridinyl)phenyl][3-(trimethylammonio)-1-propyn-1-yl]platinum(II) chloride (Pt-1), the ³IL emission intensity of its complex with CB[10] was enhanced dominantly. The [methyl 3,5-di(2-pyridyl)benzoato][3-(tri- methylammonio)-1-propyn-1-yl]platinum(II) chloride (Pt-2) showed visible red phosphorescence emission at 648 nm which was attributed to ³MMLCT in aqueous solution. Interestingly, binding with CB[10] led to a red-shift to 667 nm, which was closer to near-infrared emission. Besides, the phosphorescence lifetime is enhanced by 1.5 times (14.64 to 23.74 μs), and the quantum yield is enhanced by 15.6 times (2.7% to 42%) upon the host-guest complexation. The luminescent property of [4-methoxy-2,6-di(2-pyridinyl)phenyl][3-(trimethylammonio)-1-propyn-1-yl]platinum(II) chloride (Pt-3) was similar to that of Pt-2. Further research on the luminescence changes of Pt complexes before and after grinding in solid state indicated that the host-guest complex showed bigger red-shift of emission wavelength than free guest. The above results showed that the host-guest interactions based on CB[10] could shorten the distance between the platinum atoms of the two included guest molecules, thus enhancing metal-metal interaction and π-π interaction of the host-guest complexes.

Key words: metal complex, N^C^N ligand, Pt(Ⅱ)-Pt(Ⅱ) interaction, host-guest interaction, cucurbit[10]uril

引用此文

朱诗敏, 黄鑫, 韩勰, 刘思敏. N^C^N型Pt(II)配合物与大环主体葫芦[10]脲的识别及发光性质研究[J]. 化学学报, 2022, 80(8): 1066-1070.

Shimin Zhu, Xin Huang, Xie Han, Simin Liu. Recognition and Luminescence Properties of N^C^N Pt(II) Complexes with Macrocyclic Host Cucurbit[10]uril[J]. Acta Chimica Sinica, 2022, 80(8): 1066-1070.

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图/表 7

图式1. 配合物Pt-1, Pt-2, Pt-3和CB[10]的结构

Scheme 1. Chemical structures of host and guest molecules

图1. (a)自由客体Pt-2、(b) n(Pt-2)∶n(CB[10])=4∶1和(c) n(Pt-2)∶n(CB[10])=2∶1的1H NMR图谱(600 MHz, D2O) (b图中自由客体质子信号用*标记)

Figure 1. 1H NMR spectra (600 MHz, D2O) of (a) free Pt-2, and guest Pt-2 with CB[10] at ratio of (b) 4∶1 and (c) 2∶1 (The free guest proton signal is marked with * in Figure 1b)

图2. 客体分子Pt-2 (0.1 mmol/L)在不同溶剂以及加入饱和CB[10] (结合比为1∶2)前后的紫外吸收图谱(室温条件下)

Figure 2. UV-Vis spectra recorded for guest Pt-2 (0.1 mmol/L) in different solvents and with excess CB[10] (host and guest with 1∶2 stoichiometry, r.t.)

图3. 客体分子Pt-2 (0.1 mmol/L)在不同溶剂以及加入饱和CB[10]前后的荧光发射图谱(λex=400 nm, 室温条件下)

Figure 3. Fluorescence spectra recorded for guest Pt-2 (0.1 mmol/L) in different solvents and with excess CB[10] (λex=400 nm, r.t.)

图4. Pt-1~Pt-3自由客体和主客体包合物(结合比为1∶2)的归一化发射光谱(浓度均为0.1 mmol/L, λex=400 nm, 室温条件下)

Figure 4. Normalized emission spectrum of guests Pt-1~Pt-3 and host-guest complexes (host and guest with 1∶2 stoichiometry, c=0.1 mmol/L, λex=400 nm, r.t.)

Complex	λ_max^a/nm	τ₀/μs	φ_em/%
Pt-1	485	13.01	2.2
Pt-1+CB[10]	495	20.89	16.6
Pt-2	648	14.64	2.7
Pt-2+CB[10]	667	23.74	42.0
Pt-3	585	19.78	1.9
Pt-3+CB[10]	608	22.59	5.3

表1. 客体及主客体包合物溶液中的磷光寿命与量子产率

Table 1. Phosphorescence lifetimes and quantum yields of guest and host-guest complexes in solution

图5. 研磨前后客体Pt-2以及主客体包合物的归一化荧光光谱(λex=400 nm, 室温条件下)

Figure 5. Normalized fluorescence spectra of guest Pt-2 and host-guest complexes before and after grinding (λex=400 nm, r.t.)

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