Recognition and Luminescence Properties of N^C^N Pt(II) Complexes with Macrocyclic Host Cucurbit[10]uril

doi:10.6023/A22020078

Abstract

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

Cite this article

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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Fig. & Tab. 7

Scheme 1. Chemical structures of host and guest molecules

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)

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.)

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.)

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

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

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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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