Perylene diimide (PDI) derivatives with cyclodextrins (PDI-CD2s) exhibit specific emission properties, which depend on the type of CDs in an aqueous solution. Herein we successfully create an emission film-kneaded PDI-CD2 derivatives via effective tumbling of the altropyranose unit. PDI-6CD2s are crosslinked with PDI between 6-amino-CDs. Although the emission intensities of PDI-6CD2s in dimethyl sulfoxide are similar regardless of the type of CD, PDI-6γCD2 has a relatively high emission intensity in aqueous solutions. In contrast, for PDIC7-3CD2s, which are linked with N,N’-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (BisC7-PDI) between 3-amino-CDs, the emission intensity of PDIC7-3βCD2 is stronger than those of PDIC7-3αCD2, PDIC7-3γCD2, and PDI-6CD2s in aqueous solutions. The selective emission behavior of PDIC7-3CD2s is due to the formation of the pseudorotaxane dimer through tumbling of the altropyranose unit in an aqueous solution. PDIC7-3βCD2 in the solid state does not demonstrate a distinctive emission due to self-quenching, whereas PDIC7-3βCD2 kneaded into the polyvinyl alcohol (PVA) film exhibits a bright yellow emission. The order of the emission intensities of PDIC7-3CD2s kneaded into PVA films is similar to those in aqueous solutions.
Recently, supramolecular assemblies with extended aromatic compounds have attracted much attention.1, 2, 3, 4 Perylene diimides (PDIs) derivatives effectively form supramolecular assemblies through π–π stacking interaction.5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes.22, 23, 24, 25, 26, 27 We have prepared PDI derivatives with a high emission property in aqueous solutions.
Generally, PDI derivatives have low solubilities in aqueous solutions. Even if PDI derivatives are dissolved in aqueous solutions by introducing a hydrophilic group, the emission of PDI derivatives exhibit self-quenching in aqueous solutions due to the formation of supramolecular assemblies and folders. To create water-soluble and effective emission sensor materials with PDI derivatives, we have introduced CDs into the PDI motif. The CDs are a family of macrocyclic oligosaccharides; the most common are composed of 6 (α), 7 (β), or 8 (γ) α-1,4-linked D-glucopyranose units.28, 29, 30, 31, 32, 33, 34 The introduction of CDs should influence the molecular recognition property and increase the emission intensity. Although supramolecular assemblies based on permethylated CDPDI conjugates have been previously reported,35, 36, 37, 38 the formation of assemblies cannot prevent the decrease in the monomer emission intensity of the PDI units due to self-quenching. In addition, the affinity of permethylated CDs with guest molecules significantly decreases compared with native CDs.39
Herein we report the selective emission properties of PDI-CD2 derivatives through the tumbling of the altropyranose unit in an aqueous solution. Previously, we have reported the formation of pseudorotaxane dimer from the altro-α-CD (altro-α-CD) dimer via tumbling of altro-α-CD,40, 41 which consists of one altropyranose unit and five glucopyranose units. Although some research groups have reported the tumbling of permethylated glucopyranose type CD,42, 43, 44, 45, 46, 47 tumbling of the altropyranose unit in altro-CDs has yet to be reported. We have successfully observed the selective emission of PDI-CD2s in aqueous solutions and prepared emission films based on PDI-CD2s kneaded into polyvinyl alcohol (PVA) films. The emission depends on the cavity size of the altro-CDs formed through altro-CD tumbling.
Preparation of PDI-6αCD2
6-NH2-α-CD (100 mg, 0.103 mmol) and 3,4,9,10-perylene tetracarboxylic dianhydride (20.0 mg, 0.0511 mmol) were dissolved in anhydrous dimethyl formamide (DMF; 10 ml) and stirred at 120 °C for 24 h under Ar atmosphere. Reaction mixture was dried under vacuum and dissolved in 5 ml of water. The solution was poured into acetone (100 ml) and participate was filtered. This precipitate was absorbed on Celite and wash with acetone and chloroform. After washing, crude product was eluted from Celite with water and purified by DIAION HP-20 reverse phase column (Mitsubishi Chemical Co., Tokyo, Japan, eluent: water to water/methanol=70: 30). Fraction of water/methanol=70:30 was collected and dried to obtain the product as a red solid in the yield of 43.3 mg (36.8%). 1H nuclear magnetic resonance (NMR) and 13C NMR spectra are shown in Supplementary Figures S1 and S2. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S3 and S4.
Preparation of PDI-6βCD2
PDI-6βCD2 was synthesized in the same manner as PDI-αCD2, using 6-NH2-β-CD (113 mg, 0.103 mmol), 3,4,9,10-perylene tetracarboxylic dianhydride (20.0 mg, 0.0511 mmol) and DMF (10 ml). Crude product was purified by DIAION HP-20 reverse phase column (eluent: water to water/methanol=70:30). The product was obtained as a red solid in the yield of 66.0 mg (49.3%). 1H NMR and 13C NMR spectra are shown in Supplementary Figures S5 and S6. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S7 and S8.
Preparation of PDI-6γCD2
PDI-γCD2 was synthesized in same manner as PDI-αCD2, using 6-NH2-γ-CD (259 mg, 0.206 mmol), 3,4,9,10-perylene tetracarboxylic dianhydride (40.0 mg, 0.102 mmol) and DMF (20 ml). Crude product was purified by DIAION HP-20 reverse phase column (eluent: water to water/methanol=70:30). The product was obtained as a red solid in the yield of 53.4 mg (18.1%). 1H NMR and 13C NMR spectra are shown in Supplementary Figures S9 and S10. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S11 and S12.
Preparation of PDIC7-3αCD2
N,N’-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (32.3 mg, 0.050 mmol), 3-NH2-α-CD (97.2 mg, 0.100 mmol), PyBOP (57.2 mg, 0.110 mmol) and a drop of triethylamine were dissolved in DMF and stirred at room temperature for 48 h. DMF was evaporated and residue was dissolved in a small amount of water. Aqueous solution was poured in acetone (50 ml) and precipitate was collected (this manipulation was repeated three times). Crude product was purified by DIAION HP-20 reverse phase column (eluent: water to water/methanol=50:50). Fraction of water/methanol=50:50 was collected and dried to obtain the product as a red solid in the yield of 25.6 mg (20.0%). 1H NMR and 13C NMR spectra are shown in Supplementary Figures S14 and S15. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S17 and S18.
Preparation of PDIC7-3βCD2
PDIC7-3βCD2 was synthesized in same manner as PDIC7-αCD2, using 3-NH2-β-CD (113 mg, 0.100 mmol). Crude product was purified by DIAION HP-20 reverse phase column (eluent: water to water/methanol=50:50). Fraction of water/methanol=60:40 was collected and dried to obtain the product as a red solid in the yield of 43.6 mg (30.3%). 1H NMR and 13C NMR spectra are shown in Supplementary Figures S19 and S20. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S22 and S23.
Preparation of PDIC7-3γCD2
PDIC7-3γCD2 was synthesized in same manner as PDIC7-3αCD2, using 3-NH2-γ-CD (130 mg, 0.100 mmol). Crude product was purified by DIAION HP-20 reverse phase column (eluent: water to water/methanol=50: 50). Fraction of water/methanol=70:30 was collected and dried to obtain the product as a red solid in the yield of 33.0 mg (20.6%). 1H NMR and 13C NMR spectra are shown in Supplementary Figures S23 and S24. Contour plot of fluorescence intensity versus excitation and emission wavelengths in DMF or aqueous solution are shown in Supplementary Figures S27 and S28.
Preparation of PVA films with PDI-CD2s
The 300 μl of aqueous solution of PDI-CD2s (1 mM) was dropped on the Teflon petri. The 8 g of poly(vinyl alcohol) (Mn=2000) aqueous solution (10 wt%) was added to the PDI-CD2s aq. The PVA films with PDI-CD2s were obtained by evaporating the water at 75 °C in a thermostatic chamber.
Preparation and chemical structures of PDI-6CD2s and PDIC7-3CD2s
Figure 1 shows the six different PDI-CDs. PDI-6CD2s (PDI-6αCD2, PDI-6βCD2 and PDI-6γCD2) are directly crosslinked between CDs with PDI. PDI-6CD2s were prepared by the reaction of 6-amino-CDs with perylene dicarboxylic acid dihydride. PDIC7-3CD2s (PDIC7-3αCD2, PDIC7-3βCD2 and PDIC7-3γCD2) were prepared by the reaction of 3-amino-CDs with N,N’-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (BisC7-PDI, see in Supplementary information in Supplementary Figure S13.) using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). The photophysical properties of PDI-6CD2 and PDIC7-3CD2 were characterized by absorption and fluorescence spectroscopies. The supramolecular structures of PDI–CD derivatives were characterized by 1H NMR spectroscopic methods.
Absorption and fluorescence properties of PDI-6CD2s
Figures 2 and 3 show the absorption and fluorescence spectra of PDI-6CD2s in DMF and aqueous solutions, respectively. The absorption and fluorescence spectra of PDI-6CD2s in DMF are similar regardless of the type of CD. Table 1 summarizes the quantum yields (Φem) of PDI-6CD2s and PDIC7-3CD2s in DMF and water. The Φem values of PDI-6αCD2 and PDI-6βCD2 are slightly higher than that of PDI-6γCD2 in DMF. On the other hand, the fluorescence intensities of PDI-6CD2s in aqueous solutions significantly decrease due to self-quenching. The difference in the fluorescence intensities and Φem of PDI-6CD2s are due to self-aggregation. Φem of PDI-6γCD2 is higher than those of PDI-6αCD2 and PDI-6βCD2, and this higher value is related to the inhibition of self-aggregation through π–π stacking interactions due to the bulkiness of γ-CD in aqueous solutions.
Absorption and fluorescence properties of PDIC7-3CD2
PDIC7-3CD2s exhibit unpredictable specific emission behaviors in aqueous solutions. First, we investigated the dependence of the photophysical properties of PDIC7-3CD2s on the solvent. Figure 4, which shows the absorption and fluorescence spectra of PDIC7-3CD2s in DMF, demonstrates that the absorption and fluorescence spectra of PDIC7-3CD2s are similar for all the CDs. However, in aqueous solutions, the absorption band of PDIC7-3CD2s depends on the CD cavity (Figure 5). The absorption band of PDIC7-3βCD2 exhibits distinctive vibrational-electronic coupling and vibronic transitions on top of the allowed π–π* electronic transition can be resolved, whereas PDIC7-3αCD2 and PDIC7-3γCD2 display broad absorption bands. Φem of PDIC7-3βCD2 is significantly higher than those of PDIC7-3αCD2 and PDIC7-3γCD2 (Table 1). Φem of PDIC7-3βCD2 in an aqueous solution is close to that of PDIC7-3βCD2 in DMF.
Due to π-stacking interactions, large aromatic ring derivatives can easily form supramolecular assemblies. Hence, the strong intermolecular vibrational-electronic coupling in PDI derivatives has been well studied.6, 16, 17, 18, 19, 20, 21 The formation of PDI assemblies leads to broad vibrational-electronic coupling due to fused aromatic rings whose molecular orbital overlap with adjacent neighbors. In contrast, free PDI derivatives provide clear vibrational-electronic coupling. The Huang−Rhys factor, S=A0 → 1/A0 → 0 (A0 → 0, absorption intensity of 0 →0 band; A0 → 1, absorption intensity of 0 → 1 band), is an indicator of the formation of supramolecular assemblies.6, 16, 17, 18, 19, 20, 21 The intensities of 0 → 0 band (A0 → 0) and 0 → 1 band (A0 → 1) in DMF do not have a measurable difference between PDIC7-3CD2s (Figure 4), whereas the intensities in aqueous solutions depend on the CD cavity (Figure 5). The S ratio of PDIC7-3βCD2 in an aqueous solution is similar to that in DMF (S=0.74 (aq), S=0.64 (DMF)). The S ratios of PDIC7-3γCD2 in aqueous solutions is 1.25, which is the value intermediate between PDIC7-3αCD2 and PDIC7-3βCD2 in aqueous solutions. The S ratios of PDIC7-3αCD2 in aqueous solutions is 2.05, which is close to those of PDI-6CD2s in aqueous solutions.
Although the association behavior of PDIC7-3αCD2 is similar to the values for known PDI derivatives,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 PDIC7-3βCD2 shows a definite emission, suggesting that PDIC7-3βCD2 is relatively dispersed even in aqueous solutions. PDIC7-3αCD2 and PDIC7-3γCD2 do not show distinctive quantum yields (Φem=0.90 and 11%). However, Φem of PDIC7-3βCD2 is 43%, which is close to that in DMF. These results indicate that PDIC7-3CD2s are effectively dispersed and form monomers in DMF, but PDIC7-3αCD2 and PDIC7-3γCD2 form supramolecular assemblies in aqueous solutions. However, PDIC7-3βCD2 is effectively dispersed even in an aqueous solution.
Supramolecular structure of PDIC7-3CD2s
We hypothesized that the emission differences are due to the formation of supramolecular complexes. The two-dimensional rotating-frame overhauser spectroscopy spectrum of PDIC7-3αCD2 indicates the C7 alkyl unit and the inner protons of altro-α-CD end groups are correlated, but the PDI unit and inner protons in aqueous solutions are not (see Supporting information in Supplementary Figure S16). The two-dimensional rotating-frame overhauser spectroscopy spectrum of PDIC7-3βCD2 demonstrates that the inner protons of altro-β-CD are correlated to the protons of PDI and C7 alkyl units (Figure 6). The two-dimensional rotating-frame overhauser spectroscopy spectrum of PDIC7-3γCD2 shows the altro-γ-CD inner protons are correlated to the protons of PDI and C7 alkyl units (Supplementary Figure S25). These results show that the altro-CD unit includes the C7PDI axis molecule in aqueous solutions.
How is the altro-CD unit included the C7PDI axis molecule in the cavity? PDIC7-3CD2s are regarded to have a dumbbell shape. Other CD molecules cannot physically slip through the end of the altro-CDs of PDIC7-3CD2s to form pseudorotaxane. Previously, we have reported that an alkyl altro-α-CD dimer is converted into a pseudorotaxane dimer through tumbling of the altropyranose unit of altro-α-CD in D2O.40, 41 On the basis of these results, PDIC7-3βCD2 forms a pseudorotaxane dimer through tumbling of the altropyranose unit of altro-β-CD in aqueous solutions (Scheme 1).
PDIC7-3αCD2 forms a pseudorotaxane dimer, which includes the C7 alkyl unit in the altro-α-CD cavity (Scheme 2). The cavity size of altro-α-CD is too small to include the PDI unit. Altro-β-CD and altro-γ-CD possess a sufficient cavity size to include the PDI unit. PDIC7-3βCD2 and PDIC7-3γCD2 form pseudorotaxane dimmers, where the PDI unit is covered by the altro-CDs end groups. Coverage of the PDI unit inhibits the π–π stacking interaction between PDI units, leading to self-quenching. In contrast, PDIC7-3αCD2 cannot inhibit self-quenching due to the defective coverage of the PDI unit. Actually, we have investigated the inhibition of altro-β-CD tumbling using a competitive guest, adamantane carboxylic acid sodium salt, which is strongly included in the cavity of β-CD.39, 48, 49, 50, 51, 52 Mixing 100 equivalents of adamantane carboxylic acid sodium salt guest molecules with a PDIC7-3βCD2 aqueous solution decreases the emission intensities of PDIC7-3βCD2 (Supplementary Figure S29). The addition of an excess of adamantane carboxylic acid sodium salt into a PDIC7-3βCD2 aqueous solution causes a marked decrease in the emission intensity, which is 61% of the initial intensity. Hence, adamantane carboxylic acid sodium salt included in the altro-β-CD unit of PDIC7-3βCD2 inhibits tumbling of the altropyranose unit.
Association constants of CDs with BisC7-PDI
To investigate the differences in the correlation peaks of the two-dimensional nuclear overhauser effect spectroscopy NMR spectra and the emission intensities for the various CDs, the stoichiometric proportion and the association constants were determined by UV titration measurements (see Supporting Information, Supplementary Figures S33–S35). Job’s plots suggest that each CD forms a 2:1 complex for BisC7-PDI in aqueous solutions. (see Supporting information, Supplementary Figures S30–S32) The K1 values of α-CD and γ-CD with BisC7-PDI are 6.2 × 104 M−1 and 1.5 × 105 M−1, respectively, whereas that of β-CD with BisC7-PDI is larger (4.0 × 105 M−1; Table 2) These results indicate that the emission intensity of PDIC7-3βCD2 is selectively higher than those of PDIC7-3αCD2 and PDIC7-3γCD2 due to the suppression of self-aggregation.
Emission properties of PDIC7-3CD2 films
Figure 7 shows photographs of PDIC7-3CD2s in aqueous solutions. The emission intensities do not differ for PDIC7-3CD2s in DMF solutions, whereas in aqueous solutions, only PDIC7-3βCD2 shows a distinct green−yellow emission.
Using the emission properties in aqueous solutions, we prepared a PVA film with PDIC7-3CD2s. An aqueous solution of PDIC7-3CD2s (0.3 μmol) was mixed with an aqueous solution of PVA (0.80 g), and subsequently dried at 75 °C (see Supporting information, Supplementary Figure S36). Although the resulting PVA films with PDIC7-3CD2s are slightly red, they are the same under visible light (Figure 8). Only the film with PDIC7-3βCD2 shows a bright yellow emission under UV light. PVA films with PDIC7-3αCD2 and PDIC7-3γCD2 do not display distinct emissions; actually, the PDIC7-3αCD2 and PDIC7-3γCD2 films do not show distinct quantum yields (Φem=14 and 24%), but Φem of a film of PDIC7-3βCD2 is 54%. The PVA film with PDIC7-3βCD2 can be prepared from the dimethyl sulfoxide solutions, but this method is unsuited for a homogeneous, large-area film with a flat surface (Figure 8d). Dropping a PDIC7-3βCD2 aqueous solution onto a quartz plate and subsequent drying in air produce a PDIC7-3βCD2 solid that exhibits a weak red light instead of a bright yellow emission under UV light (λex=365 nm; see Supporting information, Supplementary Figure S37).
PDIC7-3βCD2 is self-quenching in the solid state due to self-aggregation through a π–π stacking interaction. First, we speculated that the emission intensity differences between PDIC7-3CD2s would not be observed in PVA films, because the structure of the pseudorotaxane dimer from PDIC7-3βCD2 would decompose in the PVA matrix. However, the supramolecular structure of PDIC7-3βCD2 remains in the PVA films. Only the PDIC7-3βCD2 film shows a bright green−yellow emission under UV light.
We prepared CD-PDI derivatives where the emission properties depend on the type of CD. Although PDI derivatives usually have low solubilities in aqueous solutions, the introduction of the CD units improves the solubility. PDI-6CD2s, in which the CD unit is directly introduced into the PDI unit without spaces, dissolves in water, but does not show an emission difference with the type of CD unit. In contrast to PDI-6CD2s, PDIC7-3βCD2 displays a bright yellow emission and PDIC7-3γCD2 has a weak emission. The emission properties of PDIC7-3CD2s are due to the tumbling of the altropyranose unit, which prevents self-aggregation and self-quenching in aqueous solutions.
To utilize the selective emission properties, PVA films woven with PDIC7-3CD2s were prepared. Even in PVA films, PDIC7-3CD2s show selective emission behaviors, which depend on the CD. We initially speculated that the pseudorotaxane dimer would decompose to the original dimer in the film, and the emission differences according to the type of CD would not be observed. However, the opposite results are observed, indicating PDIC7-3βCD2 forms pseudorotaxane dimers even in PVA films. The PVA films with PDIC7-3βCD2 should function as emission and quenching sensor films for chemical compounds based on the molecular recognition property of CDs.
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We thank Mr S Adachi (Osaka University) for his support of the 2D-NMR experiments. This work was supported by the ‘Core Research for Evolutional Science and Technology’ program of the Japan Science and Technology Agency, Japan.
Supplementary Information accompanies the paper on Polymer Journal website
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Takashima, Y., Fukui, Y., Otsubo, M. et al. Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling. Polym J 44, 278–285 (2012). https://doi.org/10.1038/pj.2011.128
- fluorescence property
- inclusion complex
- perylene diimide