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Dynamically switchable porphyrin-based molecular tweezer for on−off fullerene recognition
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Zhimin Sun, Xin-Hui Guo, Yue Zhao, Qing-Yu Meng, Li-Juan Xing*, He-Lue Sun*
Chinese Chemical Letters | 2024, 35(6) : 109162
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Chinese Chemical Letters | 2024, 35(6): 109162
• Communication •
Dynamically switchable porphyrin-based molecular tweezer for on−off fullerene recognition
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Zhimin Sun, Xin-Hui Guo, Yue Zhao, Qing-Yu Meng, Li-Juan Xing*, He-Lue Sun*
Affiliations
  • College of Chemistry and Materials Science, Hebei Key Laboratory of Organic Functional Molecules, Hebei Normal University, Shijiazhuang 050024, China
Published: 2024-06-15 doi: 10.1016/j.cclet.2023.109162
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Herein, a novel molecular tweezer based on 2,2′-bipyridine-bridged porphyrin subunits was constructed for efficient fullerenes recognition. The syn conformation of the molecule, which was obtained by Zn(Ⅱ) coordination, gives rise to a proper cavity to interact with fullerene guests to form a stable 1:1 complex in toluene solution. It exhibits distinct binding selectivity towards C60 over C70. Moreover, the fullerene recognition capacity can be adequately suppressed by importing H2PO4− to competitively capture Zn(Ⅱ) along with syn-anti conformational conversion. Subsequently, the molecular tweezer regenerated to bind the fullerene by introducing the Ca2+ into the system. Significantly, the association-disassociation process can be switched reversibly and repeatedly.

Molecular tweezer  /  Fullerene recognition  /  Supramolecular chemistry  /  Conformation conversion  /  Coordination
Zhimin Sun, Xin-Hui Guo, Yue Zhao, Qing-Yu Meng, Li-Juan Xing, He-Lue Sun. Dynamically switchable porphyrin-based molecular tweezer for on−off fullerene recognition[J]. Chinese Chemical Letters, 2024 , 35 (6) : 109162 - . DOI: 10.1016/j.cclet.2023.109162
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Motivated by widespread biological switches such as protein tyrosine phosphatases (PTPs), protein tyrosine kinases (PTKs), and GTPases, the construction of artificial molecular switches (AMSs), displaying dynamic stimuli-responsive behaviors, has a long history of capturing the full attention of scientists [1-5]. From the characteristics of AMS, it is considered that molecular tweezers with specific on−off switching properties are excellent candidates for building AMSs [6]. During the last decades, various molecular tweezers [7-13] have been developed via non-covalent interactions such as π–π interactions, metal–ligand coordination, ionic interactions and hydrogen bonding, which have shown fascinating applications in molecular recognition, optical switch and complex structure construction. As well known, precise regulation the conformation of the molecular tweezer is the key point in realizing their dynamic on−off switching properties. In this respect, the 2,2′-bipyridine ligand, whose conformation was able to interconvert between its anti and syn pattern when it coordinated with suitable metal ions, is an ideal allosteric center for constructing dynamic molecular tweezer [14,15].
Fullerenes are well-known carbon allotrope with defined numbers of Csp2 atoms, which own plenty of potential applications in multiple research areas [16-19]. Molecular tweezers as fullerene receptors have been thoroughly investigated due to their potential applications in the field of material science [20,21], photosynthetic techniques [22-24], and biochemistry [25,26]. More importantly, the development of dynamic molecular tweezers with on−off fullerenes recognition ability will promote the research of fullerenes. Porphyrins and their derivatives have a wide range of applications and functions regarding molecular recognition [27,28], solar cells [29-31], radical-based materials [32,33], photochemical catalysis [34], and optoelectronic materials [35]. Attributing to the highly delocalized π–electron rich characteristic, porphyrins can bind electron–deficient fullerenes through π–π interactions in the solid state [36]. Notably, when introducing porphyrin units to jaw- or pocket-like structures, the binding affinity to fullerenes can be dramatically enhanced as the result of the chelate effect for bidentate complexation [37,38]. The donor-acceptor property of the porphyrin-fullerene combination had numerous superiorities in establishing photovoltaic solar cells for mimicry of natural photosynthesis.
To develop porphyrins-based molecular tweezers as fullerenes receptors should take the following objectives into consideration: (1) high binding ability towards fullerenes, (2) distinct selectivity for either C60 or C70, and (3) dynamic performance with on−off switchable behavior. One of the possible approaches to endow the dynamic switchable property is introducing coordination units into molecular tweezers structures. Controlling the coordination and decoordination processes, their binding ability could be adjusted as the conformation fluctuated. To attain this objective, we anticipated that molecular tweezers with 2,2′-bipyridine ligand and porphyrin units could exhibit high affinity to fullerenes and dynamic switchable molecular recognition ability. When the 2,2′-bipyridine ligands coordinated with metal ions like Zn(Ⅱ) and resulted in syn conformation, molecular tweezers were in the active model with an advisable cavity for fullerenes binding. After the treatment with certain chemicals (specific anion like H2PO4− could competitively bind with Zn(Ⅱ)) that lead to the decoordination process, molecular tweezers could be unfolded into anti−conformation with the binding ability losing. Molecular tweezers could re-recognize with fullerenes after H2PO4− precipitated by Ca2+ [39]. The dynamic porphyrin-based molecular tweezer's reversible recognition of fullerenes capability was adjusted by successively introducing H2PO4− and Ca2+ (Fig. 1).
As shown in Scheme 1, anti-conformation T-ZnPP was designed and synthesized in good yield through a Suzuki coupling reaction between 4,4′-dibromo-2,2′-bipyridine and biphenyl-substituted zinc porphyrin, which was further characterized by 1H NMR, 13C NMR, and mass (HRMS) spectroscopy (Figs. S14-S16 in Supporting information). The molecular tweezer C-ZnPP, in syn-conformation, was easily prepared in situ by zinc acetate coordinating with T-ZnPP (Scheme 1). As for the complex C-ZnPP, downfield and upfield shifts of the signals corresponding to protons H3 (∆δ = 0.04 ppm), H5 (∆δ = −0.31 ppm), and H6 (∆δ = −0.49 ppm) of the 2,2′-bipyridine parts indicated the fully sufficient conversion from T-ZnPP to C-ZnPP (Fig. S19 in Supporting information).
With the molecular tweezer (C-ZnPP) in hand, a series of UV−vis and fluorescence titration experiments were performed to verify the recognition capability of C-ZnPP to the fullerenes. Compound C-ZnPP exhibited an intense Soret band at 427 nm and two less intense Q-bands in the 500−700 nm region. As shown in Fig. 2a, upon adding C60 with progressive concentrations (0−70 equiv.) to 0.5 × 10−6 mol/L solutions of C-ZnPP in toluene at 25 ℃, the Soret band at 426 nm withstood a slight bathochromic shift accompany with an obvious isosbestic point (431 nm). Small bathochromic shifts of the Soret bands of porphyrins were commonly observed on complexation of fullerenes, which here demonstrated typical π−π interaction between C-ZnPP and C60, lowering the energy of the porphyrin π to π* transition [40]. Moreover, intensities of Q-bands were gradually increased due to the charge transfer interactions between porphyrin units and fullerenes [41]. The Job's plot analysis revealed the stoichiometry of C-ZnPP and C60 was 1:1 (Fig. S20a in Supporting information). The binding constant (Ka) for the formation of C-ZnPP⊃C60 complex was 1.05 × 104 L/mol, which was evaluated (1:1 mode) spectrophotometrically by UV–vis titration data (Table S1 in Supporting information) [42]. The similar UV–vis titration experiments were conducted for C-ZnPP and C70. As shown in Fig. 2c, the Soret band at 427 nm underwent barely shifts and a little hypochromicity with the addition of C70 into the toluene solution of C-ZnPP, which suggested the binding ability was not as strong as that of C-ZnPP with C60. The binding stoichiometry of C-ZnPP and C70 was 1:1 (Fig. S20b in Supporting information) according to the corresponding Job's plot analysis (Fig. S20b), and the Ka value for the formation of complex C-ZnPP⊃C70 was 2.38 × 103 L/mol calculated from the UV–vis titration results using a 1:1 model (Table S1). Thus, the molecular tweezer C-ZnPP exhibited reasonable recognition capability towards to fullerenes (C60 and C70) and visible binding selectivity to C60. The fluorescence titration experiments were also accomplished to estimate the binding ability of C-ZnPP to fullerenes. It is generally reported that porphyrin fluorescence is quenched when fullerenes approach, as a result of photoinduced electron transfer between 1S of the porphyrins and fullerenes [43]. Upon addition of C60 and C70 to the toluene solution of C-ZnPP respectively, conspicuous quenching effect occurred when exciting at 427 nm as a result of complex C-ZnPP⊃C60 and C-ZnPP⊃C70 formation (Figs. 2b and d). Notably, the fluorescence measurements showed a larger quenching of the excited state of C-ZnPP by C60 than C70, which also reveals the binding selectivity that was consistent with the UV–vis titration results as mentioned above.
To gain further insight into the mechanism of the molecular tweezer C-ZnPP specifically binding with fullerenes, similar UV−vis and fluorescence titration experiments for T-ZnPP (anti-conformation) and control molecule 2HPP (no zinc in porphyrin units) were also performed. As for T-ZnPP, with the separate addition of fullerenes (0−50 equiv. of C60 or C70), the Soret band at 427 nm sustained no shifts and a slight lowering in intensity (Figs. S21a and c in Supporting information). Meanwhile, there was only a modest decrease in fluorescence emission intensity, which implied the fullerenes binding ability of T-ZnPP was relatively weak (Figs. S21b and d in Supporting information). Therefore, the UV–vis and fluorescence titration results affirmed that the syn-conformational structure of C-ZnPP played crucial roles in fullerenes recognition. C-ZnPP, which possesses the tweezer-like bis-porphyrin-based structure could tightly bind with fullerenes due to the appropriate cavity size between two porphyrin clefts for accepting fullerenes, while anti-conformational T-ZnPP does not. What is more, upon the separate addition of fullerenes (0−50 equiv. of C60 or C70) to a toluene solution of 2HPP, there was no obvious change in the UV–vis and fluorescence titration data (Fig. S22 in Supporting information). It is well known that metallo-porphyrins have a larger π−conjugated systems with 18 electrons, which are excellent components for binding with π−acceptor fullerenes [44]. 2HPP, without metal insertion, basically has extremely weak fullerenes recognition capability.
Diffusion ordered spectroscopy (DOSY) experiments were also conducted to prove the formation of supramolecular complexes between C-ZnPP and fullerenes (C60 or C70). With the addition of 1 equiv. of C60 to a 1.5 × 10−3 mol/L toluene solution of C-ZnPP, signals of C-ZnPP⊃C60 complex were detected with a diffusion coefficient of 2.15 × 10−6 cm2/s, which was same as signals (D = 2.14 × 10−6 cm2/s) of free molecular tweezer C-ZnPP within error (Fig. S23 in Supporting information). It was proved that C-ZnPP can bind with C60 to form a 1:1 complex and maintain its cavity size [8,45]. Furthermore, the diffusion coefficient of C-ZnPP⊃C70 (D = 1.86 × 10−6 cm2/s) was smaller than C-ZnPP⊃C60 complex, which could be believed that C-ZnPP were expanded due to its insufficient cavity for C70. The diffusion coefficient data of C-ZnPP⊃C60 and C-ZnPP⊃C70 complexes demonstrated that the cavity size of C-ZnPP was more suited for C60 than C70, explaining why it had superior selectivity towards C60 as determined by the binding constant, UV–vis, and fluorescence titration results previously.
Thereafter, a series of ion-controlled coordination/decoordination experiments were carried out to investigate the switchable fullerene recognition ability of molecular tweezer C-ZnPP. As mentioned above, the significant fluorescence quenching phenomenon occurred when excessive C60 added into the toluene solution of C-ZnPP. As shown in Fig. 3a, following the introduction of 0−5 equiv. H2PO4− (tetrabutylammonium salt) to a toluene solution of C-ZnPP/70.0 equiv. C60 mixture, it was found that the quenched fluorescence emission of C-ZnPP by C60 was reasonably restored. It is inferred that Zn cation, which coordinated with the 2,2′-bipyridine components of C-ZnPP, was gradually competitively replaced by H2PO4−, and C-ZnPP was transformed to T-ZnPP bearing anti-conformation accompany with the binding ability to C60 restraining. Therefore, the fluorescence emission intensity of the mixture solution was recovered. When 5 equiv. of H2PO4− was added, the emission intensity was able to return to its original state and kept the stated steady as up to 10 equiv. of H2PO4− was introduced (Fig. S24 in Supporting information). Moreover, the C60 recognition on−off behaviors of C-ZnPP were further monitored by 1H NMR spectroscopy in toluene-d8 (Fig. 4a). Upfield shifts (∆δ = 0.051 ppm) of the signals corresponding to the β protons of porphyrin units of C-ZnPP⊃C60 complex by virtue of shielding effect which compared to free C-ZnPP indicated that π–π stacking interactions between C-ZnPP and C60. When adding H2PO4− to the C-ZnPP⊃C60 complex solution, it was found that signals for β protons suffered downfield shifts (∆δ = 0.046 ppm) and came back to the same position as the C-ZnPP itself, within error, due to the structural transformations of the molecular tweezer from syn to anti conformation. 13C NMR spectroscopy is also very practical for disclosing the details of fullerenes complexation, since C60 has a unique signal. Obvious upfield shifts (∆δ = 0.15 ppm) of the signals ascribing to C60 belonging to C-ZnPP⊃C60 complex were found compared to free C60 because of ring current effects of porphyrins (Fig. 4b). Thus, the upfield shift should be the evidence for effective complexation between C-ZnPP and C60 [24,37]. Subsequently, upon the addition of H2PO4− to C-ZnPP⊃C60 complex solution, signals of C60 moved to downfield and returned to the free C60 state due to interactions between C-ZnPP and C60 diminishing. In general, 1H and 13C NMR spectroscopy results were consistent with the switchable ion-controlled fullerene recognition process as assumed and in line with the conclusion obtained by UV−vis and fluorescence spectroscopy experiments.
In light of the relatively poor solubility of Ca(H2PO4)2 in toluene, Ca2+ was employed to capture H2PO4− and reproduce the syn conformational C-ZnPP with the C60 binding ability recovery. The fluorescence titration experiments showed that upon 0−5 equiv. of Ca(ClO4)2 were progressively added to a toluene solution of C-ZnPP/70 equiv. C60/5 equiv. H2PO4− mixture, a distinct quenching effect took place, which suggested the regenerate of C-ZnPP (Fig. 3b). It is worth to mention that H2PO4− or Ca2+ have no interactions with the zinc ions from the porphyrin units based on the UV–vis and fluorescence spectra of 2HPP, T-ZnPP, and T-ZnPP with separate addition of H2PO4− or Ca2+ (Fig. S25 in Supporting information). With the addition of H2PO4− or Ca2+ to T-ZnPP solution, it exhibited characteristic two Q-bands of metallo-porphyrins in the 500−700 nm region, whereas porphyrins, like 2HPP, exhibited four Q-bands (Fig. S25a). What's more, when introducing H2PO4− or Ca2+ to T-ZnPP solution, the emission λmax of around 597 nm was still the same (Fig. S25b). Generally, the whole dissociation−association of C60 by C-ZnPP process controlled through alternately adding H2PO4− and Ca2+ was identified to be effectively repeatable with the excellent reversibility (Figs. 3c and d).
In conclusion, we designed and synthesized a novel molecular tweezer based on the 2,2′-bipyridine-bridged zinc-porphyrin in syn-conformation, which has the appropriate cavity to adequately bind the fullerene forming 1:1 supramolecular complex. It exhibited distinct binding selectivity towards C60 (K = 1.05 × 104 L/mol) over C70 (K = 2.38 × 103 L/mol). Furthermore, the fullerene recognition capacity of the molecular tweezer was able to be switched by introducing H2PO4− and Ca2+ successively. Upon the addition of H2PO4−, the molecular tweezer could undergo a syn−anti conformational conversion with the binding ability vanishing. After adding Ca2+ to competitively capture H2PO4−, the molecular tweezer regenerated and the fullerene binding ability was fully recovered. More importantly, the molecular tweezer underwent conformational conversion between its syn- and anti-form accompany with the association-dissociation process reversibly and repeatably, which were demonstrated by 1H NMR, 13C NMR, UV−vis, and fluorescence spectroscopy analyses. This dynamically switchable molecular tweezer with on−off fullerene recognition ability is expected to be used in the field of fullerene separation and donor−acceptor photovoltaic solar cells.
Declaration of competing interest
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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
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We acknowledge the financial support of the National Natural Science Foundation of China (No. 21801060), Natural Science Foundation of Hebei Province (Nos. B2019205172, 226Z1501G), and China Postdoctoral Science Foundation (No. 2020TQ0087). We also gratefully acknowledge the support from the National Demonstration Center for Experimental Chemistry Education of Hebei Normal University.
Supplementary materials
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Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2023.109162.
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Year 2024 volume 35 Issue 6
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doi: 10.1016/j.cclet.2023.109162
  • Receive Date：2023-08-02
  • Online Date：2025-11-21
  • Published：2024-06-15
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  • Received：2023-08-02
  • Revised：2023-09-20
  • Accepted：2023-09-28
Affiliations
    College of Chemistry and Materials Science, Hebei Key Laboratory of Organic Functional Molecules, Hebei Normal University, Shijiazhuang 050024, China
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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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