Yubin
Ding
ab,
Yunyu
Tang
a,
Weihong
Zhu
a and
Yongshu
Xie
*a
aKey Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai, 200237, China. E-mail: yshxie@ecust.edu.cn
bDepartment of Biomedical Engineering, College of Engineering and Applied Sciences, Nanjing University, Nanjing, Jiangsu 210093, China
First published on 22nd January 2015
Metal ions and anions play important roles in many industrial and biochemical processes, and thus it is highly desired to detect them in the relevant systems. Small organic molecule based sensors for selective and sensitive detection of target ions show the advantages of low cost, high sensitivity and convenient implementation. In this area, pyrrole has incomparable advantages. It can be easily incorporated into linear and macrocyclic conjugated structures such as dipyrrins, porphyrins, and N-confused porphyrins, which may utilize the imino N and amino NH moieties for binding metal ions and anions, respectively. In this tutorial review, we focus on representative examples to describe the design, syntheses, sensing mechanisms, and applications of the conjugated oligopyrroles. These compounds could be used as colorimetric or fluorescent ion probes, with the advantages of vivid colour and fluorescence changes, easy structural modification and functionalization, and tunable emission wavelengths. Compared with normal porphyrins, simple di- and tripyrrins, as well as some porphyrinoids are more suitable for designing fluorescence “turn-on” metal probes, because they may exhibit flexible confirmations, and metal coordination will improve the rigidity, resulting in vivid fluorescence enhancement. It is noteworthy that the oligopyrrolic moieties may simultaneously act as the binding unit as well as the reporting moiety, which simplifies the design and syntheses of the probes.
Key learning points(1) Fundamental knowledge of pyrrole chemistry and ion probe chemistry.(2) Synthetic chemistry of linear and macrocyclic conjugated oligopyrroles. (3) Advantages and characteristics of probes based on oligopyrroles. (4) Design strategies for metal ion and anion probes. (5) Unique ion sensing mechanisms of probes based on oligopyrroles. |
Pyrrole is a naturally occurring five-membered heterocycle (Scheme 1). It can be easily incorporated into linear and macrocyclic conjugated structures such as dipyrrins, porphyrins, N-confused porphyrins,4 and expanded porphyrins containing more than four pyrrole units, say, hexaphyrins (Scheme 1). These compounds may utilize imino N and amino NH moieties for binding metal ions and anions through metal coordination and hydrogen bonds, respectively. Meanwhile, they may also exhibit attractive and tunable colour and fluorescence changes.
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Scheme 1 Representative framework structures for conjugated oligopyrroles discussed in this tutorial review. |
This tutorial review is focused on the designing strategies, syntheses and ion sensing properties of colorimetric and fluorescent probes based on conjugated oligopyrroles. Herein, conjugated oligopyrroles refer to a class of compounds that bear two or more conjugated pyrrolic units as the central chromophore (Scheme 1), including linear ones such as dipyrrins, and tripyrrinones, as well as macrocyclic ones such as porphyrins and expanded porphyrins. In this respect, both cation and anion sensing using expanded porphyrins was first demonstrated by Sessler and coworkers.5,6 Due to the limited length of this tutorial review, these early examples as well as non-conjugated pyrrole-based probes will not be described in detail, and previous reviews may be referred to ref. 7.
The luminescent properties of dipyrrin metal complexes are influenced by many factors, such as the substituents, coordination modes, the metal ions, and the coordinated anions. In this section, the fluorescent behavior of dipyrrin complexes will be briefly described.
Bocian, Lindsey, Holten and co-workers found that introduction of a steric hindrance group into the 5-position of dipyrrins (Fig. 1) can enhance the fluorescence intensity of the zinc complexes.9 Thus, complexes 1 and 2 show very weak fluorescence with a quantum yield (ΦF) of 0.6–0.7% in toluene, while complex 3 is strongly fluorescent, showing a quantum yield of 36%. This observation may be ascribed to the fact that the bulky mesityl groups in 3 lead to steric constraints on intramolecular rotations, and thus dramatically suppress the nonradiative energy loss of the excited state, leading to the observed fluorescence “turn on”.
Using a similar strategy, Boyle, Archibald, and co-workers also developed a fluorescent dipyrrin zinc complex 4 with a quantum yield of 5.7% (Fig. 1).10 The 2-pyridyl group at the 5-position of the dipyrrin ligand is “locked” by coordination with zinc, leading to suppressed nonradiative energy loss and increased fluorescence.
By changing the metal coordination mode, Cheprakov, Vinogradov, and co-workers discovered that the fluorescence of zinc complexes of π-extended dipyrrins (Fig. 2) can be reversibly modulated.11 Free dipyrrins 5 and 6 do not fluoresce. Addition of Zn(OAc)2 to an acetone solution of dipyrrin 5 resulted in immediate vivid fluorescence enhancement with a quantum yield of 70%. Then precipitation formed in a few hours, accompanied with disappearance of the fluorescence. The “off–on–off” fluorescent behavior could be ascribed to the initial formation of heteroleptic zinc complexes in the form of MLX (M = Zn2+, L = dipyrrin ligand, X = OAc−, fluorescence on), followed by the formation of homoleptic complexes in the form of ML2 (fluorescence off) due to the presence of excess dipyrrins. And the homoleptic complexes can be converted back to the heteroleptic ones by reacting with excess Zn2+ in pyridine. In addition to the influence induced by the different metal coordination modes, the π-conjugation size also showed an important influence on the fluorescent properties of the dipyrrin complexes. Compared with 5, dipyrrin 6 has a larger π-conjugation system, and thus its Zn2+ complex showed red-shifted fluorescence in the near infrared (NIR) region around 761 nm, which is favorable for potential biomedical applications (vide infra).
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Fig. 2 Chemical structures of dipyrrins 5 and 6, and Ga(III) and In(III) complexes 7, and 8. R1 = 4-methoxycarbonylphenyl, R2 = t-Bu, Ar = 2,4,6-trimethylphenyl. |
In addition to the influence of different substituents and metal coordination modes, the types of coordinated metal ions are also very important for modulating the fluorescence of dipyrrin complexes. Cohen, Magde and co-workers found that Ga3+ and In3+ complexes of 5-mesityl dipyrrin are also fluorescent (Fig. 2).12 Complexes 7 and 8 display green fluorescence in hexanes with quantum yields of 2.4% and 7.4%, respectively. These values are much lower than that of 36% for the corresponding Zn2+ complex 3, which may be ascribed to ligand-centered lowest energy transition and existence of dominant nonradiative decay pathways in complexes 7 and 8.
Fluorescence of dipyrrin complexes can also be modulated by the coordinated anions, as demonstrated by Kawashima, Kobayashi, and coworkers.13 They synthesized a tin complex 9 by the reaction of a lithium dipyrrinate with SnCl2, and found that its fluorescence can be enhanced by 10-fold upon reacting with AgOTf in toluene to generate complex 10 (Fig. 3), which shows green fluorescence with a high quantum yield of 42%. The fluorescence enhancement may be ascribed to the formation of cationic tin species with a substantially decreased energy level of the lone-pair orbital of the tin atom.13
As described above, the fluorescence of dipyrrins may be drastically enhanced upon coordination to certain metal ions, such as Zn2+. Hence, dipyrrins may be used as fluorescence “turn-on” Zn2+ probes. In the following section, we will focus on the fluorescence “turn-on” Zn2+ probes based on dipyrrins and their tripyrrolic analogues.
Considering the fact that fluorescence wavelengths are highly dependent on the π-conjugation size of the fluorophores, Xie et al. reported four di- and tripyrrin based fluorescent Zn2+ probes, 13–16 (Fig. 4), based on the chelation enhanced fluorescence (CHEF).16 Upon addition of Zn2+, zinc complexes formed with a metal/ligand stoichiometry of 1:
2 for dipyrrins 13–15. In contrast, a 1
:
1 type of complex was formed for the tripyrrinone 16. Vivid fluorescence “turn on” was observed accompanying with Zn2+ coordination, which could be ascribed to the CHEF effect associated with the improved rigidity and planarity of the ligands in the metal complexes, as evidenced by the single crystal structures. As expected, 13–16 show tunable emission colours varying from green (514 nm) to red (637 nm) while detecting Zn2+ (Fig. 4b). Among these probes, 16 shows the highest sensitivity with a detection limit of 4.6 × 10−8 M and the longest emission wavelength at 637 nm, enabling its practical application for Zn2+ imaging in living cells (Fig. 4c).
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Fig. 4 (a) Chemical structures of dipyrrins 13–15 and tripyrrinone 16; (b) images of probes 13–16 upon addition of Zn2+ under a portable UV lamp; (c) Zn2+ imaging in living KB cells using probe 16. Reprinted with permission from ref. 16, copyright (2011) Royal Society of Chemistry. |
Recently, Dudina et al. reported the HBr salt of a 3,3′-bis(dipyrrin) 17 (Fig. 5), which can be applied as a highly selective fluorescence “turn on” probe for Zn2+.17 Addition of Zn2+ to a chloroform solution of 17 resulted in fluorescence enhancement by ∼60-fold, which can be ascribed to the CHEF mechanism due to the formation of the 2:
2 zinc complex.
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Fig. 6 (a) Proposed Zn2+ sensing mechanism for 18–20; (b) images of 18–20 (from left to right) upon addition of Zn2+ under a portable UV lamp. Reprinted with permission from ref. 19, copyright (2013) American Chemical Society. |
18–20 can coordinate with Zn2+ with vividly enhanced fluorescence. The applications of 18–20 as Zn2+ probes were demonstrated to be highly sensitive, selective, fast and applicable in a large pH range. The good selectivity towards Zn2+ may be related to the coordination preference and suitable size of Zn2+. The observed fluorescence enhancement can also be ascribed to the CHEF effect. Emission wavelengths of zinc complexes of 18–20 vary from 549 to 588 nm, due to the different numbers and acylation positions of the p-anisoyl substituents. Impressively, the unique α,β′-diacylated dipyrrin 19 shows the highest sensitivity of 4.4 × 10−8 M.
Later, the Xie group systematically investigated the electronic effect on the acylation positions.20 Acylation of 5-p-cyanophenyl dipyrromethane with p-anisoyl chloride afforded two mono- and three di-acylated products, i.e., α- and β-mono-acylated, and α,α′-, α,β′- and β,β′-diacylated. Interestingly, only the α- and β-monoacylated dipyrromethanes can be oxidized to the corresponding dipyrrin products 21 and 22 (Fig. 7). In contrast, oxidization of the diacylated dipyrromethanes afforded corresponding 5-hydroxyl substituted products 23–25. Similar to their previous work, 21–25 can be applied as fluorescence “turn on” Zn2+ probes. It is noteworthy that 23–25 has no background fluorescence due to the interruption of the conjugated framework by the sp3 carbon atom between the two pyrrolic units. Upon addition of Zn2+, these nonconjugated compounds can be oxidized to the conjugated dipyrrins, accompanied with Zn2+ coordination. Thus, 23–25 act as fluorescence “turn on” Zn2+ probes, demonstrating a high signal-to-noise ratio and high sensitivity without background fluorescence. As a result, among 21–25, compound 24 shows the best Zn2+ sensitivity with a detection limit of 1.5 × 10−8 M, and it can be applied for Zn2+ imaging in living HeLa cells.
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Fig. 7 (a) Chemical structures of dipyrrins 21 and 22, and 5-OH substituted dipyrromethanes 23, 24, and 25; (b) Zn2+ imaging in living HeLa cells using probe 24. Reprinted with permission from ref. 20, copyright (2015) Elsevier. |
Xie et al. also developed three additional 5-OH substituted dipyrromethanes 26–28 (Fig. 8), which also showed fluorescence “turn-on” sensing of Zn2+ with high sensitivity and no background fluorescence.21
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Fig. 8 (a) Chemical structures of meso-OH substituted dipyrromethanes 26–28. R = OCH3; (b) the proposed sensing mechanism of probe 26, and images of probes 26 upon addition of Zn2+ under a portable UV lamp. Reprinted with permission from ref. 21, copyright (2013) Royal Society of Chemistry. |
Based on this background, the Xie group further developed a novel tripyrrolic prodigiosin derivative. Thus, 2,2′-bipyrrole was acylated with pentafluorobenzoyl chloride. Interestingly, they separated six acylated products with rich substitution modes, i.e., α-, β-, and β1-monoacylated and α,α′-, α,β′-, and α,β1′-diacylated (29–34, Fig. 9).22 Then, the α,α′-diacylated compound, 32, was used for further reactions to synthesize a prodigiosin derivative 35, which shows very weak fluorescence with an extremely low quantum yield of 0.4% in DMF. However, addition of Zn2+ drastically enhanced its fluorescence at 622 nm with the quantum yield increased to 9.5%. As expected, 35 indeed demonstrated very high sensitivity towards Zn2+, with a detection limit of 1.1 × 10−8 M.
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Fig. 9 (a) Synthesis of acylated bipyrroles 29–34 and the prodigiosin derivative 35; (b) proposed Zn2+ sensing mechanism using 35 as the probe. Reprinted with permission from ref. 22, copyright (2014) Royal Society of Chemistry. |
These examples demonstrated that linear conjugated oligopyrroles, such as dipyrrins, tripyrrinones, and prodigiosins, can be developed as promising fluorescence “turn-on” probes for detecting Zn2+ based on the so-called chelation-enhanced fluorescence (CHEF), which is related to the suppression of nonradiative energy loss by chelation enhanced rigidity of the molecules. From the representative examples discussed above, we could briefly summarize the main points for designing fluorescence “turn-on” Zn2+ probes based on linear conjugated oligopyrroles: (1) variation in the pyrrolic unit number and the substitution modes are effective in improving the sensitivity; (2) incorporation of an OH group at the 5-position of a dipyrromethane is an effective way to obtain probes with no background fluorescence; and (3) π-conjugation frameworks of the oligopyrroles may be enlarged to red shift the emissions to the NIR wavelength range, and thus to eliminate biological damage and the interference from biological autofluorescence, which will enable the applications in biochemical analysis.
DPA is a typical Zn2+ selective binding group, which has been widely used for designing fluorescent Zn2+ probes. By introducing a DPA unit as the Zn2+ binding site and three sulfonatophenyl groups to improve the water solubility, Lippard et al. synthesized compound 36 and its manganese complex 36–Mn for Zn2+ sensing in living HEK-293 cells (Fig. 10).23
Upon addition of Zn2+ to a buffer solution of 36, vivid red fluorescence “turn on” can be detected at 648 nm and 715 nm based on a photoinduced electron transfer (PET) mechanism. A large Stokes shift of 230 nm was observed, accompanied with more than 10-fold fluorescence enhancement. Probe 36 is selective for zinc with only little interference from Cd2+ and Hg2+, and it works well in a large pH range from 4.5 to 10.1. Interestingly, its manganese complex, 36–Mn, can be applied as an MRI contrast agent for imaging Zn2+ in living HEK-293 cells. The MR signal in both the T1- and T2-weighted images decreased drastically upon interaction with Zn2+, with the T1 and T2 relaxation rates decreased and increased, respectively.
Wang, Lv and co-workers developed a ratiometric fluorescent Zn2+ probe 37 by combining a triamino Zn2+ chelating unit with a porphyrin fluorophore (Fig. 11).24 The triamino unit showed good Zn2+ affinity and improved water solubility of the probe. Addition of Zn2+ to an aqueous solution of 37 induced vivid ratiometric fluorescence changes. The fluorescence emission at 650 nm was decreased, and a new peak developed at 610 nm, which could be ascribed to the variation of the ICT effect due to the formation of a zinc complex with a 1:
1 ligand/metal ratio. Application of 37 as a ratiometric Zn2+ probe works well in the physiological pH range and shows the advantages of fast response, excellent reproducibility and high selectivity, with a detection limit of 1.8 μM.
Using a zinc porphyrin as the fluorophore and 2,2′-dipyridylamine (dpa) as the binding site, Ye et al. developed two fluorescent Cu2+ probes, 40 and 41 (Fig. 12).26,27 In CHCl3, probes 40 and 41 emit red fluorescence at 610 and 608 nm, with quantum yields of 3.6% and 5.8%, respectively. Only in the presence of Cu2+, the fluorescence can be effectively quenched, and the quenched fluorescence can be recovered by adding EDTA. The quenching process could be ascribed to the formation of corresponding copper complexes with stoichiometry of 1:
2 and 1
:
1 (probe
:
Cu2+), respectively. The Cu2+ detection limits were estimated to be 3.3 × 10−7 M and 1.5 × 10−6 M for probes 40 and 41, respectively.
As an example, Zhang et al. reported a ratiometric fluorescent Hg2+ probe 42 by linking two independent Hg2+ sensitive moieties (Fig. 13).28 In 42, the porphyrin and naphthalimide fluorophores share the same excitation wavelength and emit fluorescence at 650 and 525, respectively, with a 125 nm gap between these two emission peaks. Upon addition of Hg2+, the emissions at 650 nm decreased accompanied with an increase at 525 nm, indicative of a ratiometric response of 42 to Hg2+. NMR spectroscopy reveals that both the pyridine–piperazine moiety and the porphyrin core in 42 can bind Hg2+. Thus 42 coordinates with Hg2+ in a ligand/metal ratio of 1:
2, with Hg2+ binding constants of 4.26 × 105 M−1 and 6.31 × 105 M−1 for the pyridine–piperazine moiety and the porphyrin core, respectively. Probe 42 shows high selectivity towards Hg2+, and the binding was found to be fast, reversible and only slightly affected within a wide pH range between 4.0 and 8.0. The dynamic range for Hg2+ detection lies within 1 × 10−7 M ∼ 5 × 10−5 M, and the detection limit was found to be 2 × 10−8 M, indicative of its high sensitivity. It is noteworthy that probe 42 can be applied in living HeLa cells.
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Fig. 14 (a) Proposed sensing mechanism of probe 43 for detecting Zn2+; (b) images of probe 43 upon addition of various metal ions under a portable UV lamp. Reprinted with permission from ref. 29, copyright (2008) Royal Society of Chemistry. |
Another example of using an expanded porphyrin as the fluorescent Zn2+ probe was reported by Xie and Furuta et al.34 The pyrrolyl norrole 46 adopts a nonplanar and flexible conformation, and thus its quantum yield was found to be as low as 0.16% in CH2Cl2, while its zinc complex 46–Zn showed much stronger fluorescence with a quantum yield of 9.9% in CH2Cl2 (Fig. 17), due to the improved molecular rigidity upon coordination. Thus, addition of Zn2+ to the methanol soultion of 46 resulted in drastic fluorescence enhancement by 31-fold, with an emission wavelength of 736 nm in the NIR region.
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Fig. 17 (a) Proposed sensing mechanism of probe 46 for detecting Zn2+ (Ar = C6F5). (b) Fluorescence spectra of 46 and 46–Zn (10 μM) in CH2Cl2. Reprinted with permission from ref. 34, copyright (2013) American Chemical Society. |
Another expanded porphyrin based Hg2+ probe was reported by Rurack, You, Shen and co-workers.37 The authors envisioned that expanded porphyrins with “soft” donor sites may show higher affinity towards “soft” metal ions such as Hg2+, and thus they synthesized a rubyrin derivative, 49 (Fig. 18). Although it is insoluble in water, limiting its Hg2+ sensing application in practical systems, the authors incorporated it into a polyurethane hydrogel to improve its sensing performance in aqueous solutions. Thus, they achieved a satisfactory Hg2+ detection limit of ca. 1 ppm.
Considering that the NH moiety in pyrrole can be used as the binding site for fluoride detection. Xie et al. synthesized two pyrrole-hemiquinone compounds 50 and 51 that can be applied as colorimetric fluoride probes in DMSO (Fig. 19).42 Upon addition of F− to a DMSO solution of 50, the solution colour changed from orange to bright blue, with high selectivity for F− over competing anions such as CN−, CH3COO−, H2PO4−, Cl−, Br−, and I− due to the extremely strong hydrogen bonding ability of F−. Vivid UV-Vis spectral changes with several isosbestic points were observed during gradual addition of F−, and the NMR measurements revealed that the mechanism for the colour changes can be ascribed to F− induced deprotonation of the N–H moiety in 50. Interestingly, the NH protons in compound 51 showed two-step deprotonation processes upon addition of F−. Whereas, only one-step deprotonation was observed upon addition of CN−, CH3COO−, and H2PO4−, and no deprotonation was observed for Cl−, Br−, and I−. It is also noteworthy that in less polar solvents, such as CH2Cl2, the F− sensing process was accompanied with tautomerism shifts, which provide additional means of modulating the sensing behavior.
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Fig. 19 (a) Chemical structures of probes 50 and 51. Ar = t-Bu; (b) A photograph showing the colour changes of 50 (25 mM) upon addition of 40 equiv. of various anions in DMSO; (c) UV-vis spectral changes of 50 (10 μM) observed upon the addition of 0–180 equiv. F− in DMSO. Reprinted with permission from ref. 42, copyright (2010) Royal Society of Chemistry. |
Later, the Xie group developed a macrocyclic tetrapyrrole 52 that shows controllable and reversible tautomerism in chloroform upon alternate addition of F− and H+ (Fig. 20).43 Two sets of isosbestic points could be observed in the UV-Vis spectra when F− was gradually added to 52, which can be ascribed to the hydrogen binding between 52 and F− as well as a further deprotonation process. It is noteworthy that the macrocyclic compound 52 shows quantitative tautomeric conversion in different solvents, while the linear one 50 (vide supra) exists as a mixture of two isomers in chloroform.
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Fig. 20 Illustration of F− and H+ promoted interconversion between 52 and 52i, with the corresponding crystal structures shown adjacent to the molecular structures. |
Using triarylborane as both the recognition and energy donor unit, Shinkai and Takeuchi, et al. reported a colorimetric and fluorescent probe 53 for selective detection of F− (Fig. 21).44 NMR spectroscopy revealed that addition of F− to the solution of 53 led to the formation of the corresponding 53–F− complex, with F− coordinated at the boron centre of the triarylborane unit. UV-Vis measurements suggested a binding ratio of 1:
1 between 53 and F−, with an association constant of 99
700 M−1. Interestingly, the addition of F− induced increased fluorescence at 356 and 692 nm, accompanied with decreased fluorescence at 670 nm. These observations could be ascribed to perturbation of the π conjugation and the energy transfer between the triarylborane donor and the porphyrin acceptor in 53 by forming the 53–F− complex.
By introducing a carbonyl group to the α-position of the dipyrrin chromophore, Xie and co-workers developed three highly selective colorimetric CN− probes 54 (Fig. 22), 14 and 15 (Fig. 4).45 In dichloromethane, they showed colour changes from light yellow to orange or pink upon addition of F− and CN−, respectively. Other investigated competing anions, including CH3COO−, H2PO4−, Cl−, Br−, and I−, could not induce obvious spectral or colour changes. The vivid colour changes induced by F− and CN− indicated that these compounds may be applied as colorimetric probes for both F− and CN−. Moreover, in aqueous solutions, only the addition of CN− changed the solution colour from light yellow to pink, while F− did not induce any noticeable colour changes, which could be ascribed to the different interactions for F− and CN−. F− forms hydrogen bonds with the NH moieties, which can be displaced by water molecules in aqueous solutions. In addition to the hydrogen bonding interactions, the nucleophilic addition reactions between CN− and the probes resulted in the formation of corresponding dipyrrin adducts, and the reaction may proceed smoothly in aqueous solutions. Hence, the probes work well for sensing CN− even in the aqueous systems. The detection limits were found to be 3.6 × 10−6, 7.1 × 10−6, and 4.2 × 10−6 M, for 54, 14 and 15, respectively.
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Fig. 22 (a) Chemical structure of CN− probe 54; (b) and (c) photographs showing the colour changes of probe 54 upon addition of various anions, (b) in CH2Cl2; (c) in DMSO–H2O. Reprinted with permission from ref. 45, copyright (2012) Royal Society of Chemistry. |
In addition to the carbonyl group, the dicyanovinyl (DCV) unit is also widely employed in the design of CN− probes because of its electron deficient character and susceptibility to nucleophilic attack by the CN− anion. However, the fluorescence intensity of the probes may be either increased or decreased upon interaction with CN−, showing insufficient predictability. With the purpose to develop a general strategy for rational design of fluorescence “turn-on” CN− probes, the Xie group developed a series of such probes using DCV as the recognition unit.46 It was found that when DCV was introduced into a sterically demanding framework, fluorescence of the fluorophore can be quenched via a twisted intramolecular charge transfer (TICT) effect or just simple distortion of the π conjugation framework. One of such examples is compound 55, whose quantum yield is as low as 0.53% in CH2Cl2 (Fig. 23). After nucleophilic attack by CN− at the DCV moiety, vivid red fluorescence “turn-on” was observed.
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Fig. 23 (a) Chemical structure of CN− probe 55; (b) images of probe 55 before (left) and after (right) addition of CN− under a portable UV lamp. Reprinted with permission from ref. 46, copyright (2013) Royal Society of Chemistry. |
Despite these successful examples, research on ion probes based on conjugated oligopyrroles is still in the beginning stage. There is still a long way to go in the future. For example, water solubility of the probes needs to be improved for real applications. Besides, the metal ion probes based on metal coordination may suffer from interference of competing ions. Thus, probes based on other interactions, such as specific reactions, need to be developed. In addition, more research studies are highly desired in developing practical anion probes based on conjugated oligopyrroles.
In conclusion, successful metal ion and anion probes based on conjugated oligopyrroles with unique advantages have been developed. More research studies are desired for developing probes suitable for real applications in environmental and biochemical analyses.
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