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CHEMPHYSCHEM COMMUNICATIONS

DOI: 10.1002/cphc.201300001

A Design Strategy for Motion Control Systems with Identical Binding Sites
Wei-Tao Peng, Yu-Chang Chang, and Ito Chao*[a]
Stimuli-responsive supramolecular systems with tunable binding ability have been intensely pursued. One of their merits is that they provide opportunities in synthesizing motion control systems on the basis of controlled association/dissociation of supramolecular complexes. These motion-controllable systems can potentially lead to the design of molecular-based electronic devices,[1] molecular nanovalves for drug deliveries,[2] and stimuli-triggered supramolecular assemblies.[3] In the literature, most motion controls are accomplished through receiving stimuli on the binding sites to vary their binding ability. For example, Stoddart et al. have constructed redox-switchable bistable[2]rotaxanes with tetrathiafulvalene (TTF) and dioxynaphthalene (DNP) as the binding sites (blue and red objects in Figure 1 a), and cyclobis(paraquat-p-phenylene) (CBPQT4 + ) as the binding partner.[4] In these systems, CBPQT4 + can be reined to enclose one of the binding sites since TTF takes on the responsibility to receive the external stimulus and thus alters its binding strength (by charge transfer interaction at the neutral state or electrostatic repulsion at the oxidized state) to CBPQT4 + . Rather than directly altering the property of a binding site, we have proposed a concept of remote control of binding in which the stimulus-responsive reaction site is not directly involved in binding.[5] Instead, a conjugated bridge is employed to link the binding and reaction sites (see Figures 1 b and 1c). The concept of remote control of binding has gained support through theoretical investigations[5, 6] and experimental evidence.[7] Sessler et al. have made a metallation-enhanced fluoride binder in which the dipyrrole binding sites are not in the immediate proximity of the phenanthroline metallation site. With and without Co3 + (stimulus) bound to the phenanthroline site, a more than hundred-fold difference in fluoride binding in solution has been reported.[7a] The concept of remote control has several advantages. First of all, it can be applied to supramolecular systems whose binding sites are inert to external stimuli. Moreover, it makes the design of a multivalence binding system with only one control center conceptually easy. In Figures 1 b and 1c we have attached two binding sites to a control center. However, it is conceivable that one can attach more than two binding sites. In a study of molecular elevator, three protonation sites were needed to control the movement of a tripod elevator.[8] Within the concept of remote control of binding, one stimulus-receptive site may achieve the same control. Using one control center to manipulate several sites can be viewed as one form of atom economy. Finally, a stimulus-responsive motion control system capable of swapping preferential binding sites are usually realized with binding sites of different chemical compositions (as in the rotaxane depicted in Figure 1 a). However, within the concept of remote control, one can keep the binding sites the same but utilize different conjugated bridges to realize the goal (Figure 1 c), because a bridge can influence the binding behavior of a binding site.[5] In this study, we adopt a “same binding site/same bridge” strategy (see Figure 1 d) to go beyond the “different binding site/same bridge” or “same binding site/different bridge” approaches depicted in Figures 1 b and 1c. Identical chemical composition of bridges/binding sites means less pondering over what moieties can be used while designing a system. The foundations of the current design to achieve stimulus-responsive motion control are a three-stage redox reaction center and the position effect in this center. As shown in the Figure 1 d, identical bridges and binding sites are attached to a binding control center at chemically distinct postions (i.e. alpha vs. beta or para vs. meta); the reaction center is represented by a rhombus to emphasize that not all connection poChemPhysChem 2013, 14, 500 – 504

Figure 1. a) Model of an axle of a rotaxane without showing the macrocyclic ring (CBPQT4 + ). One of the binding sites plays the role of the stimulus-responsive reaction center. b) Remote motion-controllable system with different binding sites linked to a reaction center (solid gray circle). c) With the same binding site but different bridges. d) With the same binding site and bridges, but the bridges are linked to chemically distinct positions of the reaction center.

[a] W.-T. Peng, Dr. Y.-C. Chang, Prof. I. Chao Institute of Chemistry Academia Sinica Taipei 11529 (Taiwan) Fax: (+ 886) 2-2783-1237ca.edu.tw E-mail: ichao@gate.sini Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cphc.201300001. 

2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

500

is employed as the reaction center. when the reaction center is electrondeficient. As in our previous studies. whose NÀH hydrogen-bond-donating ability is probed with ammonia. 0.[9] Through proper modification. For example.40 À8. 500 – 504 501 .18 À9.[13] In this study.92 À6. when the reaction site becomes electron-rich.[11b.[5] In the literature there are molecular switches that undergo electrochemical control of strengthening/weakening or complexing/decomplexing of hydrogen-bonded host–guest adducts in a reversible manner.78 kcal molÀ1 to À6.02 À4. The binding energies of 1 and 2 at the neutral state (DEb(N)) are almost the same in each compound.org Figure 2. Ammonia binding energies (DEb. to the best of our knowledge. the a-binding site is then a poorer binder because an a-bridge transmits greater electron-donating effect than a b-bridge does onto the proton-donating binding site. bridges and binding sites are attached to a. 12a. Calculated ammonia binding energies to the pyrrole moiety of 1 and 2 at B3LYP. On the other hand.chemphyschem.93 À6.89 À11. while an electron-rich center will do the opposite. Weinheim Figure 3. 14. 2 a–d. all between À6.83 À9.79 À11.78 À6.94 À5.98 À6. the charged states of amphoteric phenalenyl (+ 1.89 À6.29 À4.06 ~ Table 1.[10] Phenalenyl derivatives have attracted much attention as they are promising building blocks for construction of molecular metals[11] and other functional materials. crystals of phenalenyl derivatives have been acquired at ambient conditions. For 1 and 2. some systems possess multi-stage and/or multiple binding sites. the charged states of the often employed TTF vary between 0.84 À6.82 À4. sitions are equivalent. an electron-withdrawing center will enhance the proton-donating ability of the pyrrole binding site. DEb(N) of 1 and 2 differ by only 0. Model compounds 1 a–d. with the a-bridge being more efficient than the b-bridge.39 À11.[15–16] However.94 ChemPhysChem 2013.98 kcal molÀ1. À1) change sign.83 À9.68 À4. Conversely.89 À3. + 1. pyrrole is used as a binding site.  2013 Wiley-VCH Verlag GmbH & Co.68 À6.33 À3. KGaA. there is no case in which the hydrogen bonding strengths of two identical binding sites are tuned asymmetrically with electrochemical means.86 À6.84 À11. This a/b position effect has been indicated as the origin of the conducting/semiconducting quantum transport behavior of phenalenyl.48 À11. cationic and anionic states have been generated and characterized spectroscopically. Phenalenyl is a persistent hydrocarbon radical of which neutral radical.38 À8. the charged states of most three-stage redox systems do not change sign. This means the reaction center can be switched between electron-withdrawing and electron-donating.20 À3. Furthermore. 3 and 4.85 À4.[14–16] Among them.CHEMPHYSCHEM COMMUNICATIONS www.62 À4. the phenalenyl radical (Figure 2 a). If the a.97 À6.90 À6. + 2.11 À10.or/and b-positions as shown in Figure 3 (model compounds 1 to 4). M05-2X and MP2 levels confirm the position effect and the above postulation.13 À4.77 DEb(+) À12.86 À6.and b-carbons of phenalenyl molecule can tune the bridge efficiency through the position effect.82 DEb(À) À3. d] the a/b position effect underlie differential bridge efficiency in transmitting the impact of a redox reaction on a binding site. Table 1 shows the B3LYP/6-31 + G(d) results (see the Supporting Information for the M05-2X and MP2 results). in kcal molÀ1) of 1 and 2 at the B3LYP/6-31 + G(d) level Compound 1a 1b 1c 1d 2a 2b 2c 2d 3 4 Site type a-site a-site a-site a-site b-site b-site b-site b-site a-site b-site a-site b-site DEb(N) À6. an a-binding site (as in 1) would be a stronger binder than a b-binding site (as in 2). b. A redox-active molecule. At a given bridge length.[12] Since the singly occupied molecular orbital (SOMO) of phenalenyl is only distributed on the six a-carbons and not the b-carbons (Figure 2 b). a) Phenalenyl radical with carbon labels and b) SOMO of phenalenyl.

g. 14. tuned by electron-donating or -withdrawing ability of the control center).53 kcal molÀ1 for 1 a) is more significant than the binding attenuation from the neutral to the reduction state (e. In the literature.g.08 kcal molÀ1 (1 a vs. it has better ability to donate electron (oxidation state) than to accept electron (reduction state). In this situation. The success of the switches relies on the differential bridge efficiency caused by the position effect. It will be interesting to build functional molecular devices using such multi-stage/multi-site approach. the binding enhancement from the neutral to the oxidation state (e. 2. the binding strengths DEb(+) of 1 and 2 are several kcal molÀ1 stronger than DEb(N) at the neutral state.g. the preferred binding site can be swapped.0 kcal molÀ1). 1. all DEb(N) values are again quite similar (Table 1). At this stage. TTF). Molecular electrostatic potentials (MEPs) around the pyrrole moieties of 3 and 4 at different charged states predict the preferred binding site well (see the Supporting Information) and can be employed for future molecular design. 500 – 504 502 . In a broader perspective. We can then convert this off state to an “on state” by redox reactions. ammonia will bind to both compounds in similar percentages. The essence of this study is not the use of phenalenyl radical or a pyrrolic hydrogen-bonding site as such.1 kcal molÀ1 for 3 and 4. in accord with the inferior bridge efficiency of the b-bridge. More importantly. in the reduction state. DEb(+) of 1 are always larger than that of 2 as expected. In the oxidation “on” state. so b-site is the superior binding site and the binding preference is ca. 1 b vs. However. KGaA. According to the sign of the charged states. it is the usage of position effect and of a redox-active unit with charged states of different signs. binding complications caused by the change of the charge states of a reaction center can be minimized. The SOMO of 3 and 4 at the neutral state at B3LYP/6-31 + G(d) level. DEb(+) in 3 and 4 are somewhat weaker than that in the corresponding one-bridge systems 1 b and 2 b. we propose that future endeavors along this direction may employ strong binding partners and delocalized reaction center. we have demonstrated a strategy to design electrochemically controlled three-stage/two-site hydrogen-bonding systems. The above results show that 3 and 4 can function as molecular switches and the motion of the hydrogen-bond partner can be controlled remotely. In the oxidation state. As our goal is to construct a three-stage/two-site motion control system with identical binding sites.and b-positions to enable tunable preferential binding with one stimulus-receptive center.CHEMPHYSCHEM COMMUNICATIONS 0. we call it an “off state”. Weinheim www.5 kcal molÀ1 for both 3 and 4 (cf. The binding ability of two identical hydrogen-bonding sites can be tuned symmetrically (the “off” state) or asymmetrically (the two “on” states).[17] It is noted that for a given compound. because a charged reaction center may also play the role of a binding site. In the current model study. 3. the asymmetrically controlled property needs not to be limited to binding.53 kcal molÀ1 for 1 a). molecular recognition with good fidelity often relies on multiple hydrogen bonds. With the longest bridge (n = 4). but not on the bbranch (Figure 4). bridges are attached to the a. 2 a. based on the concept of remote control. regardless of the bridge length. The results are positive.[18] In summary. 2 and ammonia are equivalent (1:1:1). 2. In nature. ChemPhysChem 2013. 2 is the preferential host to bind ammonia. tuned remotely and whether asymmetric control can be realized. On the other hand. but can also be other properties that can be tuned by electronic effects (i.2 b. the strength of the hydrogen bond of the a-site decreases more than that of b-site. With commonly used redox unit whose charged states do not change sign (e. In the “off” state. Therefore.org Figure 4. simple binding partners were employed to examine whether some local properties can be  2013 Wiley-VCH Verlag GmbH & Co. a similar switch between preferential binding between two hosts has been achieved by Rotello with the help of redox reactions and p-stacking interactions.e. Therefore.chemphyschem. revealing the electron-withdrawing effect of the reaction center. and so on). if the amount of compounds 1. 5. In 3 and 4.1 kcal molÀ1 for 1 b vs. the binding strength DEb(À) of 2 is larger than that of 1 for nearly 1 kcal molÀ1 at a given bridge length. the aforementioned binding control cannot be achieved. the ammonia binding energies of 3 and 4 were calculated (Figure 3). We ascribe this phenomenon to the fact that pyrrole is an electron-rich moiety. In the reduction state.27 kcal molÀ1 higher than that of 2 d. The frontier orbitals of 3 and 4 show electron distribution on the phenalenyl moiety and the a-branch of bridge/binding site. the binding strength of 1 d is still 1. the a-site is still significantly preferred by ca. as the electron-withdrawing effect is shared by two bridges in 3 and 4. 2 b). In other words. preferential binding of ammonia to 1 can be turned on. not very different from that between 1 b and 2 b (ca. Rather. In this way. 1.

DFT DEb(N) in this study should be reliable enough to show the trends for the purpose of molecular design. Tseng. Angew. R. Oakley. Reed. 116. the pyrrolic NÀH binding energy to ammonia was within the range of À6. 2343 – 2351. Natl. c) Y. Soc. K. J. 124. [6] a) X. C. F. 2003. Perkins. 2004. D. K. 3942 – 3951. e) J. W. R. C. Kobayashi. Itkis. K. V. Ed. D. C. R. e) S. J. b) H. J. P. Green. 296. Sato. S. J. Chem. Shin. Stoddart. J. 10029 – 10034. 2002. 1619 – 1620. 5. R. R. 124. A. J. Haddon. 2004. Chem. Cordes. I. T. Flood. F. Am.[20] Stationary points were confirmed to be local minima by means of frequency analysis.CHEMPHYSCHEM COMMUNICATIONS Computational Methods All calculations were performed with Gaussian 03. M. b) T. Stoddart. 2003. Angew. C. Y. D. W. Angew. Reed. d) C. X. Castellano. F. T. Sato. Ouyang. Li. S.75 for our neutral pyrrole-bearing phenalenyl derivatives. 21. Y. c) D. H. 115. B. C. 5884 – 5889. J. Ed. 256. Delonno. M. b) J. V. Coti. J. Cooke. X. J. C. Kubo. Yakusi. Chao. Stoddart. 2002. H. Weinheim ChemPhysChem 2013. J.-S. Donnadien. 626 – 634. Am. Erina. K. C. A.-R. T. T. It is shown in Table S4 that 1) most B3LYP/6-31 + G(d) values deviated from the ideal value by less than 10 %. 123. Donnadieu. Z. Tseng. Chem. J. S. M. Bunimovich. Tseng. f) S. Faraday Discuss. As shown in Tables S1 and S2. Aprahamian. 10395 – 10402. 1224 – 1226. Yang. Tanabe. Heath. Chen. R. one imaginary frequency) and À12. Peters. K. H. [9] a) P. 2005. W. W.org [1] a) Y. so we did not use finer grids and fix all the imaginary frequencies at the M05-2X level. T. E. QuiÇonero. 2007. Acknowledgements Computational time was granted by the National Center for High-Performance Computing and the Academia Sinica Computing Center. Zink. A. Badjic S. Hwang. 2222 – 2226. Johnston-Halperin. Shiomi. J. 2001.77 (fine. J. P. 8816 – 8818. Nielsen. Kubota. [2] a) R. R. 2006. H. A. 7. respectively) were well within the range. 2004. Stoddart. Cheng. 1975. 1871 – 1874. ChemPhysChem 2002. F. 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Stoddart.-S. 6348 – 6350. Steuerman. Haddon. 1793 – 1796. 6232 – 6233. Stoddart. e) S. B. [10] a) K. Luo. H. Sarkar. Reed. Chi. K. I.-M. Yamamoto. K. E. 1491 – 1495.-S. J. Jursíkovµ. C. Science 2004. Perkins. Angelos. W. M. F. Reid. K. 131. Tham. J. Stoddart. J. Jeppesen. O. Johnston-Halperin. 309. F. Silvi. Chi. Am.-F. J. Nakasuji. Haddon. Liu. [11] a) R. Int. Haddon. Beer. E. Chem.-R.. 1616 – 1624. W. Koutentis. E. Hwang. D. 2009. Chen. Chem. Chem. Stoddart.-R. Zink. b) H. < S2 > . 28. Morita. 3. Aust. 2008. 1845 – 1849. M. Wei. M. ChemPhysChem 2004. R.5 kcal molÀ1. Stoddart. Haddon. H. Heath. Y. S.-J. W.-Y. A small imaginary frequency (< 25i cmÀ1) remained for 3/4 of the M05-2X results calculated with the fine grid (see the Supporting Information. M. 2) the M05-2X results have larger spin contamination than the B3LYP results. Chem. Chem. USA 2005. Itkis. 10. 2008. Research was funded by the National Science Concil of Taiwan (project number: NSC 97-2113M-001-018-MY3). Zink. 2004. N. A. J. D. 2703 – 2705. Tseng. Haddon. Haddon. Chem. Zhao. I. Chem. T. R. 6486 – 6491. H. Fukui. W. F. 306. 2226 – 2237. J. K. I. 2009. The energy differences were too small to affect the predicted trend of binding strength for our systems. DEb(À)). K. c) A. Rotello. [8] a) J. C. c) T. 2007. N. Yasuda. With the use of the ultrafine grid. L. Steuerman. Chen. Reed. C. Therefore. 111 – 116. K. Y. J. Cordes. Chem.51 (ultrafine grid) kcal molÀ1. D. Tseng. Luo. Asian J. Chem. Boukai.[19] The geometries of all systems were fully optimized with the 6-31 + G(d) basis set at the B3LYP and M05-2X levels. T. R. Stoddart. The ammonia binding energies for neutral 1 a were À7. L. Hernandez. H. Credi. Green. K. E. Jeppesen. Lo. Frontera. C. Cryst. J. but still checked the trends of the closed-shell ionic systems (Table S3). W. Ballardini. 2002. Science 2005. F. Angew. Tseng. H.[5] Single-point MP2/6-31 + G(d)//B3LYP/631 + G(d) calculations have been carried out to confirm the trends.-R. Am. F. 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