Double-Circularly Connected Saloph-Belt Macrocycles Generated

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Double-Circularly Connected Saloph-Belt Macrocycles Generated from a Bis-Armed Bifunctional Monomer Takashi Nakamura, Shinnosuke Tsukuda, and Tatsuya Nabeshima J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 08 Apr 2019 Downloaded from http://pubs.acs.org on April 8, 2019

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Journal of the American Chemical Society

Double-Circularly Connected Saloph-Belt Macrocycles Generated from a Bis-Armed Bifunctional Monomer Takashi Nakamura, Shinnosuke Tsukuda, and Tatsuya Nabeshima* Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.

Supporting Information Placeholder ABSTRACT: Belt-shaped macrocycles possessing saloph

units as their walls have been generated by the doublecircular connection of a bis-armed bifunctional monomer bearing both o-phenylenediamine and salicylaldehyde functionalities. The saloph-belt macrocycles showed unique properties, such as the selective inclusion of fullerenes (Ka(C70)/Ka(C60) > 100), utilizing their rigid scaffolds.

Belt-shaped macrocycles, which possess a cavity surrounded by a wide wall, have attracted much attention.1– 11 They can be synthesized by the connection of multiple units via two or more bonds in a circular manner along the macrocycle. Compared to ring-shaped macrocycles, whose monomeric unit is typically linked by a single bond, each unit of the belt-shaped macrocycles does not have a rotational freedom, and thus its relative position is fixed (Figure 1a). This structural feature is advantageous in designing the functional macrocycles aimed at specific molecular recognition1,4,10,11 and unique photophysical properties2,5,6. Despite its usefulness, the double-circular connection for making the belt-shaped compounds is synthetically challenging. One approach to achieve such a macrocyclization is the employment of reversible non-covalent interactions, such as hydrogen bonds7,8 and metalligand coordination9–11, in order to realize an efficient self-correction process. For the synthesis of the covalentbonded belt-shaped macrocycles, one strategy is the formation of two cyclic connections in a stepwise manner, that is, linking each adjacent unit of a single-circularly connected ring-shaped macrocycle with a secondary bond formation.5 Another strategy is the use of two kinds of multivalent monomers, such as the synthesis of the porphyrin nanobarrel4 via a 2:2 cyclization of a tetraborylporphyrin and a tetrabrominated porphyrin unit. In this context, the one-pot oligomerization of one type of monomer offers a simple and novel approach to the synthesis of covalent-bonded belt-shaped macrocycles. To realize the double-circular connection, four connection

points (two each for one forming bond) have to be introduced to the employed monomer, and each monomer must be joined in a ladder-like fashion without resulting in random network structures.

Figure 1. (a) Comparison of a ring-shaped macrocycle with a single-circular connection and a belt-shaped macrocycle with double-circular connections. (b) A schematic representation of the synthesis of a belt-shaped macrocycle by the oligomerization of a bis-armed bifunctional monomer.

We now report the belt-shaped macrocycles generated by the oligomerization of a bis-armed bifunctional monomer (Figure 1b). Compound 1´ bearing two salicylaldehyde units and one o-phenylenediamine unit within one molecule has been designed for this purpose (Figure 2). It is well known that the condensation of two components (salicylaldehydes and o-phenylenediamines) leads to the Schiff-base saloph, an N2O2 chelating ligand.12 In this study, the saloph is used as a dynamic bond formation unit13–17 in the oligomerization. The bifunctional monomer 1´, which is generated in-situ from the acetal-protected precursor 1, reacts in a head-to-tail manner to form the double-circular connection. The wall of the resulting

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belt-shaped compounds after the metal complexation is comprised of multiple saloph units that are perpendicular to the macrocyclic plane. Therefore, effective interactions utilizing the aromatic face of the saloph or the axial ligand of the saloph metal complex are expected for the included molecules inside the cavity. This structural feature is unique compared to the other salen/saloph-based macrocycles, in which each unit is arranged in a coplanar manner.18–28

1,5-Dibromo-2,4-dihexyloxybenzene (2)33 was converted to the bis(pinacol) ester 334 by the Miyaura-Ishiyama borylation reaction. One of the two pinacolatoboron groups reacted with the salicylaldehyde unit 5 (a 1,3-dioxane derivative of 435) to form an “arm” 6. The twofold Suzuki-Miyaura coupling reaction of 6 and 1,2-dibromo4,5-dinitrobenzene (7)36 afforded 8, and subsequent treatment of 8 with hydrogen on Pd/C produced the monomer 1 (1H NMR, Figure 3b). Scheme 1. Synthesis of bis-armed bifunctional monomer 1.

Figure 2. Belt-shaped macrocyclic tetramer [S4M4X4n] and trimer [S3M3X3n] (M, metal; X, ligand, see Notes) with saloph units as their walls, which are generated from the bisarmed bifunctional monomer 1´ (a deprotected form of 1) bearing both o-phenylenediamine and salicylaldehyde functionalities. R: n-hexyl.

Conditions: (a) Bis(pinacolato)diboron, Pd(dppf)Cl2, AcOK, DMF, 115 °C, 14 h, 51%. (b) 1,3-propanediol, pTsOH, CH(OMe)3, toluene, 85 °C, 6 h, 92%. (c) 3, Pd(PPh3)4, Cs2CO3, DMF, 90 °C, 12 h, 41%. (d) Pd(PPh3)4, K2CO3, Dioxane/H2O, 100 °C, 12 h, 69%. (e) H2, 10% Pd/C, EtOH, 50 °C, 5 h, quant.

Compound 1, an acetal-protected derivative of bis-aldehyde 1´, is designed as an isolable bifunctional monomer3,29–32 for the saloph-belt macrocycles. The formyl groups were protected in order to prevent its self-oligomerization. The two acetal-protected salicylaldehyde units were attached to the central o-phenylenediamine via m-phenylene linkers. The two n-hexyloxy groups were introduced to the m-phenylene in order to enhance the solubility of the macrocycles without hampering the guest inclusion inside the cavity. Monomer 1 was synthesized by Scheme 1 (see also Schemes S1–S4, Figures S1–S10).

The oligomerization was performed by the deprotection of the formyl groups of 1 and the intermolecular head-totail formation of the Schiff-base saloph units in one pot. Among the investigated conditions (see Table S1 and Figure S39 for details), heating 1 in CHCl3/CH3OH = 3/1 in the presence of 1 equiv. of MsOH and molecular sieves 3A (MS3A) produced the macrocyclic tetramer H8S4 the most efficiently (~40%, 1H NMR yield), together with the macrocyclic trimer H6S3 (~32%) (Table S1, entry 1). The increased ratio of methanol suppressed the formation of trimer H6S3, but more unidentified oligomers were


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produced (Table S1, entries 3,4). The use of toluene instead of chloroform preferentially yielded the trimer H6S3 (Table S1, entry 5). The purification by alumina column and gel permeation chromatography of the reaction mixture of CHCl3/CH3OH =3/1 gave H8S4 and H6S3 in 28% and 8% isolated yields, respectively (Figure 3a) (see also Scheme S5, Figures S11–S22, S26, S27, S35, S36). In the 1H NMR spectra of H8S4 and H6S3, the signals characteristic of the saloph units were observed (hydroxy, 13.2–13.3 ppm; aldimine, 8.48–8.49 ppm) (Figure 3c,d). There are four different signals for the oxymethylene protons a, suggesting their diastereotopic environments as the result of the macrocyclization.

are 8.4–8.6 Å. This cavity size of the trimer H6S3 is smaller than that of the tetramer H8S4 calculated by molecular mechanics (N–N between the opposite face: 13.3– 14.0 Å) (Figure S40).

Figure 4. Structure of macrocyclic trimer H6S3 determined by X-ray crystallography. n-Hexyloxy groups are omitted. (a,b) An ellipsoidal model (50% probability, hydrogens not shown). A top view (a) and a side view (b). (c,d) A spacefilling model. A top view (a) and a side view (b).

The metal complexation of H8S4 to form a Zn-saloph37– derivative was next investigated. The reaction of H8S4 with Zn(OAc)2 in a toluene-methanol mixed solvent produced a tetranuclear Zn complex [S4Zn4X4] (X: ligand, see Note) (Figure 5a, Scheme S6, Figures S23–S25, S28, S33). Complexation at the saloph unit is considered to restrict the conformational freedom in the macrocyclic framework, thus strong interactions with the included molecule are expected. The fullerenes were then investigated as the guest for the macrocycle.4,11,23,40–56 Studies of preferential binding of fullerenes by designed receptors have been reported,28,46–56 which can lead to its efficient separation method. However, the selective binding of a specific fullerene over the others by 2-orders in magnitude is challenging.52–56 The formation of a new species was indicated by 1H NMR upon the addition of 1 equiv. of C60 to [S4Zn4X4] (Figure 5b, Figure S41). ESI TOF-MS measurement of the sample gave the signals assigned to [C60·S4Zn4·Hn]n+ (n = 2,3), a 1:1 host-guest complex (Figure 5c). Interactions between [S4Zn4X4] and C60 were also monitored by UV-vis absorption and emission titration experiments (Figure 5d,e). [S4Zn4X4] showed a broad absorption at 422 nm (toluene/CH3OH = 9/1) characteristic of the Zn-saloph unit. The strength of this band decreased upon the incremental addition of C60. The emission of [S4Zn4X4] (lmax = 536 nm, quantum yield FF 39

Figure 3. Formation and characterization of saloph-belt macrocycles. (a) Formation of saloph-belt macrocycles H6S3 and H8S4. (b–d) 1H NMR spectra (CDCl3, 600 MHz). (b) A bis-armed bifunctional monomer 1. (c) Trimer H6S3. (d) Tetramer H8S4.

The structure of trimer H6S3 was successfully revealed by X-ray crystallography (Figure 4). When viewed from the pseudo threefold axis, H6S3 has a triangular shape with o-phenylenediamine units at its side (Figure 4a). On the other hand, the salicylaldimine units as well as m-phenylene linkers were tilted outside to make the corners of the triangle. Thus, the saloph units in H6S3 are not planar. The two circular frameworks along the macrocycle are not identical in the crystal (Figures 4b,d). The three salicylaldimine units of the upper half are projected, which makes the shape of H6S3 like a crown. H6S3 has a cavity whose nitrogen-nitrogen distances between the salophs



= 0.06) also decreased (FF = 0.02) after the addition of C60 (7 equiv). One possible explanation for these spectral changes is the photoinduced electron transfer from Znsaloph to C60.57

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C60 contacted face-to-face with only the two diagonal Znsaloph units. The C-H ··· p interaction with the m-phenylene linker (~2.9 Å) as well as the p-p interactions with the saloph units (~3.2 Å) are the main intermolecular forces between C60 and the saloph-belt complexes (Figure 6d).

Figure 6. Structure of [C60ÌS4Zn4(CH3OH)4] determined by X-ray crystallography. n-hexyloxy groups and solvents are omitted. (a,b) An ellipsoidal model (30% probability, hydrogens not shown). A top view (a) and a side view (b). (c) A space-filling model. (d) Intermolecular interactions between C60 and S4Zn4(CH3OH)4.

Figure 5. Encapsulation of fullerene by saloph-belt. (a,b) 1 H NMR spectra (toluene-d8/CD3OD = 9/1 (v/v), 600 MHz). (a) [S4Zn4X4]. (b) [C60ÌS4Zn4X4] ([S4Zn4X4] + C60 (1 eq)). (c) ESI-TOF mass spectrum of [C60ÌS4Zn4X4] (CH3CN, 0.25 µM, positive). (d,e) Titration experiments of C60 against [S4Zn4X4] monitored by absorption (d) and emission (e) (toluene/CH3OH = 9/1 (v/v), [S4Zn4X4] = 0.83 µM, l = 1.0 cm).

An X-ray crystallographic analysis showed the detailed structure of the 1:1 inclusion complex [C60ÌS4Zn4(CH3OH)4] (Figure 6). The belt-shaped framework of S4Zn4 circularly surrounded C60. The crystal’s space group is P-1 with its inversion point at the center of the [C60ÌS4Zn4(CH3OH)4]. Each Zn atom was coordinated by CH3OH (a crystallization solvent) from the outside of the macrocycle. The shape of S4Zn4 viewed from its top is more a parallelogram than a square (Figure 6a). The diagonal Zn-Zn distances are 15.61 and 13.58 Å. As can be recognized from Figure 6c, the fullerene

The 1:1 binding constant Ka [M–1] between [S4Zn4X4] and C60 was determined to be logKa = 6.27(5) from the UV-vis titration experiment (toluene/CH3OH = 9/1) (Figure 5d, Figures S42, S43). The interaction of [S4Zn4X4] with C70 was also investigated, and the binding is too strong to be determined by an ordinary UV-vis titration experiment (logKa > 7) (Figures S45–S46). The competitive 1H NMR titration experiment of C70 in the presence of excess C60 (6 equiv.) showed that [C70ÌS4Zn4X4] quantitatively replaced [C60ÌS4Zn4X4] by the addition of 1 equiv. of C70 (Figure S47). Based on this result, we can safely estimate that the binding constant of C70 is higher than that of C60 by over two orders of magnitude (Ka(C70)/Ka(C60) > 100). To the best of our knowledge, the best reported selectivity for C70 over C60 is Ka(C70)/Ka(C60) ~ 1000 (in toluene) achieved by the quadruply-bridged porphyrin dimer with three-dimensional shape-persistent framework synthesized via alkyne metathesis.53 As for the macrocycles, many fullerene receptors display moderate selectivity (up to one order of magnitude),40,43,46–48,51 and limited examples with rigid frameworks exhibit the selectivity of Ka(C70)/Ka(C60) > 100.52,54–56 Thus, the rigid belt-shaped scaffold of


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[S4Zn4X4] is considered to be a key factor to realize the strong binding and selectivity toward C70. The cavity size of [S4Zn4X4] probably matched better with C70, as can be inferred from the compressive deformation of [S4Zn4X4] into a parallelogram when including C60 (Figure 6c). Comparing the 1H NMR chemical shifts of [C70ÌS4Zn4X4] and guest-free [S4Zn4X4], the protons near the horizontal pseudo-mirror plane of the macrocycle (g, h, i and j) shifted downfield upon the inclusion of C70, while the protons at the edge of the belt (m, l, k) shifted upfield (Figure S44). These changes are mainly caused by the anisotropic ring current of the ellipsoidal C70. Based on previous studies,28,43 the pattern of the shielding/deshielding effect in [C70ÌS4Zn4X4] suggests that C70 orients itself so as to place its longer axis along the horizontal plane of the macrocycle. The metal-free ligand H8S4 also encapsulated C60, but its binding is weaker (logKa = 5.82(4)) than that of [S4Zn4X4] (Figures S49, S50). One explanation for this difference is that the complexation of the saloph units with zinc resulted in the rigidification of the macrocyclic framework to favor the guest inclusion. The appropriate cavity size of the macrocyclic tetramers is important for the fullerene binding, as slight or no interactions with C60 were observed for the macrocyclic trimer H6S3 and a monomeric Zn-saloph derivative (Figures S51, S52). The affinity of fullerenes to the macrocyclic tetramer can be employed to shift the equilibrium of the cyclization reaction by the template effect. In the presence of fullerenes C60 or C70, the oligomerization of monomer 1 in toluened8/CD3OD = 2/1 produced (C60 or C70)ÌH8S4 in 75% or 67%, respectively (1H NMR yields, Figure S53 and Table S2). In an attempt to apply the saloph-belt compounds as catalysts, tetrameric and trimeric Mn-saloph complexes [S4Mn4X4n] and [S3Mn3X3n] were synthesized from the corresponding ligands and Mn(OAc)2 (Schemes S7–S8, Figures S29–S32, S37, S38). As a preliminary trial, their catalytic activity toward epoxidation of olefins58–60 using the PhIO oxidant was investigated using a-linolenic acid (all-cis-9,12,15-octadecatrienoic acid) as a substrate. So far, the site-selective epoxidation of a-linolenic acid and its ester has been investigated by the systems employing enzymes (100% selectivity to produce 15,16-monoepoxide;61 92% yield to produce 9,10-15,16-diepoxide62) or lipid bilayers (82% selectivity to produce 15,16-monoepoxide)63. However, the non-enzymatic reactions in homogenous systems generally show little regioselectivity.64 The analysis on the site-selectivity in the monoepoxidated products revealed that the Mn-saloph-belt complexes [S4Mn4X4n] and [S3Mn3X3n] proceeded with the epoxidation at the terminal olefin (D15,16) (15,16epoxide/12,13-epoxide/9,10-epoxide = 63/17/20 ([S4Mn4X4n]) and 58/19/23 ([S3Mn3X3n])), which is in contrast to the result of a reference monomeric Mn-saloph complex that displayed little selectivity (15,16-

epoxide/12,13-epoxide/9,10-epoxide = 36/28/36) (Figures S54–S56). The development of the saloph-belt derivatives as supramolecular catalysts65,66 is now being investigated. In conclusion, novel belt-shaped macrocycles possessing multiple saloph units as their walls have been synthesized. The double-circular connection of the bisarmed bifunctional monomer 1 via the formation of the salophs produced the macrocyclic tetramer H8S4 and trimer H6S3. The tetranuclear zinc complex [S4Zn4X4] exhibited a firm and selective binding of the fullerenes (C60 and C70, Ka(C70)/Ka(C60) > 100) by the effective interaction with its belt-shaped framework. The belt complexes can offer a cavity surrounded by the catalytically-active saloph units, thus have great potentials as supramolecular catalysts exhibiting unique selectivities. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.#######. Detailed synthetic procedures and characterization data (PDF) Crystallographic data (CIF)

AUTHOR INFORMATION Corresponding Author

[email protected] Funding Sources

No competing financial interests have been declared. Notes

In the structures of the saloph-belt complexes, the axial coordinating ligand is written as X for its lability and ambiguity in solution. X is specified only when unambiguously characterized.

ACKNOWLEDGMENT This research was supported by JSPS KAKENHI Grant Numbers JP17H05351 (Coordination Asymmetry), JP17K14455, JP18H01959, and the research grant of Astellas Foundation for Research on Metabolic Disorders.

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Figure 1 84x75mm (300 x 300 DPI)



Figure 2 84x125mm (300 x 300 DPI)


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Figure 3 84x111mm (300 x 300 DPI)





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Figure 5 84x138mm (300 x 300 DPI)





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Scheme 1 84x116mm (300 x 300 DPI)



Table of Contents 125x81mm (300 x 300 DPI)


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Double-Circularly Connected Saloph-Belt Macrocycles Generated

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