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Truncated Sierpi#ski Triangular Assembly from a Molecular Mortise-Tenon Joint Mingzhao Chen, Jun Wang, Shi-Cheng Wang, Zhilong Jiang, Die Liu, Qianqian Liu, He Zhao, Jun Yan, Yi-Tsu Chan, and Pingshan Wang J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 28 Aug 2018 Downloaded from http://pubs.acs.org on August 29, 2018

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Journal of the American Chemical Society

Truncated Sierpiński Triangular Assembly from a Molecular MortiseTenon Joint †,⊥

†,⊥

§

Mingzhao Chen, Jun Wang, Shi-Cheng Wang, Zhilong Jiang,* ,§ ,†,‡ Yi-Tsu Chan,* Pingshan Wang*

,†,‡

†,‡

Die Liu,

†

†

†

Qianqian Liu, He Zhao, Jun Yan,

†

Department of Organic and Polymer Chemistry, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan-410083, China ‡

Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Institute of Environmental Research at Greater Area, Guangzhou University, Guangzhou-510006, China §

Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan

Self-Assembly • Metallo-Organic Ligands • Multitopic Terpyridines • Mortise-and-Tenon Joint ABSTRACT: The amalgamation of different components into a giant and intricate structure that makes quantitative and spontaneous assembly through molecular design is indispensable but challenging. To construct novel metallosupramolecular architectures, here we present an architectural design principle based on multicomponent self-assembly. Using a carefully designed hexatopic terpyridine-based metallo-organic ligand (MOL), [Ru2T2K], we report on the formation of supramolecular trapezoid Zn5[Ru2T2K]V2, hollow hexagon Zn15[Ru2T2K]3K3, and giant star-shaped supramolecule Zn18[Ru2T2K]3[Ru2X2V]3, all of which were assembled by one-pot, nearly quantitative assembly of [Ru2T2K] with the ditopic 60°-directed bisterpyridine V, tetrakisterpyridine K, and MOL [Ru2X2V], respectively. The complementary ligands were selected on the basis of the size- and shape-fit principles, actually similar to the mortise– tenon joint that aligns and locks the two complementary wood components. This strategy is expected to open the door to sophisticated designer supramolecules and nonbiological materials. The multivalent connections within the mutual ligands give rise to the formation of stable assemblies, which are unambiguously characterized by NMR, ESI-MS, TWIMMS, and TEM analyses.

INTRODUCTION In primitive society, our wise ancestors developed a variety of woodworking skills for building construction. One of the commonly used techniques is the mortise-and-tenon joint1 (Figure 1) that can efficiently connect two pieces of wood to create needed geometry.2 This basic method has inspired scientists in many fields like engineering, biology, chemistry, and materials science. In most cases, an integrated whole is gathered by different functional modules in a controlled manner. Some protein assembly processes in biological systems also follow such a design. 3-6 The

Figure 1. Cartoon illustration of a mortise-and-tenon joint in building construction.

biomolecular subunits often require the precisely preorganized donor and acceptor that resemble the tenon tongue and mortise hole. As the germination and maturity of metallosupramolecular chemistry, assembling complicated and functional supramolecular structures also simultaneously possessing the mathematics and art aesthetics draws more and more concerns. Whether for twodimensional (2D) or three-dimensional (3D) metallosupra-architectures, synthesis of giant rigid and ordered species is extremely challenging, not only in the troublesome synthesis process, but also in the reasonable characterization. An effective strategy for assembling more massive metallosupramolecular species is modular construction, which connects within mutual subunits through a multiple interlocking process. From supramolecular chemistry perspectives, to date numerous 2D and 3D architectures7-25 have been constructed based on coordination-driven self-assembly,26-31 while most of them were assembled from only one kind of ligands. Although some examples of using more than one ligand type have been reported by Lehn,32,33 Stang,34,35 Fujita,36,37 38,39 40-47 Schmittel, and others, owing to the multiple

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equilibria for each species that have a great impact on the final assemblies,48,49 it still remains a formidable challenge for successful multicomponent selfassembly of well-defined metallo-supramolecules. 2,2’:6’,2”-Terpyridine (tpy)-metal complexes, due to the tunable bond strength,50-53 are excellent coordination motifs for construction of various 2D54-58 and 3D59-64 metallosupra-architectures, which potentially could be used to prepare functional materials and devices.65 It is worth mentioning that metallo-organic ligands (MOLs) derived from kinetically inert connectivity can be a useful strategy to prepare diverse multitopic ligands for further self-assembly of sophisticated structures. Previously we have applied this methodology to the construction of a giant supramolecular nut, 66 a hexagram67 and Pascal's Triangle.68 To propel the field of supramolecular artificial synthesis further into artistic and mathematical synthetic chemistry and further understand the impact of complementary multitopic MOLs on the resultant assemblies, here we raise an analogic concept, mortise-and-tenon joint, in virtue of its similar stability characteristics. We design and synthesize a novel hexatopic MOL, [Ru2T2K], and treat it with V and K shape ligands in the presence of Zn(II) ions to afford the supramolecular trapezoid Zn5[Ru2T2K]V2 and hollow hexagon Zn15[Ru2T2K]3K3, which can be regarded as truncated first- and secondgeneration Sierpiński triangles. In addition, when an equimolar mixture of [Ru2T2K] and [Ru2X2V] are complexed with Zn(II) ions, the star-shaped metallosupramolecule Zn18[Ru2T2K]3[Ru2X2V]3 with a molecular weight of ca. 34,047 Da is assembled in nearly quantitative yield. Specifically, the giant star-shaped 2D-supra-structure consisting of twelve little triangles exhibits a huge central hollow without any solid support, what's interesting is that the giant central hollow part equates to complex Zn15[Ru2T2K]3K3. When viewed at it as a whole, Zn18[Ru2T2K]3[Ru2X2V]3 was constituted by three trapezoids and three little triangles by utilizing vertex connectivity; it looks like a big triangle and a truncated triangle that formed a star like David by crossing and overlapping. To the best of our knowledge, there is no report about such giant rigid 2D metallosupramolecular architecture by multicomponent modular construction without a troublesomely isolating process. Differing from our previous work, it can be

organic ligand [Ru2X2V] were synthesized according to the reported procedures.48,67 The key metalloorganic ligand (MOL) [Ru2T2K] with six free terpyridines was achieved by a six-fold Suzuki-Miyaura coupling reaction of 4’-(4-boronophenyl)-tpy with the hexabromo-substituted dinuclear Ru(II) complex 9 (Scheme 1). Compound 4 was synthesized by reacting bisterpyridine V with a solution of Br2 in CHCl3. TpyRuCl3 adduct 8 and the hexabromo-substituted dinuclear Ru(II) complex 9 were synthesized via a similar procedure that we have reported. 66 The detailed synthetic routes and procedures were available in the supporting information. 1H NMR spectra of 10 (Figure 3C) displayed four singlets at 9.29, 8.89, 8.82, and 8.76 ppm with a 1:1:1:2 integration ratio attributed to Scheme 1. Synthesis of Metallo-organic Ligand [Ru2T2K]

Scheme 2. Self-assembly and Structures of Metallosupramolecular Truncated First- and SecondGeneration Sierpiński Triangles, Zn5[Ru2T2K]V2 and Zn15[Ru2T2K]3K3

expected that the larger pre-organized modular units could make multiple components accurately assemble into larger desirable architectures. These species of gi-

ant rigid 2D metallosupra-architectures show potential applications in making materials for molecular electronics, bioimaging, and energy storage.

RESULTS AND DISCUSSION Ligands Synthesis. Ditopic 60°-directed bisterpyridine 3, tetrakisterpyridine 11, ligand 7, and metallo-


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Journal of the American Chemical Society

Figure 2. ESI-MS spectra of (A) 12 and (C) 13. 2D ESI-TWIM-MS plots of (B) 12 and (D) 13.

the four kinds of 3’,5’-tpy protons. In addition, three singlets at 4.16, 3.89, and 3.82 ppm with a 1:1:2 ratio assigned to the three kinds of -OCH3 were consistent with the proposed structure. The complete 1H NMR peak assignments were confirmed by 2D COSY and NOESY experiments (Figures S20 and S21).

Self-Assembly and Characterization of the First and Second Generation of Sierpiński Triangles. In order to generate the desired supramolecular trapezoid (Scheme 2), the self-assembly was conducted by mixing [Ru2T2K] (seen as mortise) and ligand V (seen as tenon) with Zn(II) ions in a precise stoichiometric ratio of 1:2:5 in a mixed solvent of MeCN/CHCl3/MeOH (4:1:1, v/v/v). The reaction mixture was stirred at 75°C for 12 h. After cooling to room temperature, a slight excess of NH 4PF6 was added to give a red precipitate, which was thoroughly washed with MeOH and H2O, and then dried in vacuo at 50°C for 12 h. The chemical composition of Zn5[Ru2T2K]V2 was verified by a series of major ESI-MS peaks with the charge states from 4+ to 11+ due to the loss of the corresponding number of PF6− units during ionization (Figure 2A). The isotope distributions for each state were closely matched with the corresponding simulated patterns for the desired structure with a molecular weight of ca. 7,612 Da (Figure S29). The 1H NMR spectrum of the resultant complex (Figure 3B) exhibited four characteristic peaks at 4.18, 4.05, 3.95, and 3.88 ppm with an integration ratio of 1:2:1:2 derived from two singlets and one pair of two overlapped singlets for the six types of methoxy units. As compared with the uncomplexed tpy units in ligand V and [Ru2T2K], after complexation with Zn(II) ions, all the 6,6”-tpy protons revealed significant upfield shifts due to the inter-ligand shielding effects, strongly supporting the formation of octahedral connectivity.69 Moreover, the 1H NMR

signals for ligand V and the purple tpy motifs of [Ru2T2K] were split into two sets of peaks (Figures 3A-3C), which were consistent with the molecular symmetry of trapezoid Zn5[Ru2T2K]V2 possessing seven kinds of tpy chemical environments. Again, the proper assignments were confirmed by COSY and NOESY spectra (Figures S2-S3). Notably, in this selfassembly process, no detectable signals were found for the metallo-triangle [Zn3V3] possibly assembled from ligand V alone. Traveling wave ion-mobility mass spectrometry (TWIM-MS) has been widely employed to obtain structural information and to differentiate isomeric separation process. 70-73 In the TWIMMS plot of Zn5[Ru2T2K]V2 (Figure 2C),the narrow drift time distributions for each charge state reflected the absence of isomers as well as the high structural rigidity of the trapezoid. The experimental collision cross-sections (CCSs) derived from the drift times were also in good accord with the simulated values (Table S1). Building on the trapezoid structure, the complexation reaction of MOL [Ru2T2K] and ligand K with Zn(II) ions was carried out under the same conditions. Since tetrakisterpyridine K can be regarded as a 120°directed tenon consisting of two 60°-bent bisterpyridines that is complementary to the 120°-directed mortise [Ru2T2K], it was envisioned that ligand K could connect three trapezoids to form a cyclic structure (Scheme 2). As expected, the 1H NMR spectrum of Zn15[Ru2T2K]3K3 (Figure 3D) exhibited a very complicated pattern because the resultant architecture gave rise to seven sets of tpy peaks. The broad peaks presumably resulted from the conformational heterogeneity, and the higher conformational flexibility was supported by the increased standard deviation for the CCSs in comparison with Zn5[Ru2T2K]V2 (Tables S1S2). Similarly, the 1H NMR signals for the 6,6”-tpy



1

Figure 3. H NMR spectra (500 MHz, 298K) of (A) 3 in CDCl3, (B) 12 in CD3CN, (C) 10 in CD2Cl2, (D) 13 in CD3CN, and (E) 11 in CDCl3.

protons of the free tpy units were shifted markedly upfield after coordination to metal centers. In addition, the nonaromatic region exhibited multiple peaks at about 3.89-4.18 ppm with an integration ratio of 5:3:6 corresponding to three peaks for –OCH3 and a triplet for –OCH2– (Figure 3D, Figure S8). The ESI-MS spectrum of Zn15[Ru2T2K]3K3 (Figure 2B) displayed prominent peaks with explicit isotope patterns (Figure S30) attributed to the ions with 12+ to 22+ charge states, confirming the composition of Zn15[Ru2T2K]3K3. No isomeric structures were found in the TWIM-MS plot (Figure 2D), and the experimental average CCS agreed well with the theoretical ones (Table S2).74

Self-Assembly and Characterization of Giant Star-shaped Metallo-supramolecule. Although we recently reported a 2D metallo-supramolecular hexagram67 assembled from MOL [Ru2X2V] (ligand 17) and ligand V, self-assembly of two multitopic MOLs into a well-defined structure has not yet been demonstrated. To this end, we attempted to use [Ru2T2K] along with [Ru2X2V] to construct a bimetallic star-shaped structure (Scheme 3). Because [Ru2X2V] can be seen as a lengthened ligand K, it might also function as a 120°-directed tenon and replace building block K in the framework of 13. The self-assembly of complex 18 was carried out by using the similar procedure to that for 13. Large preorganized modular units, and moreover, error checking and self-correction in the self-assembly process may contribute to the generation of the void star-

shaped structure. The resultant complex still showed good solubility in CH3CN, DMF, DMSO and DMAC. Its 1H NMR spectrum revealed broad and complicated signals (Figure S9) in the aromatic region as a result of the target complex possessing ten sets of tpy peaks. Nevertheless, the nonaromatic region exhibited a singlet for the –OCH3 resonances and the –OCH2– triplet at about 3.89-4.19 ppm implied the formation of a single molecular metallo-supramolecular starshaped Zn18[Ru2T2K]3[Ru2X2V]3 (Figure S11). The molecular formula of star-shaped complex Zn18[Ru2T2K]3[Ru2X2V]3 was further definitively determined by the ESI-MS analysis, which displayed a distribution of distinct signals generated from the continuous multiply charged ions from 15+ to 29+ (Figure 4A). The experimental m/z values for the main peaks were perfectly consistent with the theoretical ones derived from the assembled composition of Zn18[Ru2T2K]3[Ru2X2V]3 with a molecular weight of ca. 34,047 Da. For each charge state, besides the major peaks, the minor signals coming from {18+ nCH3CN} (n = 2−5) and {18 − nPF5} (n = 1−2) were observed (Figure S38), most likely because a few solvent molecules were included in the giant framework and PF6− counterions were dissociated into neutral PF5 and F− ions during ionization.75 Hence, due to the high molecular weight and the encapsulated solvent molecules, the satisfactory isotope patterns could not be acquired (Figure S34).76 However, no isomeric structures were detected in the TWIM-MS analysis (Figure 4B), and the experimental CCSs were in good agreement with the simulated values (Table S3).


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Journal of the American Chemical Society Scheme 3. Self-assembly and Structure of Metallo-supramolecular Star-shaped Zn18[Ru2T2K]3[Ru2X2V]3.

outcomes showed a single band at log D = −9.60, −9.92, and −10.05 m 2s−1 for 12, 13, and 18, respectively (Figure 5), indicating the formation of a sole species in CD3CN, and showed the experimental hydrodynamic radius rH = 2.3, 4.4, and 5.9 nm, respectively. The TEM images obtained by drop casting 13 and 18 onto carbon-coated copper grids (400 mesh) from dilute MeCN solutions (∼10−6 M) are presented in Figure 6. The averaged calculated diameters from 4 and 12 candidates in the TEM images of hexagon 13 and star-shaped complex 18 were 8.6±0.1 and 12.0±0.1 nm, respectively, which agreed well with the dimensions of the corresponding geometry-optimized structures (Figures S40-S41).

Figure 4. (A) ESI-MS spectrum and (B) ESI-TWIM-MS plot of 18.

Size Characterization by Diffusion-ordered Spectroscopy (DOSY) NMR and Transmission Electron Microscopy (TEM). Attempts to grow crystals of those metallo-supramolecular complexes suitable for X-ray single-crystal structure analysis have been proven to be failed to date. Instead, DOSY NMR28 and TEM experiments were performed in order to gain additional structural insights. The DOSY

Figure 5. DOSY spectra (500 MHz, 298K) of metallospramolecular (A) 12, (B) 13, and (C) 18.

CONCLUSIONS In summary, hexatopic MOL [Ru2T2K] has been successfully synthesized, whose preprogrammed geometry can be considered as a building block with two mortise sites. When



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ORCID Mingzhao Chen: 0000-0002-4692-7114 Yi-tsu Chan: 0000-0001-9658-2188 Pingshan Wang: 0000-0002-1988-7604

Author Contributions ⊥

M.C. and J.W. contributed equally to this work.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This research was supported by the Distinguished Professor Research Fund from Guangzhou University of China (P.W.). Y.-T.C. acknowledges the support from the Ministry of Science and Technology of Taiwan (MOST106-2628M-002007MY3). Authors acknowledge the NMR and TEM measurements from The Modern Analysis and Testing Center of CSU.

REFERENCES Figure 6. TEM images of metallo-supramolecular (A) 13 and (B) 18.

[Ru2T2K] was assembled with tenon ligands V and K in the presence of Zn(II) ions, the trapezoid Zn5[Ru2T2K]V2 and hollow hexagon Zn15[Ru2T2K]3K3 were produced respectively in quantitative yields. The combination of multitopic MOLs [Ru2T2K] and [Ru2X2V] gave rise to the nearly quantitative formation of our first bis-MOL-based biggest star-shaped supramolecule Zn18[Ru2T2K]3[Ru2X2V]3. The attached 12 dodecyl side chains around the ligand X ensure a good solubility of the 34,047 Da metallo-supramolecule in common organic solvents. We anticipate that the presented method for multicomponent self-assembly will provide a new molecular assembly tactic for facile construction of functional discrete and shape-persistent metallosupramolecules with next level of complexity and functionality. Further investigations of supramolecular electronics and material properties on such ultra large planar supramolecules are currently under way.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org at DOI. Experimental procedures and characterization data, including 1 13 H, C, COSY, NOESY, and DOSY spectra of the new compounds and ESI-MS spectra of related compounds (PDF)

AUTHOR INFORMATION Corresponding Author * Z. Jiang: [email protected] * Y. Chan: [email protected] * P. Wang: [email protected]

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Truncated Sierpiński Triangular Assembly From a Molecular Mortise-Tenon Joint Mingzhao Chen, Jun Wang, Shi-Cheng Wang, Zhilong Jiang, Die Liu, Qianqian Liu, He Zhao, Jun Yan, Yi-Tsu Chan, Pingshan Wang


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