pubs.acs.org/JACS Article Construction of Macromolecular Pinwheels Using Predesigned Metalloligands Jun Wang,# He Zhao,# Mingzhao Chen,* Zhiyuan Jiang, Feng Wang, Guotao Wang, Kaixiu Li, Zhe Zhang, Die Liu, Zhilong Jiang, and Pingshan Wang* Downloaded via SAN FRANCISCO STATE UNIV on November 19, 2020 at 20:32:31 (UTC) See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles Cite This: https://dx.doi.org/10.1021/jacs.0c08020 ACCESS Metrics & More Read Online Article Recommendations sı Supporting Information * ABSTRACT: Developing a methodology to build target structures is one of the major themes of synthetic chemistry However, it has proven to be immensely challenging to achieve multilevel elaborate molecular architectures in a predictable way Herein, we describe the self-assembly of a series of pinwheel-shaped starlike supramolecules through three rationally preorganized metalloligands L1−L3 The key octa-uncomplexed terpyridine (tpy) metalloligand L3, synthesized with an 8-fold Suzuki coupling reaction to metal-containing complexes, has four different types of terpyridines connected with three ⟨tpy-Ru2+-tpy⟩ units, making this the most subunits known so far for a preorganized module Based on the principle of geometric complementation and the high “density of coordination sites”, these metalloligands were assembled with Zn2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields With molecular weights ranging from 16756 to 56053 Da and diameters of 6.7−13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy ■ INTRODUCTION Molecular nanotechnology is one strategy for addressing beauty in molecules.1 Structures of various shapes have been created over the last few decades.2 Significant advances in the synthesis of beautiful molecular objects at the nanometer scale have been elegantly realized, including geometric stars,3 selfsimilar fractals,4 Archimedean polyhedrals,5 mechanically interlocked objects,6 and others.7 Among these, geometric star structures are common in nature and art, such as in multipetal flowers, snowflakes, Star of David, and pinwheels In addition, pentameric and hexameric cyclic shapes have symbolic significance in many cultures and religions, such as the Star of David These well-organized molecular systems can reach an amazing level of sophistication and functionality in molecular reactors,8 photonics,9 drug delivery,10 sensing,11 catalysis,12 and other systems.13 For example, Leigh et al synthesized a pentafoil knot that promotes catalyzed chemical reactions through the breakage of carbon−halogen bonds and anion abstraction.14 However, routes to build for the multilevel geometric structures in a predictable way still remain a challenge Noncovalent interactions, which are common behaviors in natural biological systems and can provide access to highly complex proteins, have inspired chemists to employ selfassembly to fabricate many types of molecules.15 Coordina© XXXX American Chemical Society tion-driven self-assembly is an important noncovalent interaction that has been utilized to construct supramolecular architectures with definite sizes and shapes.16 In the last few decades, Lehn,17 Fujita,18 Stang,19 Leigh,20 Nitschke,21 and others22 have reported numerous examples of beautiful 2D and 3D supramolecular architectures using this strategy One Ndonor bridging ligand that has received immense attention is 2,2′:6′,2″-terpyridine, which possesses octahedral ⟨tpy-M2+tpy⟩ connectivity bound to geometrically oriented ligands.23 Notably, the molecular design of supramolecular architectures with definite sizes and shapes essentially relies on the control of angled vectors and the coordination geometry.2b Despite this, it has been proven that the self-assembly process of extended ligands might not strictly follow their angular direction, which increases the challenge of assembling an ideal single product.24 For instance, a mixture of macrocycles (from pentamer to nonamer) was generated in the self-assembly of a ditopic 120° angle ligand with Zn2+, however, discrete hexagon Received: July 25, 2020 A https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Scheme Self-Assembly of Pinwheel-Shaped Star Trigon, Pentagram, and Hexagram rhombuses by utilizing vertex connectivity, and possess a triangle and pentagon, respectively, in the center More importantly, a larger and more complicated pinwheel-shaped hexagram P3 (a hexamer product) could be generated via the coordination of an octaterpyridine metalloligand (L3) and Zn2+ ions (Scheme 1) These species with rigid pinwheelshaped architectures possess central symmetry, which may show potential applications in selective catalysis and molecular machines wreaths can be achieved by increasing the density of the coordination sites, which provides the final architectures with more geometric and rigidity constraints.25 Moreover, we have previously proposed a stepwise strategy for constructing preblocked metallo-organic ligands to reduce the fragmentation of the final constructs.26 We expected that high generation of metallosupramolecules might be exclusively produced in a roundabout way by using multinuclear metalloligands to increase the terminal coordination sites Note that pinwheelshaped compounds in N-donor-based supramolecular structures have been unknown until now, although the design principles via coordination-driven self-assembly have been well understood and employed with high success for the synthesis of 2D supramolecular polygons Herein, we present our preparation of different pinwheelshaped stellated metallosupramolecules using a rationale terpyridine-based precursor design Three novel multitopic metalloligands, L1, L2, and L3, were designed and synthesized by taking advantage of the inert ⟨tpy-Ru2+-tpy⟩ in a stepwise manner (Scheme 1) Key metalloligands L1 and L2 with four uncomplexed free terpyridines are featured in a truncated rhombus bound to a V-directed tenon They were assembled with Zn2+ ions to introduce a discrete pinwheel-shaped star trigon P1 and pentagram P2 (the trimer and pentamer product, respectively), attributed to the intramolecular mortise−tenon joint.27 Both P1 and P2 were composed of ■ RESULTS AND DISCUSSION Self-Assembly of Pinwheel-Shaped Star Trigon P1 via Preorganized Metalloligand L1 A multistep route and a final Suzuki-coupling reaction26a were utilized to synthesize the tetra-uncoordinated metallo-organic ligand L1 Tetrabromosubstituted Ru2+ complex was first obtained by connecting bisterpyridine and two bromo-containing components with two Ru2+ metal ions (Scheme S1) Metalloligand L1 with four free terpyridines was achieved through a 4-fold Suzukicoupling reaction of 4-terpyridinyl-B(OH)2 with 1, using Pd0 as the catalyst, K2CO3 as the base, refluxing for days, and purifying by column chromatography (Al2O3) with a mixed CH2Cl2/CH3OH eluent (Scheme 2) The key bismetallic ligand L1 possesses three types of components that are presented as a truncated rhombus bound to a V-directed tenon in a 60° orientation B https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Scheme Synthesis of the Rationally Preorganized Metallo-organic Ligands L1−L3a a Reagents and conditions: (i) Tpy-B(OH)2, Pd(PPh3)4, K2CO3, CH3CN/CH3OH (2/1, v/v), reflux; (ii) N-ethylmorpholine, CH3OH/CHCl3 (1/ 1, v/v), reflux; (iii) RuCl3·3H2O, EtOH, reflux; (iv) N-ethylmorpholine, CHCl3/CH3OH (3/1, v/v), reflux The 1H NMR spectrum of L1 (Figure 1A) shows two distinct singlets at 9.20 and 8.99 ppm in a 1:1 ratio, which were assigned to the H3′,5′ protons of the Ru-connected terpyridine; the other H3′,5′ terpyridine protons overlapped with other peaks The nonaromatic region displays one multiplet and three singlets in a 4:3:3:3 ratio attributed to a pair of −OCH2− protons and three −OCH3 protons, which agrees very well with the theoretical proportions The other assignments were fully confirmed with the assistance of homonuclear chemical shift correlation spectroscopy (COSY), and nuclear Overhauser effect spectroscopy (NOESY) (Figures S50−S52) Moreover, diffusion-ordered spectroscopy (DOSY) was used to confirm the purity of ligand L1; only one narrow band corresponding to the 1H NMR spectrum was observed, confirming the absence of other byproduct (Figure 1B) Additional evidence for ligand L1 was confirmed by electrospray ionization mass spectrometry (ESI−MS) experiments, which exhibited peaks at m/z 802.51, 1164.64, and 1886.89, in good agreement with charge states of 4+ to 2+ obtained by losing NTf2− (Figure S91) Direct self-assembly was conducted by mixing metalloligand L1 with Zn(NTf2)2 in a precise stoichiometric ratio of 1:2 in a mixed solvent of CH3CN/CH3OH (v/v, 1/1) for 12 h under reflux After the mixture was cooled to room temperature, excess LiNTf2 (dissolved in CH3OH) was added and the mixture was then filtered to obtain a red precipitate In our original design, we anticipated that the complementarity of the ligand drives the formation of a surrounding rhombus pinwheel-shaped star trigon The resultant assembly was initially identified by 1H NMR and ESI−MS, which indicated that the target product P1 was formed in nearly quantitative yield (>95%) As shown in Figure 1A, in comparison with the 1H NMR spectrum of ligand L1, well-split and similar signals in the nonaromatic region of P1 were observed, indicating the formation of a single and symmetrical complex One multiplet and three singlets at 4.26−4.24, 3.97, 3.94, and 3.16 ppm in a 4:3:3:3 ratio were attributed to a pair of −OCH2− protons and three −OCH3 protons, which only showed small shifts from the −OCH2− and −OCH3 groups in L1 (Figure 1A) In the aromatic region, six singlets and one overlapping signal at 9.16, 9.11, 9.08, 9.06, 9.03, 8.93, and 8.87 ppm in a 1:1:2:1:1:1:1 ratio were attributed to the H3′,5′ protons of the eight types of terpyridines In addition, all H6,6′′ protons from free terpyridines were characteristically shifted upfield owing to the electron-shielding effects of the metal ions Other assignments were confirmed by 2D COSY and 2D NOESY spectra (Figures S2−S4) In comparison with the DOSY spectrum of ligand L1, an increasing diffusion coefficient was observed in P1, which showed narrow bands at log D = −9.60 and −9.75 m2 s−1 for L1 and P1, respectively (Figure 1B,C), demonstrating the expected size increase from ligand L1 to C https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Figure NMR study of metallo-organic ligand L1 and star trigon P1: (A) comparison of 1H NMR (500 MHz, in CD3CN) of L1 (top) and P1 (bottom); (B,C) DOSY NMR spectra (500 MHz, 298 K) of L1 and P1 in CD3CN, respectively Figure Mass spectrometry for pinwheel-shaped star trigon P1 and pentagram P2: (A) ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of P1; (C) ESI-MS spectrum and (D) 2D ESI-TWIM-MS plot of P2 Insets: theoretical and experimental isotopic patterns derived from the simulated molecular size (∼3.3 nm) The single band in the DOSY spectrum of P1 also confirmed that only one species was present in the solution complex P1 In addition, the experimental hydrodynamic radius (rH) of P1 was 3.3 nm, which was calculated by the Stocks−Einstein equation and agreed well with the outer radii D https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Figure NMR study of metallo-organic ligand L2 and pinwheel-shaped pentagram P2: (A) comparison of 1H NMR (500 MHz, in CD3CN) of L2 (top) and P2 (bottom); (B, C) DOSY NMR spectra (500 MHz, 298 K) of L2 and P2 in CD3CN, respectively observed at 4.21−4.18, 3.91, 3.89, 3.28, 3.22, and 3.15 ppm with a 4:3:3:3:3:3 ratio, corresponding to a triplet for −OCH2− and five peaks for −OCH3 (Figure 3A) The other assignments were fully confirmed with the assistance of 2D COSY and NOESY (Figures S58−S61) Similarly, the DOSY spectrum of L2 displayed one narrow band at log D = −9.49 m2s−1, suggesting the absence of other byproducts (Figure 3B) The intense signals for charge states 4+ (m/z 811.49), 3+ (m/z 1174.95), and 2+ (m/z 1903.35) in the ESIMS spectrum also verified the successful synthesis of L2 (Figure S93) The reaction of L2 with equiv of Zn(NTf2)2 in a mixed solvent of CH3CN/CH3OH (v/v, 1/1) at 75 °C for 12 h resulted in the pinwheel-shaped pentagram P2, which was isolated in 95% yield as a red solid after precipitation with excess LiNTf2 in MeOH Both NMR and ESI-MS analyses supported the predicted structure The 1H NMR signals of P2 were similar to those for L2, which proves the P2 symmetry As shown in Figure 3A, a multiplet and four singlets were observed in the methoxy region at 4.23, 3.99, 3.97, 3.34, and 3.19 ppm with a 7:3:3:3:3 ratio In addition, eight types of tpy-H3′,5′ protons were observed at 9.10, 9.07, 9.04, 9.00, and 8.97 ppm with a 1:2:2:2:1 integration ratio All H6,6′′ protons (marked by the dotted lines in Figure 3A) from free terpyridines dramatically shifted upfield owing to electron-shielding effects, which indicate the formation of bistpy−metal coordination All other assignments were successfully confirmed on the basis of 2D COSY and NOESY spectra (Figures S6−S8) In The composition of the assembled supramolecule P1 was supported by ESI-MS experiments As shown in Figure 2A, a series of peaks with successive charge states from 16+ to 9+ was observed at m/z 767.04, 836.91, 916.75, 1008.72, 1116.02, 1243.01, 1395.39, and 1581.43, which was due to the loss of different numbers of NTf2− anions during ionization The calculated molecular weight exactly matched the desired structure with a molecular weight of 16756 Da, in accordance with the formula (Zn6L13)24+(NTf2)24−, and the isotope patterns for all charge states were consistent with the corresponding theoretical values of P1 (the detailed isotope patterns are summarized in Figure S100) Traveling wave ion mobility mass spectrometry (TWIM-MS) was also used to investigate the isomeric separation process.28 The narrow drift time distributions for states from 14+ to 10+ indicate the absence of isomers and oligomers resulting from self-assembly (Figure 2B) Self-Assembly of Pinwheel-Shaped Pentagram P2 via Pre-Organized Metalloligand L2 Subsequently, a similar metallo-organic ligand L2 with a truncated rhombus bound to a V-directed tenon in a 120° orientation was designed and synthesized from the tetrabromo-substituted Ru complex (Scheme S2) The 1H NMR spectrum of metalloligand L2 exhibited clean, sharp signal peaks and showed six singlets at 9.08, 9.01, 8.98, 8.89, 8.87, and 8.80 ppm with a 1:1:1:1:1:1 integration ratio attributed to the H3′,5′ protons of the six types of terpyridines; the other two signal peaks of the tpy-H3',5' protons overlapped with the tpy-H6,6" protons at 8.75−8.73 ppm In the methoxy region, a multiplet and five singlets were E https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Figure NMR study of metallo-organic ligand L3 and pinwheel-shaped hexagram P3: (A) comparison of 1H NMR (500 MHz) of L3 in CD2Cl2 (top) and P3 in CD3CN (bottom); (B, C) DOSY NMR spectra (500 MHz, 298 K) of L3 in CD2Cl2 and P3 in CD3CN, respectively shown in Figure 4A, there were broad peaks in the aromatic region owing to the plentiful peak overlaps derived from the 14 terpyridine environments Fortunately, the 1H NMR spectrum showed clear, sharp peaks in the methoxy region One overlapped signal and six distinct signals at 4.01, 3.99, 3.89, 3.23, 3.20, 3.17, and 3.16 ppm with a 1:1:2:1:1:1:1 ratio were observed in the spectrum, which were attributed to the protons of eight types of −OCH3 with the expected ratio All protons were assigned based on 2D COSY and 2D NOESY experiments (Figures S79−S81) In the DOSY spectrum of L3, one narrow band at log D = −9.60 m2 s−1 was observed, suggesting that only one species was present in the CD2Cl2 solution (Figure 4B) In addition, metalloligand L3 was further analyzed by ESI-MS experiments The ESI-MS spectrum of L3 exhibited a series of peaks from 6+ to 3+ from the loss of the corresponding NTf2− anions (Figure S98), and the calculated molecular weight completely matched the simulated data, confirming the successful synthesis of L3 After mixing metalloligand L3 with equiv of Zn(NTf2)2 in a mixed solvent of CH3CN/CH3OH (v/v, 1/1) at 75 °C for 24 h, a red precipitate of P3 was obtained by adding an excess amount of LiNTf2 into the assembly solution and precipitating by deionized water Compared to pinwheel-shaped pentagram P2, hexagram P3 possesses an extra outer constraint, which may break the structural flexibility and provide the metalloligand with greater rigidity, leading to the assembly preferring the formation of a hexagram rather than a pentagram Figure 4A shows a comparison of the 1H NMR spectra of ligand L3 and P3, and the same number of terpyridine environments (14) leads to similar complicated peaks Moreover, peaks broader than those in L3 were observed in P3, which also supports the formation of a large product owing to the slow tumbling motion on the NMR time scale However, the nonaromatic region exhibited two multiplets and three singlets at 4.04, 3.92, 3.33, 3.30, and 3.18 ppm in a addition, the 2D DOSY spectrum (Figure 3C) of complex P2 showed a distinct narrow band at log D = −9.90 m2 s−1, indicating the formation of a single discrete product in CD3CN, with an experimental hydrodynamic radius of 4.7 nm, which agrees well with the simulated molecular size (∼4.8 nm) The formula of (Zn10L25)40+(NTf2)40− for P2 was accurately identified by ESI-MS As shown in Figure 2C, a series of peaks with continuous charge states (m/z) from 22+ to 11+ was observed, as indicated by the loss of different numbers of NTf2− anions; the experimental m/z values and their corresponding isotope patterns were completely consistent with the desired P2 structure with a molecular weight of 28088 Da The TWIM-MS plots of P2 displayed a series of narrow drift time distributions for charge states from 18+ to 11+, and no plots of oligomer and isomeric structures were found, indicating that pinwheel-shaped pentagram P2 is a discrete and rigid product without other structural conformers (Figure 2D) Self-Assembly of Pinwheel-Shaped Hexagram P3 via an Octaterpyridine Metalloligand L3 Encouraged by the successful synthesis of a pinwheel-shaped star trigon and pentagram, we expected that the pinwheel-shaped hexagrams could be exclusively produced by increasing the terminal coordination sites to restrict the flexibility of the metalloligand An extremely complex metalloligand L3 was designed by connecting four different organic components with Ru2+ connectors (Scheme S3) To the best of our knowledge, there is no report on a man-made metallo-organic ligand with four different components and eight free terpyridines in one molecule Structurally, metalloligand L3 contains 14 types of terpyridines, including six coordinated (three ⟨tpy-Ru2+-tpy⟩ connectors) and eight uncomplexed terpyridines Therefore, the 1H NMR spectrum of L3 displayed a set of rather complicated signal peaks owing to its structural asymmetry As F https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS 2:2:1:1:1 ratio, which were derived from seven −OCH3 protons Another −OCH3 proton overlapped with the solvent peak at 3.25 ppm, which was confirmed by 2D NOESY and 2D DOSY, and all other assignments were carefully assigned based on 2D COSY and 2D NOESY spectra (Figures S10−S12) DOSY was also conducted to test the purity and size of the pinwheel-shaped hexagram P3 A distinct narrow band at log D = −10.04 m2 s−1 corresponding to the 1H NMR signal peaks also confirmed that only one discrete product was present in the solution (CD3CN) Along with the increase in the pinwheel-shaped architecture generation (P1−P3), it was found that the absolute value of log D was gradually increasing This expected trend provided indirect support for the successful synthesis of a larger structure Again, according to the Stokes−Einstein formula, the experimental hydrodynamic radius of 6.5 nm was similar to that of the simulated molecular size (∼6.8 nm) More evidence for the successful synthesis of pinwheelshaped hexagram P3 was provided by the ESI-MS analysis The ESI-MS spectrum of P3 showed a series of peaks at m/z 1194.50, 1235.07, 1277.08, 1321.60, 1368.94, 1418.77, 1471.93, 1528.36, 1588.73, 1653.13, 1722.01, 1796.08, 1875.95, 1962.24, 2066.67, 2157.11, and 2268.04, which were obtained by losing successive NTf2− groups and correspond to charge states from 38+ to 22+ After deconvolution and analysis, these values corresponded well with the theoretical values of [(C326H222N42O8Ru3)6Zn24(C2F6NO4S2)84] with a molecular weight of 56053 Da (Figure 5) Owing to the very large Article found, suggesting the successful formation of a single discrete assembly Stability Study of Macromolecular Pinwheels P1−P3 To investigate the stability of P1, P2, and P3, gradient tandemmass spectrometry (gMS2), variant-temperature NMR, pH, and solvent-dependent stability experiments have been performed (Figures S104−S115) The gMS2 results of P1− P3 by applying a graduated increase of the collision energy suggested a higher stability of P1 than that of P2 and P3 By refluxing P1−P3 in 0.1 mol/L CH3COOH and 0.1 mol/L Na2CO3, 1H NMR spectra and ESI-MS data indicated that the Zn-based macromolecular architectures reported here were not acid and alkali resistant Besides, upon increasing the fraction of CH3OH from 0% to 70% in the mixed solvents of CH3CN and CH3OH, there were no other pieces observed in ESI-MS data, proven the good solvent-dependent stability of P1, P2, and P3 Intermolecular interactions (such as electrostatic interactions) might affect the stability of the complexes.2b Transmission Electron Microscopy After confirming the formation of these three pinwheel-shaped architectures, we did our best to provide direct evidence for their configuration Unfortunately, even after multiple attempts, growing single crystals of P1−P3 that are suitable for X-ray analysis has failed to date, and only powder-like solids have been obtained Transmission electron microscopy (TEM) experiments, which have been widely used to characterize microstructures, were alternatively performed to obtain structural insights.29 Figure shows the TEM images of pinwheel-shaped P1−P3 The averaged measured diameters of P1 (from 10 candidates), P2 (from candidates), and P3 (from candidates) were 6.8 ± 0.2, 9.2 ± 0.2, and 13.5 ± 0.1 nm, respectively, which were comparable to the molecular modeling diameters (6.7 nm for Figure Mass spectrometry for pinwheel-shaped hexagram P3: (A) ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of P3 molecular weight and the resolution limits of the instrument, it is difficult to obtain a satisfactory isotopic pattern Two minor peaks behind each charge state were found, probably from the ionization of the NTf2− counterions (Figure S103) More importantly, the TWIM-MS plots of P3 displayed a series of narrow drift time distributions at charge states from 38+ to 22+, and no plots of oligomer or isomeric structures were Figure Transmission electron microscopy for pinwheel-shaped P1P3 TEM images of (A) P1, (B) P2, and (C) P3 G https://dx.doi.org/10.1021/jacs.0c08020 J Am Chem Soc XXXX, XXX, XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China He Zhao − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China Zhiyuan Jiang − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China Feng Wang − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China Guotao Wang − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China Kaixiu Li − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China Zhe Zhang − Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China Die Liu − Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China Zhilong Jiang − Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China P1, 9.6 nm for P2, and 13.6 nm for P3) More importantly, the TEM images clearly showed each individual pinwheel-shaped molecule with vertices and fan blades; P3 was observed as a dispersion of hexagrams with a clear hollow structure ■ CONCLUSIONS Pinwheels are fantastic memories of childhood; here, we describe three nanometer-scale pinwheel-shaped metallo-supra molecules, including a starlike trigon, a pentagram, and a hexagram In the same way that DNA and proteins are made up of specific sequences of nucleotides and amino acids,30 we prepared three intricate asymmetric metalloligands with selfcomplementary features through delicate molecular designs by first connecting three or more different individual organic moieties with Ru2+ ions These were then assembled with Zn2+ ions to form the pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 in nearly quantitative yields In contrast with most previously reported metallosupramolecules, this formation is able to combine multiple components (up to four) into one building block, which prevents the self-sorting and restricts structural flexibility To the best of our knowledge, there is no previous report on metallo-organic ligands with multiple different components (≥4) and multiple free terpyridines (≥8) The successful manufacture of pinwheelshaped scaffolds of controlled shape provides a feasible and effective strategy to construct increasingly complex molecular topological structures Further investigations on the properties of these giant supramolecules with special shapes are currently underway ■ ASSOCIATED CONTENT sı Supporting Information * The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c08020 ■ Article Experimental procedures and characterization data, including 1H, 13C, COSY, NOESY, and DOSY spectra of the new compounds and ESI-MS spectra of related compounds (PDF) Complete contact information is available at: https://pubs.acs.org/10.1021/jacs.0c08020 AUTHOR INFORMATION Corresponding Authors Mingzhao Chen − Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China; Email: jinyulinzhao@foxmail.com Pingshan Wang − Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China; Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China; orcid.org/0000-0002-1988-7604; Email: chemwps@ csu.edu.cn Author Contributions # J.W and H.Z contributed equally to this work Notes The authors declare no competing financial interest ■ ACKNOWLEDGMENTS We acknowledge support from the National Natural Science Foundation of China (21971257 to P.W and 22001047 to D.L.) and Guangdong Natural Science Foundation (2019A1515011358 to Z.Z.) 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XXX−XXX Journal of the American Chemical Society pubs.acs.org/JACS Article Figure NMR study of metallo-organic ligand L1 and star trigon P1: (A) comparison of 1H NMR (500 MHz, in CD3CN) of L1 (top)