Constituent Isomerism Induced Quasicrystal and Frank-Kasper Σ

IMMEDIATE ONLINE ACCEPTED (IOA) ARTICLE

This article presented here has been peer reviewed and accepted for publication in CCS Chemistry. The present version of this manuscript has been posted at the request of the author prior to copyediting and composition and will be replaced by the final published version once it is completed. The DOI will remain unchanged.

IOA Posting Date: July 16, 2020

TITLE: Constituent Isomerism Induced Quasicrystal and Frank-Kasper  Superlattices Based on Nano-sized Shape Amphiphiles

AUTHORS: Zebin Su, Jiahao Huang, Wenpeng Shan, Xiao-Yun Yan, Ruimeng Zhang, Tong Liu, Yuchu Liu, Qing-Yun Guo, Fenggang Bian, Xiaran Miao, Mingjun Huang, Stephen Z.D. Cheng

DOI: 10.31635/ccschem.020.202000338 Page 1 of 16 CCS Chemistry

1 2 3 Constituent Isomerism Induced Quasicrystal and Frank-Kasper σ Superlattices 4 5 Based on Nano-sized Shape Amphiphiles 6 7 Authors: Zebin Su,1,2† Jiahao Huang,2† Wenpeng Shan,2 Xiao-Yun Yan,2 Ruimeng Zhang,2 8 9 Tong Liu,2 Yuchu Liu,2 Qing-Yun Guo,2 Fenggang Bian,3 Xiaran Miao,3 Mingjun Huang,1* 10 Stephen Z.D. Cheng1,2* 11 12 13 Affiliations: 14 1 15 South China Advanced Institute for Soft Matter Science and Technology, School of Molecular 16 Science and Engineering, South China University of Technology, Guangzhou, 510640. 17 2Department of Polymer Science, College of Polymer Science and Polymer Engineering, 18 19 University of Akron, Akron, OH, 44325. 20 3Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced 21 Research Institute, Chinese Academy of Sciences, Shanghai, 201204. 22 23 Corresponding Author: [email protected]; [email protected]; 24 25 Z. Su and J. Huang contributed equally to this work 26 27 28 Abstract 29 30 Naturally, subtle variations in the chemical structure of constituent molecules may significantly 31 affect their multiscale spatial arrangements, properties and functions. Deceptively simple 32 33 spherical assemblies supply an ideal platform to investigate how subtle chemical differences 34 affect hierarchical assembled structures. Here, we report two sets of nano-sized shape 35 amphiphiles, which are constructed by a triphenylene core and six polyhedral oligomeric 36 silsesquioxane cages at periphery grafted onto it through linkers. The slight differences of these 37 38 samples are merely several methylene units in their linkers, including several pairs of 39 constituent isomers. These nano-sized shape amphiphiles self-assemble into a variety of 40 unconventional spherical packing structures, which include the F-K σ phase and dodecagonal 41 quasicrystal. Several types of unconventional phase transitions were systematically 42 investigated. We alternate the conventional columnar phases of discotic molecules to 43 44 unconventional spherical packing phases. These unconventional structures may shed a light 45 into discovering discotic mesogens based materials with new properties and functions. 46 47 48 49 Keywords: Self-assembly, Frank-Kasper Phase, Quasicrystal, Shape-amphiphile, Constituent 50 Isomer. 51 52 53 54 Introduction 55 56 It is well recognized that not only the chemical structure of soft matter determines many 57 associated physical properties, but also the spatial arrangements of constituent molecules in 58 multiple length scales. Subtle variations in chemical structures of constituent molecules may 59 induce considerable transformation on their spatial arrangements and further affect their 60

This article presented here has been accepted for publication in CCS Chemistry and is posted at the request of the author prior to copyediting and composition. © 2020 Chinese Chemical Society. CCS Chemistry Page 2 of 16

1 2 3 functions and properties.1-3 One of the well-known examples is the sickle cell anemia, just a 4 5 single amino residue mutation where the glutamic acid is substituted by the valine, leads to the 4 6 sickle-like shape red blood cell and results in an abnormality in oxygen-carrying function. 7 Moreover, even for the isomer case, a single leucine to isoleucine substitution in the envelope 8 code 348 of friend murine leukemia virus could dramatically alter the hemolytic effect.5 Tiny 9 10 mutation in the primary structure of a protein may affect its secondary, tertiary and tertiary 11 structure. Furthermore, it could dramatically change the function of those protein. Similar to 12 biomacromolecules, in the case of the soft matter self-assembly, a small difference in the 13 molecular chemical structure may result in a distinct self-assembled structure. For example, 14 one methylene difference in the repeat unit of polymer can turn the right-handed helix lamellar 15 6 16 crystal into left-handed helix lamellar crystal. Specifically, Percec and coworker reported 17 constituent isomers of 3,4- and 3,5- disubstituted phenyl ether dendrons self-assemble into a 18 series of dissimilar phase structures.7-9 19 20 Particularly, spherical assemblies are highly sensitive to a balance of enthalpic and entropic 21 interactions induced by subtle change of chemical structure. Besides the ubiquitous densely 22 23 packed structures, such as body-centered cubic phase (BCC), hexagonal close packed phase 24 (HCP), and face-centered cubic phase (FCC), there is a class of complex spherical packing 25 phases named Frank-Kasper (F-K) phases, which are originally discovered in metal alloys.10- 26 11 F-K phases are exclusively constructed with tetrahedrally arranged spherical motifs, 27 10-11 28 resulting in so-called tetrahedrally close packing. Often, dodecagonal quasicrystal (DDQC) 29 phase with 12-fold orientational symmetry and only one-dimensional translational symmetry 30 are closely associated with FK phases, due to the similarity in local tetrahedral packing rules.12- 31 14 Complex F-K phases and DDQC phase have not only observed in broad soft matter systems, 32 15-23 13, 24-31 32 33 including diblock copolymers, dendrimers, polymer colloids, small molecular 33-35 36-40 41-42 34 surfactants, giant molecules, and very recently, sugar-polyolefin conjugates, but 35 also mesoporous silica,43-44 binary nanocrystal superlattice,45-46 and DNA functionalized 36 nanoparticles.47-48 Several types of F-K phases only have considerably small differences 37 between their overall free energies. Therefore, self-assembled F-K phases are ideal platform 38 39 for investigating how subtle chemical differences affect hierarchical assembled structures. 40 41 Recently, we observed F-K Z phase (space group P6/mmm), F-K A15 phase (space group Pm3 38 42 푛), and BCC phase (space group Im3 m) in a set of nano-sized shape amphiphiles. Shape 43 amphiphiles refers to molecules with defined shape and competing interactions.49-51 These 44 dissimilar structures were induced by varying the number of a few methylene units in the 45 linkers between a core and periphery groups. In this article, we design and systematically 46 investigate two new sets of nano-sized shape amphiphiles, in which a triphenylene core is 47 48 attached with six identical polyhedral oligomeric silsesquioxane (POSS) cages at the periphery 49 through covalent linkers containing amide groups (Figure 1). The only slightly difference of 50 these samples are their linkers. For the first set of samples, Tp-Ph-Cn-6BP (n=3-11), in which 51 the phenyl group of the linker is conjugated with the triazole group, contains n (n=3-11) 52 methylene units between the amide group and BPOSS cage. The second set of samples, Tp- 53 Bn-Cm-6BP (m=2-5), in which the benzyl group of the linker connects with the triazole group, 54 contains m (m=2-5) methylene units between the amide group and BPOSS cage. Moreover, 55 56 Tp-Bn-Cm-6BP (m=2-5) and Tp-Ph-Cn-6BP (n=3-6) construct four pairs of constituent 57 isomers. 58 59 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Figure 1. Molecular cartoon model and chemical structures of the nano-sized shape 29 amphiphiles. (a) Schematic representation of a nanosized shape amphiphile, in which the light- 30 31 yellow disc and blue cube present the triphenylene core and BPOSS cages, respectively. The 32 chemical structures of the different linkers are presented in blue dashed box and illustrated by 33 grey wavy segments. The red chips on the grey wavy segment present the amide groups. (b) 34 The chemical structure of molecule Tp-Ph-C3-6BP. Hydrogen atoms of this molecule are not 35 shown for clarity. 36 37 The relatively weak π-π interaction supplied by triphenylene cores, together with the hydrogen 38 39 bonding interaction supplied by amide groups in the linkers provide the enthalpic driving force 40 for the self-assembly of these nano-sized shape amphiphiles. The relatively bulky BPOSS 41 cages at the periphery significantly increase the steric hindrance as an entropic reason to limit 42 these molecules to form columnar structure as which are often observed in discotic liquid 43 44 crystals. Therefore, tuning the link length and type may manipulate the finely balance between 45 the enthalpic and entropic contributions towards free energies of the phases. Through 46 systematically investigating the self-assembly behaviors of these giant shape amphiphiles, we 47 report the observation of various of phases, including DDQC phase, F-K σ phase (space group 48 49 푃42/푚푛푚), BCC phase and hexagonal columnar (HEX) phase (planar symmetry group p6mm). 50 Triphenylenes usually utilized as mesogenic units in discotic liquid crystals and side group 51 liquid crystalline polymers for applications in semiconductors.52-53 The discovery of a series of 52 spherical packing phases in these triphenylene-based nano-sized shape amphiphiles enrich the 53 54 self-assembled hierarchical structures of triphenylenes, which may facilitate the development 55 of triphenylene based materials for new properties and applications. 56 57 Experimental Methods 58 59 The syntheses of the two sets of giant shape amphiphiles are described in supporting 60 information. The purity and molecular structural precision were characterized by 1H, 13C

1 2 3 Nuclear Magnetic Resonance (NMR) spectra (Figures S1-S13) and matrix assisted laser 4 5 desorption/ionization-time of flight (MALDI-TOF) mass spectra (Figure S14). We measured 6 the characteristics thermal properties of these samples by thermal gravimetric analysis (TGA) 7 (Figure S15) and differential scanning calorimetry (DSC) (Figure S16). TGA results 8 demonstrate that these two sets of samples are thermally stable up to 250 ℃ (no weight loss up 9 10 to 300 ℃ at a heating rate of 1 ℃/min under nitrogen atmosphere). DSC results indicate that 11 the crystallization of BPOSS cages is strongly depressed, when the number of methylene group 12 (n or m+1) in each linker is less than seven. We observed a weak peak with d-spacing of 0.33 13 nm in WAXD profile (Figure S17), which is corresponding to the characteristic π-π stacking 14 15 distance between triphenylenes and indicates π-π stacking interactions between triphenylene 16 units. The feature of the π-π stacking interactions between triphenylene units is similar to the 17 previous reports.30, 52 We also confirmed the hydrogen bonds between amide group by Fourier- 18 transform infrared spectroscopy (FTIR), in which the bands at about 3320 cm-1 could be 19 attributed to H-bonded N-H stretching (Figure S18). After thermal annealing process, these 20 21 nano-sized shape amphiphiles self-assemble into a variety of supramolecular phase, as 22 confirmed by both synchrotron small angle X-ray scattering (SAXS) profiles and bright field 23 (BF) transmission electron microscopy (TEM) images. 24 25 26 27 Results and Discussion 28 29 For the nano-sized shape amphiphile, Tp-Ph-C3-6BP, was freeze-dried to obtain disordered 30 state and then annealed at 150 ℃. It self-assembles into spherical motifs and further forms a 31 DDQC phase (Figure 2a). The bulky BPOSS cages at the periphery of a amphiphile prevent 32 33 the formation of long columnar motifs. Therefore, several molecules stacked into short 34 fragment and forms a spherical motif, as illustrated in Figure 2g. The DDQC phase is 35 demonstrated by a typical SAXS profile in which the scattering vector (q) ratios and intensity 36 of peaks are nearly identical to previous report.13, 17, 37 All the diffraction peaks in the SAXS 37 38 profile can be indexed using a five-dimensional (5D) reciprocal lattice in which a1 = a2 = a3 = 39 a4 = 13.93 nm and a5 =8.10 nm (Figure 2a and Table S1). This structure was further confirmed 40 by BF TEM image along [00001] direction, four kinds of typical tiling patterns including 33.42, 41 324.3.4, 36, 44 were all observed (Figure 2b). We next elevated the annealing temperature to 42 43 170 ℃, the DDQC phase transformed into a BCC phase (Figure 2c), based on the SAXS profile 44 with typical q ratios of 1: 2: 3: 4: 5 (Figure 2c) and BF TEM image from [001] direction 45 (Figure 2d). The phase transition from DDQC phase to BCC phase was also monitored by in 46 situ SAXS experiment (Figure 3a). The well-developed DDQC phase transforms into BCC 47 48 phase after annealing at 170 ℃ for 30 minutes (Figure 2g). We next cooled the well-formed 49 BCC phase to 150 °C for as long as 10 days, the BCC structure remained (Supporting S19), 50 indicating the DDQC phase is the metastable phase for this sample at experimental temperature, 51 a typical monotropic phase behavior.54 This phenomenon was similar to the DDQC phases 52 17 31 53 observed in other soft matter systems such as block copolymers, and dendrimers, since the 54 DDQC phase generally are found to have compatible stability with F–K phases at relatively 55 low temperature in both experimental results and simulations.14, 17 56 57 58 59 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 Figure 2. The self-assembly behaviors of Tp-Ph-Cn-6BP (n = 3-11) samples. (a) SAXS profile 46 of the DDQC phase self-assembled by Tp-Ph-C3-6BP after annealing at 150 ℃. (b) TEM 47 image taken along the [00001] direction of the DDQC phase. Bottom left inset: The Fourier 48 49 filtered images of the local TEM image marked by corresponding yellow and red square box. 50 Top right inset: FFT pattern. (c) SAXS profile of the BCC phase self-assembled Tp-Ph-C3- 51 6BP after annealing at 170 ℃. (d) TEM image taken along the [001] direction of the BCC phase. 52 Top right inset: FFT pattern. Bottom left inset: The Fourier filtered images of the local TEM 53 54 image marked by red square box. (e) SAXS profile of the HEX phase obtained from Tp-Ph- 55 C11-6BP after annealing at 180 ℃. (f) TEM image taken along the columnar axis of the HEX 56 phase self-assembled by Tp-Ph-C11-6BP. Top right inset: FFT pattern. Bottom left inset: The 57 Fourier filtered images of the local TEM image marked by red square box. (g) The schematic 58 59 illustration of the self-assembly of Tp-Ph-C3-6BP. (h) The schematic illustration of the self- 60 assembly of Tp-Ph-C7-6BP.

1 2 3 We next investigated the impact of the length of the linkers on self-assembly. We increased the 4 5 length of linkers by adding methylene unit one by one into the linker, resulting in Tp-Ph-C4- 6 6BP, Tp-Ph-C5-6BP, and Tp-Ph-C6-6BP with four, five and six methylene units between the 7 BPOSS cage and amide group, respectively. They self-assemble into BCC phases identified by 8 SAXS at the annealing temperature range from 150 ℃ to 220 ℃ (Figures S20-S22). Further 9 10 analysis demonstrates that each spherical motif in the BCC phases formed by Tp-Ph-C4-6BP, 11 Tp-Ph-C5-6BP, and Tp-Ph-C6-6BP contains approximately 8, 9, and 11molecules, 12 respectively. The increasing numbers of molecules in each spherical motif of these three 13 samples indicates the longer linkers enable more molecules to assemble into a spherical motif. 14 15 Moreover, we further increased the number of methylene groups in the linkers, we got samples 16 Tp-Ph-C -6BP, Tp-Ph-C -6BP, Tp-Ph-C -6BP, and Tp-Ph-C -6BP. All of these three 17 7 8 9 10 18 samples self-assemble into HEX phases with the q ratios 1: 3: 4: 7 in the SAXS profiles 19 after annealing at 180 ℃ (Figures S23-S26). Next, we increased the annealing temperature 20 above 200 ℃, the HEX phases transform into BCC phases by breaking the stacking column 21 and those broken motifs further deformed into spherical motifs (Figure 2h and Figures S23- 22 23 S26). This phase transition was also observed by the in situ SAXS experiment (Figure 3b). As 24 the annealing temperature increased, on one hand, the thermal expansion of BPOSS cages 25 makes the periphery more and more crowded. On the other hand, the π-π interaction between 26 triphenylene cores and intermolecular hydrogen-bonding interactions at the linkers become 27 28 weaker and weaker. The combination of these two effects drive the columnar motifs in HEX 29 phase break into spherical motifs and further assemble into BCC phases. These BCC phases 30 can transform back to HEX phase at annealing temperature 180 ℃, which means the phase 31 transition between HEX phase and BCC phase are reversible (Figures S24 and S26). However, 32 33 Tp-Ph-C11-6BP, with the longest linkers in this set of samples, self-assembles into HEX phase 34 at the annealing temperature range from 180 ℃ to 240 ℃ (Figures 2e, 2h, and S27), without 35 phase transition to any spherical packing phase (Figures 2g and 2h). In this case, the longest 36 linkers of Tp-Ph-C -6BP enable the formation of columnar motifs with relatively large radius, 37 11 38 which can facilitate π-π stacking between triphenylenes and significantly reduce the steric 39 hindrance of the BPOSS cages. The relatively long linkers of Tp-Ph-Cn-6BP (n=7-11) render 40 the BPOSS cages have enough mobility and can crystallize after cooling the temperature below 41 their melting points. 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Figure 3. Investigations of the phase transition behaviors through in-situ SAXS experiments. 23 24 (a) SAXS profiles demonstrate the formation of DDQC phase from sample Tp-Ph-C3-6BP 25 after annealing at 150 ℃ for 1 hour, which transform completely into BCC phase after 26 annealing at 170 ℃ for 30 minutes. (b) SAXS profiles demonstrate the formation of HEX phase 27 from sample Tp-Ph-C -6BP after annealing at 180 ℃ for 1 hour, which transform completely 28 7 29 into BCC phase after annealing at 200 ℃ for 1 hour. 30 31 For the second set of samples, the Tp-Bn-Cm-6BP (m=2-5) samples demonstrate different 32 phase behaviors, although their chemical structures are just different in several methylene 33 groups of each linkers. Moreover, Tp-Bn-Cm-6BP (m=2-5) are constituent isomers of Tp-Ph- 34 Cn-6BP (n=3-6). Surprisingly, they exhibit distinct self-assembly behaviors compared with 35 their constituent isomers. Tp-Bn-C -6BP self-assembles into BCC phase at the annealing 36 2 37 temperature range from 160 ℃ to 220 ℃ (Figure S28). Tp-Bn-C3-6BP and Tp-Bn-C4-6BP 38 also self-assemble into BCC phase at relatively low annealing temperature range from 160 ℃ 39 to 210 ℃ (Figures 4a, S29 and S30). Order-order transition takes place when the temperature 40 41 is close to yet below temperature of order-disorder transition (TODT), Tp-Bn-C3-6BP and Tp- 42 Bn-C4-6BP transform from the BCC phase into F-K σ phase at 230 ℃ and 220 ℃, respectively 43 (Figures 4a, S29 and S30). The σ phase was identified by SAXS profiles which can be 44 unambiguously indexed based on space group P42/mnm (Figure 4a). The corresponding BF 45 2 46 TEM images long [001] direction display the distinctive 3 .4.3.4 tiling pattern corroborate the 47 formation of σ phase (Figure 4b). The phase transitions between BCC phase and σ phase of 48 these two samples are reversible (Supporting X), indicating the enantiotropic phase 49 54 behaviors. Compared with these two samples, Tp-Bn-C5-6BP only self-assembled into σ 50 phase at the annealing temperature range from 180 to 220 (Figure S31). We summarize 51 ℃ ℃ 52 all the self-assembled structures of these two set of nano-sized amphiphiles in Table 1. 53 54 55 56 57 58 59 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 Figure 4. The self-assembly behavior of Tp-Bn-C4-6BP. (a) High quality SAXS profile of the 33 σ phase self-assembled by Tp-Bn-C -6BP after annealing at 220 ℃. (b) TEM image taken along 34 4 35 the [001] direction of the σ phase. Bottom left inset: The Fourier filtered image of the local 36 TEM image marked by red square box. Top right inset: FFT pattern. (c) SAXS profile shows 37 the formation of BCC phase assembled by Tp-Bn-C4-6BP after annealing at 160 ℃ for 30 38 minutes, then transform completely into σ phase after annealing at 220 ℃ for 1 hour. (d) The 39 40 schematic illustration of the transition from BCC lattice to σ lattice. 41 42 43 44 The self-assembly behaviors of these nano-sized shape amphiphiles are dominated by 45 combination of the enthalpic and entropic contributions from both the relatively rigid core and 46 relatively soft corona of the spherical motifs. The free energy competence between the 47 spherical packing phases formed by nano-sized shape amphiphiles is highly sensitive to the 48 radius of relatively rigid core (R ) and the thickness of soft corona (L ). In this article, the R 49 c c c 50 is mainly determined by the size of triphenylene core and keeps a constant. Considering the 51 length of soft corona from short to long, the packing structure evolution can be partitioned into 52 three stages (Figure 5a). At stage I, the Lc is rather short (Lc << Rc) or the linker is rather rigid 53 which can be treated as core part, a spherical motif is close to an ideal rigid sphere, which 54 55 favors lattices with higher packing efficiency to minimize the bulk free energy. Therefore, a 56 relatively dense-packed BCC phase or a closest-packed FCC phase is usually observed in 55-56 57 materials formed by rigid spherical motifs. If Rc keeps constant and the Lc increases to a 58 considerable length, the packing of spherical motifs steps into stage II. The soft corona of 59 60 spherical motifs plays a vital role in determining the spherical packing lattice. The soft corona

1 2 3 tends to minimize the surface contact area, since the larger overlap between the neighboring 4 5 spherical motifs would constrain the conformation of molecules, and cause the smaller 55-56 6 orientational entropy. The surface area of lattices can be described by the average sphericity 7 of its constructing motifs of a lattice based on Voronoi cells. Sphericity are quantified by the 8 isoperimetric quotient, 퐼푄 = 36π푉2/푆3 (where V is polyhedral volume and S is polyhedral 9 10 surface area, based on Voronoi cells), with an upper limit equals to 1.0 reached by ideal sphere. 11 The higher average sphericity means the constructing motifs of a lattice are closer to an ideal 12 sphere and have smaller surface area for higher orientational entropy.55-56 The average IQ value 13 of σ phase (0.7623), A15 phase (0.7618), and Z phase (0.7634) is higher than either BCC phase 14 (0.7534) or FCC phase (0.7405).17-18, 57-58 However, when soft spherical motifs assemble into 15 16 an ordered structure, the spherical symmetry of the motifs must be broken by the lattice 17 symmetry to maintain a uniform space filling. Therefore, spherical motifs deform into 18 polyhedra corresponding to the Voronoi Cells, with increasing deformation energy as penalty. 19 If the L further increased, the packing of spherical motifs comes to stage III. The soft corona 20 c 21 is thick enough, therefore, the deformation energy of the spherical domains become negligible. 22 Hence, the BCC phase is favored since the more deformed Voronoi cell of a BCC phase can 23 accommodate more uniform space filling and higher conformation entropy of soft linkers. 24 25 For the Tp-Bn-Cm-6BP (m=2-5) samples, they mainly stay at stage I and stage II. The corona 26 of the Tp-Bn-C2-6BP is more rigid than any other samples of Tp-Bn-Cm-6BP, attributing to 27 28 the shortest linkers among these samples. Tp-Bn-C2-6BP stays at stage I and favored the 29 densely packed BCC phase. Tp-Bn-C3-6BP and Tp-Bn-C4-6BP contain softer corona than 30 Tp-Bn-C2-6BP and stay in the boundary between the stages I and II. At relatively low 31 temperature, Tp-Bn-C3-6BP and Tp-Bn-C4-6BP formed BCC phase for higher packing 32 33 efficiency. At relatively high temperature, Tp-Bn-C3-6BP and Tp-Bn-C4-6BP transform into 34 σ phase for a higher sphericity, and thus, higher orientational entropy for the BPOSS cages and 35 the whole spherical motifs. Tp-Bn-C5-6BP with the longest linkers in this set of samples step 36 into stage II, and directly self-assembled into σ phase at 180 ℃. Compared with Tp-Bn-C5- 37 6BP, Tp-Bn-C -6BP and Tp-Bn-C -6BP reach σ phase at higher annealing temperatures. 38 3 4 39 Because both of them contain relatively short linkers and stay at the boundary between stage I 40 and stage II, higher annealing temperature is necessary for the entropy-driven phase transition 41 from BCC phase to σ phase. 42 43 44 45 The comparison of the self-assemblies of four pairs of constituent isomers Tp-Bn-Cm-6BP 46 (m=2-5) and Tp-Ph-Cn-6BP (n=3-6) are more intriguing, since the chemical composition of 47 48 each pair of isomers are exactly same. However, the position of a single methylene unit may 49 significantly affect the mobility of the linker and further intermolecular hydrogen bonding in a 50 nano-sized shape amphiphiles. For Tp-Bn-Cm-6BP (m=2-5), the phenyl group and triazole 51 group in each linker are separated by a methylene group. The methylene group between these 52 two aromatic rings supplies considerably orientational freedom, and facilitate the 53 54 intermolecular hydrogen bonding among amide linkers. The resulting more rigid linker can be 55 treated as part of rigid core. In contrast, for Tp-Ph-Cn-6BP (n=3-6), the phenyl group 56 conjugates with the triazole group. The two conjugated aromatic rings significantly constrain 57 the conformation of the amide group in the linkers and further partially impede the 58 59 intermolecular hydrogen bonding. In this sense, the linkers in Tp-Ph-Cn-6BP series keep their 60 softness. To support this comparation, we apply density functional theory (DFT) calculations

1 2 3 for relatively potential energy of these two types of linkers at different conformations at M06- 4 5 2X/Def2-TZVP level (Supporting information). The two local maximum potential energy of 6 linker in Tp-Bn-Cn-6BP are 6.963 kJ/mol and 15.388 kJ/mol, respectively (Figure 5b). 7 However, the two local maximum potential energy of linker in Tp-Ph-Cm-6BP are 15.243 8 kJ/mol and 16.293 kJ/mol (Figure 5c), respectively, which are obviously larger than 9 10 corresponding values in Tp-Ph-Cn-6BP. These results indicate the linkers in Tp-Ph-Cn-6BP 11 probably have limited rotational freedom. Therefore, the amide groups in the linkers of Tp- 12 Ph-Cm-6BP (m=3-6) are more difficult to form intermolecular hydrogen bonding than the 13 linkers of Tp-Bn-Cn-6BP (n=2-5). On the contrary, more and stronger intermolecular 14 hydrogen bonding among amide groups results in less flexibility of these linkers in Tp-Bn-Cn- 15 16 6BP, and these rigidity enhanced linkers can even be treated as part of core in supramolecular 17 spherical motif. Hence, we speculate that the less and weaker hydrogen bonding between the 18 linkers of Tp-Ph-Cn-6BP makes the corona of Tp-Ph-Cn-6BP softer. 19 20 As a result, Tp-Ph-Cn-6BP (n=3) stays at the edge of stage II and stage III. For Tp-Ph-Cn- 21 6BP (n=3) with the shortest linker among this set of samples, it self-assembles into DDQC 22 23 phase at relatively low temperature. DDQC phase are speculated to have an average IQ similar 24 to σ phase and contains smaller surface area than BCC phase. At relatively high temperature, 25 the enhanced thermal fluctuation weakens the hydrogen bonding between the linkers of Tp- 26 Ph-Cn-6BP (n=3) and, further soften the conformation of the corona of the spherical motif. 27 28 Hence, Tp-Ph-Cn-6BP (n=3) steps into stage III due to the lower deformation energy and 29 forms BCC phase for more uniform packing. Because of the longer linkers, Tp-Ph-Cn-6BP 30 (n=4-6) stays in stage III and only self-assemble into BCC phase. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 Figure 5. (a) The three stages of spherical packing with constant rigid core and increasing 38 thickness of soft corona. (b) and (c), the relatively potential energy of the linkers in Tp-Ph-Cn- 39 6BP and Tp-Bn-C -6BP, respectively. Four representative conformations and their 40 m 41 corresponding relatively potential energy are shown in corresponding figures. 42 43 Conclusions 44 45 In summary, we designed two sets of nanosized shape amphiphiles with tunable linker length 46 and investigated their self-assembly behaviors. Various supramolecular lattices formed by 47 these two sets of samples, including BCC phase, HEX phase, σ phase, and unconventional 48 DDQC phase. These distinct phase structures are merely induced by varying the number of a 49 few methylene units in the linkers, or even induced by corresponding constituent isomer with 50 51 minor difference of the arrangement of methylene units in the linkers. This work not only 52 supply a protype to investigate how subtle difference in chemical structure determines 53 hierarchical phase structure, but also sheds a light into discovering discotic mesogens based 54 materials with new properties and functions. 55 56 Table 1. Summary of the supramolecular lattices formed by two sets of nano-sized amphiphiles 57 58 59 60

1 2 3 -1 b c d Molecules Phase T (℃) Lattice Mwt (g mol ) Rsphere(nm) μ 4 dimension (nm)a 5 6 Tp-Ph-C3-6BP DDQC 150 - 6670.81 - - 7 BCC 170 a = 5.08 2.50 6.92 8 Tp-Ph-C4-6BP BCC 150 a = 5.29 6754.97 2.61 7.72 9 10 Tp-Ph-C5-6BP BCC 150 a = 5.52 6839.14 2.72 8.66 11 Tp-Ph-C6-6BP BCC 150 a = 6.00 6923.30 2.95 10.99 12 Tp-Ph-C7-6BP HEX 180 d = 5.30 7007.46 - - 13 BCC 200 a = 6.17 3.04 11.80 14 15 Tp-Ph-C8-6BP HEX 180 d = 5.53 7091.62 - - 16 BCC 200 a = 6.28 3.09 12.30 17 Tp-Ph-C9-6BP HEX 180 d = 5.67 7175.78 - - 18 BCC 200 a = 6.44 3.17 13.11 19 20 Tp-Ph-C10-6BP HEX 180 d = 5.86 7259.95 - - 21 BCC 200 a = 6.56 3.23 13.69 22 Tp-Ph-C11-6BP HEX 180 d = 6.05 7344.11 - - 23 Tp-Bn-C -6BP BCC 160 a = 4.77 6670.81 2.35 5.73 24 2 25 Tp-Bn-C3-6BP BCC 160 a = 4.94 6754.97 2.43 6.30 26 σ 230 a = 15.73 c = 8.21 2.52 7.06 27 Tp-Bn-C -6BP BCC 160 a = 5.11 6839.14 2.52 6.87 28 4 29 σ 220 a = 15.90 c = 8.31 2.61 7.21 30 Tp-Bn-C5-6BP σ 180 a = 16.61 c = 8.76 6923.30 2.68 8.19 31 32 33 34 Supporting Information Description 35 Supporting Information is available, including synthetic procedures and additional 36 experimental details. 37 38 Conflict of Interest 39 40 The authors declare no competing interests. 41 Funding Information 42 43 This work was supported by Key-Area Research and Development Program of Guangdong 44 Province (2019B010941002, 2020B010182002), the National Natural Science Foundation of 45 China (71890871, U1832220), Guangdong Provincial Key Laboratory of Functional and 46 47 Intelligent Hybrid Materials and Devices (2019B121203003) and Guangdong Project 48 (2016ZT06C322), and the Fundamental Research Funds for the Central Universities 49 (2019JQ05). 50 51 Acknowledgments 52 We thank technical support from Shanghai Synchrotron Radiation Facility (SSRF). We express 53 54 our appreciation to State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen 55 University for the computer clusters with Gaussian 09D software package. 56 57 References 58 59 1. Lehn, J. M., Supramolecular chemistry—scope and perspectives molecules, supermolecules, 60 and molecular devices (Nobel Lecture). Angew. Chem., Int. Ed. 1988, 27 (1), 89-112.

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 TABLE OF CONTENTS (TOC) GRAPHIC 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60