Multiple‐Stimulus‐Responsive Supramolecular Gels and Regulation of Chiral Twists: The Effect of Spacer Length

A new class of homologous gelators, LG₁₂‐(CH₂)_n‐BSA, composed of bipyridinyl groups, L ‐glutamic moieties having double dodecyl chains, and linked alkyl spacers with different lengths were synthesized. It was found that these gelators could immobilize medium‐polarity solvents readily and the behaviors of these gels showed a dependence on the spacer length. Of all the gels, the LG₁₂‐(CH₂)₁₁‐BSA gels exhibited self‐healing property and multiple‐stimulus responsibility, such as heating, shaking, and sonication. The investigation of CD spectra indicated that the supramolecular chirality, which was attributed to the chiral transfer from the chiral center to the assemblies, was also closely related to the length of methylene spacers. The longer the alkyl spacers, the weaker the transmitted supramolecular chirality. Only LG₁₂‐(CH₂)₁‐BSA gelators, which had the shortest spacers, formed right‐handed nanoscale chiral twists owing to crowded hydrogen bonding interactions. Moreover, the high‐polarity solvent DMF was found to be able to regulate the chiral twist as well as its pitch length readily.     

New interpretation of progression bands observed in infrared spectra of nylon‐m/n

A series of progression bands observed in the infrared spectra of nylon‐m/n and their model compounds have been interpreted in a new manner on the basis of simply coupled oscillator models of zigzag alkyl chains. Nylon‐m/n possesses the methylene sequences of (CH₂)_m and (CH₂)_n?2, and so the effective models of m and n ? 2 coupled oscillators, respectively, had previously been assumed for the methylene rocking–twisting mode, for example. However, the spectral patterns of progression bands predicted by this previously proposed model have been found to be inconsistent with those observed for many kinds of nylon samples with various m and n values. It is rather reasonable to assume that the effective numbers of oscillators should be m ? 2 and n ? 4 for the methylene rocking, twisting, and wagging modes of the (CH₂)_m and (CH₂)_n?2 sequences, respectively. In other words, the infrared progression bands observed for methylene local modes of nylon‐m/n may be interpreted reasonably with the data of n‐alkane molecules with the chemical formulae CH₃(CH₂)_m?2CH₃ and CH₃(CH₂)_n?4CH₃. For the C? C stretching modes, the equivalent n‐alkanes are CH₃(CH₂)_m?1CH₃ and CH₃(CH₂)_n?3CH₃, respectively. In the simply coupled oscillator model, the vibrational mode of one methylene group is represented by an oscillator, for example. Our new concept is to isolate the terminal oscillator adjacent to the amide group from the other oscillators in the inner parts of the methylene zigzag sequence. This corresponds to a physical situation in which the methylene group adjacent to the amide group shows a different vibrational behavior of larger amplitude than those of the inner methylene sequence, as supported by broad‐line NMR data and molecular dynamics calculations reported in the literature. Another possibility is a difference in the electron structure of the methylene unit adjacent to the amide group from that of the inner methylene sequence, resulting in a difference in the force constant and giving a vibrational decoupling between these two types of methylene units. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1294–1307, 2003     

2-萘-(OCH2CH2)n-金刚胺与6-单取代环糊精衍生物的光诱导电子转移反应

A number of naphthalene donor compounds that possess an adamantanamine binding moiety and an (OCH2CH2)n (nn1, 2, 3, 4, 6, 8) spacer were synthesized. The fluorescence quenching between these donor substrates and mono-6-O-p-nitrobenzoyl-β-cyclodextrin (pNBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin(mNBCD) was studied in detail. It was found that very efficient fluorescence quenching could occur in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer inside the supramolecular assembly between the naphthalene donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern-Volmer quenching constants and static binding constants. It was demonstrated that the binding constants between all the naphthalene compounds and cyclodextrins are the same as they possess the same binding site, i.e., adamantanamine.     

The effect of twin‐tailed sidearms on sodium cation transport in synthetic hydraphile cation channels

The preparation of novel tris(macrocycle)s that transport Na⁺ through phospholipid bilayers is reported. All of the reported structures have the following structural elements: sidechain‐macrocycle‐spacer‐macro‐cycle‐spacer‐macrocycle‐sidechain. The overall extension of the channel system is defined by the lengths of the spacer chains. The flexible sidearms are thought to be aligned with the lipid axis and opposite to the spacer chains. To the extent the spacer chains contribute to organization of the structure and isolation of the cation‐containing pore from the surrounding lipid chains, more hydrophobic chains are expected to enhance cation transport. A comparison of C₁₂H₂₅<N18N>(CH₂)₁₂<N18N>(CH₂)₁₂<N18N> C₁₂H₂₅, 1, with (C₁₂H₂₅)₂N(CH₂)₂<N18N>(CH₂)₁₂<N18N>(CH₂)₁₂<N18N>(CH₂)2N(C₁₂H₂₅)₂, 11, shows that the Na⁺ transport is, indeed, enhanced.     

The Versatile,Efficient, and Stereoselective Self‐Assembly of Transition‐Metal Helicates by Using Hydrogen‐Bonds

A diverse range of dinuclear double‐stranded helicates in which the ligand strand is built up by using hydrogen‐bonding has been synthesized. The helicates, formulated as [Co₂(L)₂(L‐H)₂X₂], readily self‐assemble from a mixture of a suitable pyridine–alcohol compound (L; for example, 6‐methylpyridine‐2‐methanol, 1 ), and a CoX₂ salt in the presence of base. Nine such helicates have been characterized by X‐ray crystallography. For helicates derived from the same pyridine–alcohol precursor, a remarkable regularity was found for both the molecular structure and the crystal packing arrangements, regardless of the nature of the ancillary ligand (X). A notable exception was observed in the solid‐state structure of [Co₂( 1 )₂( 1 ‐H)₂(NCS)₂] for which intermolecular nonbonded contacts between the sulfur atoms (S???S=3.21 Å) lead to the formation of 1D chains. Helicates derived from (R)‐6‐methylpyridine‐2‐methanol ( 2 ) are soluble in solvents such as CH₃CN and CH₂Cl₂, and their self‐assembly could be monitored in solution by ¹H NMR, UV/Vis, and CD titrations. No intermediate complexes were observed to form in a significant concentration at any point throughout these titrations. The global thermodynamic stability constant of [Co₂( 2 )₂( 2 ‐H)₂(NO₃)₂] was calculated from spectrophotometric data to be logβ=8.9(8). The stereoisomerism of these helicates was studied in some detail and the self‐assembly process was found to be highly stereoselective. The chirality of the ligand precursors can control the absolute configuration of the metal centers and thus the overall helicity of the dinuclear assemblies. Furthermore, the enantiomers of rac‐6‐methylpyridine‐2‐methanol ( 3 ) undergo a self‐recognition process to form exclusively homochiral helicates in which the four pyridine–alcohol units possess the same chirality.     

Three Octacyanometallate‐Based LnIII–MV (Ln = La,Ce; M = Mo,W) Bimetallic Assemblies with a One‐Dimensional Rope‐Ladder Chain Structure

Three octacyanometallate‐based hetero‐bimetallic complexes, [Ln(H₂O)₄(CH₃CN)₂][M(CN)₈] · CH₃CN [Ln = La, M = Mo( 1 ), W( 2 ); Ln = Ce, M = W( 3 )], were synthesized and characterized structurally. Single‐crystal X‐ray analysis reveals that 1 – 3 are isomorphous and consist of infinite one‐dimensional (1D) 3,3 rope‐ladder chains, in which the 12‐membered puckered square Ln₂M₂(CN)₄ is the basic building unit. The 1D chains are further linked through interchain hydrogen bonds, resulting in a three‐dimensional (3D) supramolecular network.     

Macroscopic Chirality of Supramolecular Gels Formed from Achiral Tris(ethyl cinnamate) Benzene‐1,3,5‐tricarboxamides

A C₃‐symmetric benzene‐1,3,5‐tricarboxamide substituted with ethyl cinnamate was found to self‐assemble into supramolecular gels with macroscopic chirality in a DMF/H₂O mixture. The achiral compound simultaneously formed left‐ and right‐handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester–amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.     

Synthesis,Structure, and Fluorescent Properties of Lanthanide Complexes Based on 8‐Hydroxyquinoline‐7‐carboxylic Acid

The lanthanide complex [Eu₃(8‐HQCA)₃(COOH)(OH)₂(H₂O)₃]_n · nH₂O (8‐HQCA = 8‐hydroxyquinoline‐7‐carboxylic acid) was synthesized and characterized. Single‐crystal X‐ray diffraction shows that the trinuclear structures are linked by ligands to form 2D layers. The results of DFT calculation shows that energy can be transferred effectively from the ligand to Eu^III ions. A series of heteronuclear complexes {[(Eu_1–xY_x)₃(8‐HQCA)₃(COOH) (OH)₂(H₂O)₃]_n · nH₂O (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8)} were synthesized and their luminescent properties were studied. The results showed that the doping of Y^III ions could change the fluorescent intensity of the Eu^III complex, but could not change their positions.     

Electrochemically reduced tungsten‐based active species as catalysts for cross‐metathesis reactions: cross‐metathesis of erucic acid with 2‐octene

The cross‐metathesis of erucic acid, (CH₃(CH₂)₇CH?CH(CH₂)₁₁COOH), with an excess of 2‐octene in the presence of an electrochemically produced tungsten‐based catalyst has been studied. Cross‐ and self‐hydrocarbon products, viz. 2‐undecene (C₁₁), 6‐dodecene (C₁₂) and 6‐pentadecene (C₁₅), were detected. The influence of several parameters, such as the 2‐octene/erucic acid and 2‐octene/catalyst ratios and the reaction time, on the yield of the cross‐metathesis product, 6‐pentadecene, was studied. The cross‐metathesis of functionalized olefins in the presence of an Al–e^?–WCl₆–CH₂Cl₂ system has not been reported in the literature so far. The cross‐metathesis products in the presence of this catalyst system can be obtained with high yield and high specificity. Copyright © 2004 John Wiley & Sons, Ltd.     

Angle‐resolved XPS of fluorinated and semi‐fluorinated side‐chain polymers

Angle‐resolved XPS data (elemental quantification and high‐energy‐resolution C 1s) are presented for ten polymers with side‐chains of the form ? OCO(CF₂)_yF, ? COO(CH₂)₂OCO(CF₂)_yF (y = 1, 2, 3) and ? COO(CH₂)_x(CF₂)_yF (x = 1, y = 1, 2, 3; x = 2, y = 8). Particular attention was paid to charge compensation and speed of data acquisition, with co‐addition from multiple fresh samples to give spectra with good energy resolution and good signal‐to‐noise ratio free from the effects of x‐ray‐induced degradation. Water contact angles for the polymers are also reported. The XPS data demonstrate preferential surface segregation of fluorine‐containing groups for all but the shortest side‐chain polymer, where the ? OCOCF₃ side‐chain either does not surface segregate or is too short for surface segregation to be detectable by angle‐resolved XPS. In the other polymers studied the relative positions of functional groups in the side‐chains correlate with the angle‐resolved behaviour of the corresponding C 1s components. This shows that the surface side‐chains are oriented towards the polymer surface. For the ? COO(CH₂)₂OCO(CF₂)_yF (y = 1) side‐chain, the angle‐resolved C 1s data suggest reduced ordering and linearity compared with y = 2 and 3. For any particular series of polymers, e.g. ? COO(CH₂)_x(CF₂)_yF, the water contact angles increase with y, consistent with burying of the hydrophilic ester groups as y increases. For any particular value of y the sequence of water contact angles is ? COO(CH₂)_x(CF₂)_yF > ? OCO(CF₂)_yF ～ ? COO(CH₂)₂OCO(CF₂)_yF, suggesting greater ordering and density of fluorocarbon species at the surface of the ? COO(CH₂)_x(CF₂)_yF side‐chain polymers compared with the other polymers studied. For the ? COO(CH₂)₂(CF₂)₈F polymer a water contact angle of 124° is measured, which is greater than that of poly(tetrafluoroethene). The ? COO(CH₂)₂OCO(CF₂)F polymer is unusual in that it shows a particularly low water contact angle (83° ), suggesting that the probe fluid is able to sense both ester groups, consistent with the reduced ordering of the side‐chain detected by angle‐resolved XPS. Copyright © 2004 John Wiley & Sons, Ltd.     

Novel Method of Producing Polymer Gels in Aqueous Solution Using UV Irradiation

Summary: We developed a novel method of producing polymer gels in aqueous solution using UV irradiation. Persulfates were effective photosensitive initiators of polymerization and/or gelation of acryloyl‐type monomers/polymers. The gelation was confirmed by an abrupt increase in light scattering intensity, 〈I(q)〉_T, at the gelation point. The gelation method entails significant advantages: it does not need any cross‐linkers, temperature control (heating), and additives except the persulfate.

The UV irradiation time dependence of light scattering intensity, 〈I(q)〉_T, for pre‐gel solutions containing N‐isopropylacrylamide (NIPAm) and/or ammonium persulfate (APS).     

Metallo‐Supramolecular Gels that are Photocleavable with Visible and Near‐Infrared Irradiation

A photolabile ruthenium‐based complex, [Ru(bpy)₂(4AMP)₂](PF₆)₂, (4AMP=4‐(aminomethyl)pyridine) is incorporated into polyurea organo‐ and hydrogels via the reactive amine moieties on the photocleavable 4AMP ligands. While showing long‐term stability in the dark, cleavage of the pyridine–ruthenium bond upon irradiation with visible or near‐infrared irradiation (in a two‐photon process) leads to rapid de‐gelation of the supramolecular gels, thus enabling spatiotemporal micropatterning by photomasking or pulsed NIR‐laser irradiation     

Synthesis,characterization, and self‐assembly of ion‐bonded A2B rod‐coil copolymer with oligo(para‐phenyleneethynylene) as rod segment

Supramolecular A₂B rod‐coil copolymer, composed of two polystyrene (PSt) arms and one oligo(para‐phenyleneethynylene) (OPE) arm linked via ionic bond, has been designed and successfully synthesized. First, a trifunctional initiator, methyl 1,3‐bis(bromomethyl)benzonate, was prepared and used to initiate the polymerization of styrene under atom transfer radical polymerization (ATRP) condition to provide polystyrene (PSt) carrying monoester group at the middle of polymer chain. Then, the ester group was transferred into tertiary amino group to give amino‐functionalized PSt, (PSt)₂? N(CH₃)₂. Subsequently, the ion‐bonded rod‐coil copolymer, (PSt)₂? OPE, was obtained by the reaction of (PSt)₂? N(CH₃)₂ with carboxy‐terminated OPE (OPE? COOH). The resulting copolymer was characterized by nuclear magnetic resonance (NMR), Fourier transformer infrared (FTIR), and gel permeation chromatography (GPC) techniques. Vesicles and spherical micelles were generated from this supramolecular rod‐coil copolymer through the manipulation of the initial polymer concentration in toluene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7667–7676, 2008     

Zweikernige Palladium(II)‐, Platin(II)‐ und Iridium(III)‐Komplexe von Bis[imidazol‐4‐yl]alkanen

Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH₂)_n bridged imidazoles L(CH₂)_nL, n = 3–6) with chloro bridged complexes [R₃P(Cl)M(μ‐Cl)M(Cl)PR₃] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl₂(R₃P)M–L(CH₂)_nL–M(PR₃)Cl₂] 1 – 17 . The structures of [Cl₂(Et₃P)Pd–L(CH₂)₃L–Pd(PEt₃)Cl₂] ( 1 ), [Cl₂(Bu₃P)Pd–L(CH₂)₄L–Pd(PBu₃)Cl₂] ( 10 ), [Cl₂(Et₃P)Pd–L(CH₂)₅L–Pd(PEt₃)Cl₂] ( 3 ), [Cl₂(Et₃P)Pt–L(CH₂)₃L–Pt(PEt₃)Cl₂] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl₂(Cp*)Ir–L(CH₂)_nL–Ir(Cp*)Cl₂] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)₂Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).     

Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions

Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me₂Si(CH₂SnMe₂X)₂ ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH₂(SnMe₂CH₂I)₂ ( 7 ), CH₂(SnMe₂CH₂Cl)₂ ( 8 ), cyclo‐Me₂Sn(CH₂SnMe₂CH₂)₂SiMe₂ ( 6 ), cyclo‐(Me₂SnCH₂)₄ ( 9 ), cyclo‐Me_(2?n)X_nSn(CH₂SiMe₂CH₂)₂SnX_nMe_(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt₄[cyclo‐ Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?F] ( 13 ), PPh₄[cyclo‐Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?Cl] ( 14 ), NEt₄[cyclo‐Me(F)Sn(CH₂SiMe₂CH₂)₂Sn(F)Me?F] ( 15 ), [NEt₄]₂[cyclo‐Cl₂Sn(CH₂SiMe₂CH₂)₂SnCl₂?2 Cl] ( 16 ), M[Me₂Si(CH₂Sn(Cl)Me₂)₂?Cl] ( 17 a , M=PPh₄; 17 b , M=NEt₄), NEt₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?F] ( 18 ), NEt₄[Me₂Si(CH₂Sn(F)Me₂)₂?F] ( 19 ), and PPh₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and ¹H, ¹³C, ¹⁹F, ²⁹Si, and ¹¹⁹Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.     

nido‐Undecaboranes and ‐borates of the Type B11H13L and B11H12L‐

The Lewis base SMe₂ in 7‐B₁₁H₁₃(SMe₂) ( 1a ) can be replaced by the amines L = NH₂(CH₂tBu), NH₂Cy, NH₂Ph, NH₂(4‐C₆H₄Me), py, chinoline or the phosphanes L = PPh₃, PMePh₂, yielding 7‐B₁₁H₁₃L ( 1b ‐ i ). The borane 1a can be deprotonated by certain amines, alkanides, or hydrides to give the anion 7‐B₁₁H₁₂(SMe₂)^‐ ( 2a ). Replacing the base SMe₂ in the anion 2a by weak bases gives B₁₁H₁₂L^‐ (L = PPh₃, MeCN; 2h , j ). Upon reaction of 1a with the amine NH₂(CH₂tBu) in the ratio 1:2, a deprotonation and the substitution of SMe₂ by the amine are observed, 7‐B₁₁H₁₂[NH₂(CH₂tBu)]^‐ ( 2b ) being formed. At 170 °C, the 7‐isomers 1b , f are isomerized into a mixture of the corresponding 1‐ and 2‐isomers ( 1b′ , f′ and 1b″ , f″ , respectively).     

Effect of the length of the substituents on the phase structure and transition behavior of a series of laterally attached side‐chain liquid‐crystalline polynorbornenes

A series of polynorbornenes (PNBEs) with 1,4‐bis[(3′‐fluoro‐4′‐n‐alkoxyphenyl)ethynyl]benzene mesogens (n = 1–12, where n is the number of methylene units in the substituents of the mesogens) laterally attached to polymer backbones through a one‐carbon spacer were previously synthesized by the ring‐opening metathesis polymerization of the corresponding norbornene‐based monomers. Differential scanning calorimetric results showed that the first‐order transition temperatures exhibit an odd–even alternation, especially when PNBEs have lower values of n. PNBE (n = 8), similar to the previously studied PNBEs (n = 9–12), shows a smectic C (S_C) phase at room temperature (Kim, Pugh, and Cheng, Macromolecules, 33, 8983, 2000.) According to one‐ and two‐dimensional wide‐angle X‐ray scattering experiments, PNBEs (n = 2–7) exhibit a nematic (N) phase with S_C fluctuations, whereas for PNBE (n = 1), only an N phase is observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3029–3037, 2001     

Packing forces in dichloridobis(3,5‐diphenyl‐1H‐pyrazole‐κN2)cobalt(II) dichloromethane hemisolvate

The title compound, [CoCl₂(C₁₅H₁₂N₂)₂]·0.5CH₂Cl₂, was crystallized from a binary mixture of dichloromethane and hexane and a dimeric supramolecular structure was isolated. The Co^II centre exhibits a distorted tetrahedral geometry, with two independent pyrazole‐based ligands occupying two coordination sites and two chloride ligands occupying the third and fourth coordination sites. The supramolecular structure is supported by complementary hydrogen bonding between the pyrazole NH group and the chloride ligand of an adjacent molecule. This hydrogen‐bonding motif yields a ten‐membered hydrogen‐bonded ring. Density functional theory (DFT) simulations at the PBE/6‐311G level of theory were used to probe the solid‐state structure. These simulations suggest that the chelate undergoes a degree of conformational distortion from the lowest‐energy geometry to allow for optimal hydrogen bonding in the solid state.     

Water Soluble Gold(I)‐diacetyl‐1,3,5‐triaza‐7‐phosphaadamantane‐arylazoimidazole Complexes: Synthesis and Spectroscopic Study

Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA＝diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’＝p-R-C6H4-N＝N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R＝H (a), Me (b), Cl (c) and R’＝Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure.     

Self‐Assembly of Discrete Homochiral,Helical, Hydrogen‐Bonded Nanocages: From Vesicles to Microspheres and Tubules Capable of Gelating Solvents

The chiral tris‐monodentate imidazolinyl ligands 1 a – c exhibit a strong tendency to form the discrete, helical [2+3] nanocages 3 ([ 1 ₂ ?2 ₃]) with tartaric acids 2 . Circular dichroism (CD) spectra and theoretical calculations reveal that supramolecular handedness of capsulelike architectures is determined only by the chirality of the imidazolinyl ligands rather than tartaric acids. The chirality of imidazolinyl ligands is transferred to the helicity of the complexes through the directed hydrogen bonds between the N3 atom of imidazoline rings and the carboxyl of tartaric acids. These hydrogen‐bonded nanocages can spontaneously self‐assemble into spherical vesicles, during which the hydrogen bonding that arises from the hydroxyl groups of tartaric acids plays a crucial issue. The vesicles formed by [{(S,S,S)‐ 1 a }₂( 2 ^L)₃] ( 3 a ) may further evolve into microspheres that gelate organic solvents after being aged at ?20 °C for 24 h, and can also be unprecedentedly transformed to tubular assemblies capable of rigidifying the solvents when subjected to ultrasound irradiation.