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The combination of a bent diamino(nickel(II) porphyrin) with 2‐formylpyridine and FeII yielded an FeII4L6 cage. Upon treatment with the fullerenes C60 or C70, this cage was found to transform into a new host–guest complex incorporating three FeII centers and four porphyrin ligands, in an arrangement that is hypothesized to maximize π interactions between the porphyrin units of the host and the fullerene guest bound within its central cavity. The new complex shows coordinative unsaturation at one of the FeII centers as the result of the incommensurate metal‐to‐ligand ratio, which enabled the preparation of a heterometallic cone‐shaped CuIFeII2L4 adduct of C60 or C70.  相似文献   

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The components of a 1:2 mixture of meso‐tetrakis(4‐dodecyl‐3,5‐dihydroxyphenyl)porphyrin ( 1 ) and a bowl‐shaped tetrakis(4‐pyridylethynyl)cavitand ( 2 ) in CDCl3 or C6D6 self‐assemble quantitatively into the doubly cavitand‐capped porphyrin capsule 2?1?2 through eight ArOH ??? Npy hydrogen bonds. Capsule 2?1?2 possesses two cavities divided by the porphyrin ring and encapsulates two molecules of 1‐acetoxy‐3,5‐dimethoxybenzene ( G ) as a guest to form G / G @( 2?1?2 ). Remarkable solvent effect was observed, in which the apparent association constant of 2?1?2 with G in C6D6 was much greater than that in CDCl3.  相似文献   

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There is broad interest in molecular encapsulation as such systems can be utilized to stabilize guests, facilitate reactions inside a cavity, or give rise to energy‐transfer processes in a confined space. Detailed understanding of encapsulation events is required to facilitate functional molecular encapsulation. In this contribution, it is demonstrated that Ir and Rh‐Cp‐type metal complexes can be encapsulated inside a self‐assembled M6L4 metallocage only in the presence of an aromatic compound as a second guest. The individual guests are not encapsulated, suggesting that only the pair of guests can fill the void of the cage. Hence, selective co‐encapsulation is observed. This principle is demonstrated by co‐encapsulation of a variety of combinations of metal complexes and aromatic guests, leading to several ternary complexes. These experiments demonstrate that the efficiency of formation of the ternary complexes depends on the individual components. Moreover, selective exchange of the components is possible, leading to formation of the most favorable complex. Besides the obvious size effect, a charge‐transfer interaction may also contribute to this effect. Charge‐transfer bands are clearly observed by UV/Vis spectrophotometry. A change in the oxidation potential of the encapsulated electron donor also leads to a shift in the charge‐transfer energy bands. As expected, metal complexes with a higher oxidation potential give rise to a higher charge‐transfer energy and a larger hypsochromic shift in the UV/Vis spectrum. These subtle energy differences may potentially be used to control the binding and reactivity of the complexes bound in a confined space.  相似文献   

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Two bowl‐shaped cavities , each having three OH? hydrogen‐bond donors at its base, are present in double‐cone‐shaped metallacrown anion host [Co6(μ‐OH)6(μ‐L)6]m+ ( 1 m + ; HL=3{5}‐(pyrid‐2‐yl)‐5{3}‐(tert‐butyl)pyrazole). Depending on its affinity for the anions present, it can be isolated in its CoIII3CoII3 (m=3; e.g., 1 (ClO4)3) and CoIII2CoII4 (m=2; e.g., 1 (BF4)2 ? n H2O) oxidation states. See picture for photographs of isolated salts.

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Solvothermal reactions of the calix[4]arene tetraacetic acid (H4CTA) with zinc nitrate in the presence of α,ω‐diaminoalkanes afford two‐dimensional metallopolycapsular networks of the formula {[Me2NH2]2[G@(Zn2(CTA)2)] ? (DMF)2 ? (H2O)4}n (G=+NH3–(CH2)n–NH3+, n=2, 3, 4; DMF=N,N‐dimethylformamide). These metallopolycapsular networks are built up of metallocapsules that consist of two CTA and two ZnII ions. Short alkanediyldiammonium (+NH3–(CH2)n–NH3+, n=2, 3, 4) guest ions are accommodated in each capsule of the metallopolycapsular network through a variety of supramolecular interactions. The thermal behaviours and the solid‐state photoluminescent properties of these complexes were also investigated.  相似文献   

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Guest‐induced M18L6–M24L8 capsule–capsule conversion is reported. Both capsules are composed of PdII ethylenediamine units (M) and 1,3,5‐tris(3,5‐pyrimidyl)pyrimidine (L), and form trigonal bipyramidal (M18L6) and octahedral (M24L8) closed‐shell structures with huge hydrophobic inner spaces. The M18L6 trigonal bipyramid is converted to the M24L8 octahedron through encapsulation of large aromatic guests, with the latter capsule possessing a cavity volume three times larger than the former. Despite the dynamic properties of the capsule host, the encapsulated guests are difficult to extract and are thus isolated from the external environment.  相似文献   

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A methodology for preparing supramolecular hydrogels from guest‐modified cyclodextrins (CDs) based on the host–guest and hydrogen‐bonding interactions of CDs is presented. Four types of modified CDs were synthesized to understand better the gelation mechanism. The 2D ROESY NMR spectrum of β‐CD‐AmTNB (Am=amino, TNB=trinitrobenzene) reveals that the TNB group was included in the β‐CD cavity. Pulsed field gradient NMR (PFG NMR) spectroscopy and AFM show that β‐CD‐AmTNB formed a supramolecular polymer in aqueous solution through head‐to‐tail stacking. Although β‐CD‐AmTNB did not produce a hydrogel due to insufficient growth of supramolecular polymers, β‐CD‐CiAmTNB (Ci=cinnamoyl) formed supramolecular fibrils through host–guest interactions. Hydrogen bonds between the cross‐linked fibrils resulted in the hydrogel, which displayed excellent chemical‐responsive properties. Gel‐to‐sol transitions occurred by adding 1‐adamantane carboxylic acid (AdCA) or urea. 1H NMR and induced circular dichroism (ICD) spectra reveal that AdCA released the guest parts from the CD cavity and that urea acts as a denaturing agent to break the hydrogen bonds between CDs. The hydrogel was also destroyed by adding β‐CD, which acts as the competitive host to reduce the fibrils. Furthermore, the gel changed to a sol by adding methyl orange (MO) as a guest compound, but the gel reappeared upon addition of α‐CD, which is a stronger host for MO.  相似文献   

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Despite the remarkable progress made in controllable self‐assembly of stimuli‐responsive supramolecular polymers (SSPs), a basic issue that has not been consideration to date is the essential binding site. The noncovalent binding sites, which connect the building blocks and endow supramolecular polymers with their ability to respond to stimuli, are expected to strongly affect the self‐assembly of SSPs. Herein, the design and synthesis of a dual‐stimuli thermo‐ and photoresponsive Y‐shaped supramolecular polymer (SSP2) with two adjacent β‐cyclodextrin/azobenzene (β‐CD/Azo) binding sites, and another SSP (SSP1) with similar building blocks, but only one β‐CD/Azo binding site as a control, are described. Upon gradually increasing the polymer solution temperature or irradiating with UV light, SSP2 self‐assemblies with a higher binding‐site distribution density; exhibits a flower‐like morphology, smaller size, and more stable dynamic aggregation process; and greater controllability for drug‐release behavior than those observed with SSP1 self‐assemblies. The host–guest binding‐site‐tunable self‐assembly was attributed to the positive cooperativity generated among adjacent binding sites on the surfaces of SSP2 self‐assemblies. This work is beneficial for precisely controlling the structural parameters and controlled release function of SSP self‐assemblies.  相似文献   

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Nitroxide free radicals have been used to study the inner space of one of Rebek’s water‐soluble capsules. EPR and 1H NMR spectroscopy, ESI‐MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka) in the order of 107 M ?2. EPR spectral‐shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed.  相似文献   

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Positive cooperativity achieved through activating weak non‐covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO‐based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion‐pairing interactions. The X‐ray single‐crystal structure revealed that the strong positive cooperativity likely originates from eight C?H???O hydrogen bonds between the two head‐to‐head‐arranged syn tube molecules. These relatively weak hydrogen bonds were not observed in the free hosts and only emerged in the complex. Furthermore, this complex was used as a basic motif to construct a robust [2+2] cyclic assembly, thus demonstrating its potential in molecular self‐assembly.  相似文献   

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A new host molecule consists of four terpyridine groups as the binding sites with zinc(II) ion and a copillar[5]arene incorporated in the center as a spacer to interact with guest molecule was designed and synthesized. Due to the 120 ° angle of the rigid aromatic segment, a cross‐linked dimeric hexagonal supramolecular polymer was therefore generated as the result of the orthogonal self‐assembly of metal–ligand coordination and host–guest interaction. UV/Vis spectroscopy, 1H NMR spectroscopy, viscosity and dynamic light‐scattering techniques were employed to characterize and understand the cross‐linking process with the introduction of zinc(II) ion and guest molecule. More importantly, well‐defined morphology of the self‐assembled supramolecular structure can be tuned by altering the adding sequence of the two components, that is, the zinc(II) ion and the guest molecule. In addition, introduction of a competitive ligand suggested the dynamic nature of the supramolecular structure.  相似文献   

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