Gated molecular baskets

Hermann, Keith; Ruan, Yian; Hardin, Alex M.; Hadad, Christopher M.; Badjić, Jovica D.

doi:10.1039/c4cs00140k

Cited by 81 publications

(60 citation statements)

References 121 publications

(178 reference statements)

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“…In spite of the postulated one-step mechanism (Figure 2D), the exchange process may also be a two-step process including rapid opening of the basket's one gate (first step) followed by a slower swapping of the entrapped with the incoming compounds and the simultaneous opening of two additional gates (second step). It is indeed difficult to repudiate this particular mechanistic scenario, although we have not observed any intermediate either spectroscopically or kinetically (the saturation kinetics) [18] to suggest the two-step process [23]. In addition, en earlier study [26] indicated that for a guest populating the basket's inner space to a greater extent (PC > 0.3, Table 1) the basket's racemization necessitates simultaneous opening of all three gates.…”

Section: Resultsmentioning

confidence: 59%

“…To our knowledge, there has been no particular study [21] about the nature of transition states characterizing gated encapsulations, and this is the objective of our paper. Gated molecular baskets [22] have been designed and studied in our laboratory for almost a decade [23]. These hosts comprise a flat aromatic base that is fused to three bicycle[2.…”

Section: Introductionmentioning

confidence: 99%

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On the Nature of the Transition State Characterizing Gated Molecular Encapsulations

Wang

Chen

et al. 2014

Molecules

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Gated molecular encapsulations, with baskets of type 1, are postulated to occur by the mechanism in which solvent molecule penetrates the inner space of 1, through one of its apertures, while the residing guest simultaneously departs the cavity. In the transition state of the exchange, three pyridine-based gates are proposed to assume an open position with both incoming solvent and departing guest molecules interacting with the concave surface of the host. The More O'Ferrall-Jencks diagram and linear free energy relationships (LFERs) suggest a more advanced departure of the guest when bigger solvents partake in the displacement.

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Section: Resultsmentioning

confidence: 59%

Section: Introductionmentioning

confidence: 99%

On the Nature of the Transition State Characterizing Gated Molecular Encapsulations

Wang

Chen

et al. 2014

Molecules

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“…The design of chiral molecular hosts is very attractive, since they can be used for the stereoselective recognition of chiral guest molecules or in asymmetric catalysis . Among the inherently chiral cage compounds such as calixarenes and cavitands, the cryptophane and hemicryptophane hosts, both based on the cyclotriveratrylene (CTV) unit, arouse a growing interest ,.…”

Section: Introductionmentioning

confidence: 99%

Closed vs Open‐Shell CTV Based Host Compounds: A Direct Comparison

et al. 2016

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International audienceNew hemicryptophane compds. combining a cyclotriveratrylene (CTV) unit, three binaphthol moieties in the linkers and closed by a simple benzene unit have been synthesized enantiomerically and diastereomerically pure. Assignment of their abs. configuration was achieved by chem. correlation. These closed shell host compds. were then tested in the recognition of carbohydrates and compared with their open-shell counterparts. Closing the mol. cage induces a slight drop in affinity, assocd. with an improvement in the stereoselectivity of the recognition process, probably related to the higher preorganization of the cage compds

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“…Since the positively and negatively charged (LiF) n clusters and their neutral parents are well-known systems [29][30][31][32][33], the knowledge of their equilibrium structures might be of great help while designing the anions containing an additional fluorine atom. The preliminary considerations of the shape and size that one might expect of the Li n F − n+1 structures for n > 5 led us to the Li 12 F 13 − anion that we initially predicted to be large enough to form a high-symmetry negatively charged molecular basket [34]. If such predictions were confirmed, the Li 12 F 13 − anion could be considered useful as a steric shielding agent (enabling the introducing of selected metal ions into various solutions).…”

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confidence: 99%

Polynuclear Li12F13 − anion as a steric shielding agent with respect to selected metal ions

Czapla

2016

Theor Chem Acc

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Boldyrev [1]. In general, the superhalogens were defined as a group of compounds matching the MX k+1 formula (where M is a metal atom having the maximal formal valence k, while X corresponds to the halogen atom) and characterized by the electron affinity (EA) higher than that of the chlorine atom (EA = 3.62 eV) [2]. It implies that superhalogens form very strongly bound and thermodynamically stable molecular anions [3][4][5] which are characterized by the enormous values of vertical electron detachment energies (VDEs) approaching 14 eV in certain cases [6,7]. The very first experimental evidence of the superhalogen existence was provided in 1999 by the Wang's group who reported the photoelectron spectra of the selected triatomic MX 2 − superhalogen anions (M = Li, Na; X = Cl, Br, I) [8]. Since then, many other superhalogen anions [e.g., Na k Cl − k+1 (k = 1-4) and MX 3 − (where M = Be, Mg, Ca; X = Cl, Br)] have also been identified experimentally [9,10]. As indicated by both theoretical predictions and experimental measurements, the original superhalogen formula (MX k+1 ) can be extended to include the polynuclear M n X nk+1 neutral superhalogen compounds (containing n central atoms) whose corresponding polynuclear M n X − nk+1 anions exhibit even larger electron binding energies than their mononuclear counterparts [11][12][13][14][15][16][17]. In addition to numerous applications of superhalogens, we have recently pointed out their possible usage as strong oxidizing agents [18][19][20][21] and Lewis-Brønsted superacid precursors [7,22, 23]. It should also be mentioned that some recent works revealed novel superhalogen applications in Li-ion batteries, solar cells, and hydrogen storage materials [24][25][26][27].It was also established that one of the important features characterizing superhalogen anions is their tendency to adopt high-symmetry compact structures [10]. Recent report concerning the properties of the Li n F − n+1 (n = 2-5) superhalogen anions confirmed that observation, as the Abstract Polynuclear superhalogen anion Li 12 F 13 − and its ionic complexes formed by the interaction with selected metal ions (i.e., Li 12 F 13 − Na + , Li 12 F 13 − K + , Li 12 F 13 − Mg 2+ , and Li 12 F 13 − Zn 2+ ) are proposed and investigated on the basis of ab initio calculations. The thermodynamic stability, vertical excess electron detachment energy, and binding energies between ionic components were examined and discussed. The Li 12 F 13 − anion has been proved stable against fragmentation and its vertical electronic stability was found to approach 10 eV. Due to its specific equilibrium structure that resembles a molecular basket, the Li 12 F 13 − anion was found capable of trapping positively charged metal ions inside to form strongly bound ionic complexes. The large values of binding energies predicted for the Li 12 F 13 − Na + , Li 12 F 13 − K + , Li 12 F 13 − Mg 2+ , and Li 12 F 13 − Zn 2+ systems and their specific equilibrium structures indicate that the Li 12 F 13 − anion can be useful as a steric shielding...

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Gated molecular baskets

Cited by 81 publications

References 121 publications

On the Nature of the Transition State Characterizing Gated Molecular Encapsulations

On the Nature of the Transition State Characterizing Gated Molecular Encapsulations

Closed vs Open‐Shell CTV Based Host Compounds: A Direct Comparison

Polynuclear Li12F13 − anion as a steric shielding agent with respect to selected metal ions

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