Selectivity in Gas Adsorption by Molecular Cucurbit[6]uril

Pan, Sudip; Saha, Ranajit; Mandal, Subhajit; Mondal, Sukanta; Gupta, Ashutosh; Fernández-Herrera, María A.; Merino, Gabriel; Chattaraj, Pratim Kumar

doi:10.1021/acs.jpcc.6b02545

Cited by 54 publications

(25 citation statements)

References 85 publications

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“…We further extended our work to the cucurbit[n]uril (CB[n]) taking CB[6] as a case study. CB[n] is well-known for its host-guest chemistry [134,135,136]. We employed them to encapsulate Ng atoms as well [137].…”

Section: Discussionmentioning

confidence: 99%

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

et al. 2019

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Noble gases (Ngs) are the least reactive elements in the periodic table towards chemical bond formation when compared with other elements because of their completely filled valence electronic configuration. Very often, extreme conditions like low temperatures, high pressures and very reactive reagents are required for them to form meaningful chemical bonds with other elements. In this personal account, we summarize our works to date on Ng complexes where we attempted to theoretically predict viable Ng complexes having strong bonding to synthesize them under close to ambient conditions. Our works cover three different types of Ng complexes, viz., non-insertion of NgXY type, insertion of XNgY type and Ng encapsulated cage complexes where X and Y can represent any atom or group of atoms. While the first category of Ng complexes can be thermochemically stable at a certain temperature depending on the strength of the Ng-X bond, the latter two categories are kinetically stable, and therefore, their viability and the corresponding conditions depend on the size of the activation barrier associated with the release of Ng atom(s). Our major focus was devoted to understand the bonding situation in these complexes by employing the available state-of-the-art theoretic tools like natural bond orbital, electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. Intriguingly, these three types of complexes represent three different types of bonding scenarios. In NgXY, the strength of the donor-acceptor Ng→XY interaction depends on the polarizing power of binding the X center to draw the rather rigid electron density of Ng towards itself, and sometimes involvement of such orbitals becomes large enough, particularly for heavier Ng elements, to consider them as covalent bonds. On the other hand, in most of the XNgY cases, Ng forms an electron-shared covalent bond with X while interacting electrostatically with Y representing itself as [XNg]+Y−. Nevertheless, in some of the rare cases like NCNgNSi, both the C-Ng and Ng-N bonds can be represented as electron-shared covalent bonds. On the other hand, a cage host is an excellent moiety to examine the limits that can be pushed to attain bonding between two Ng atoms (even for He) at high pressure. The confinement effect by a small cage-like B12N12 can even induce some covalent interaction within two He atoms in the He2@B12N12 complex.

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Section: Discussionmentioning

confidence: 99%

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

et al. 2019

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“…Both methods show a stronger binding of CO 2 over CO in CB [6], which is in line with previously reported DFT results. 40 A free-energy profile based on umbrella sampling of MD simulations of CO 2 and CO is shown in Figure 3a. The results suggest that CO 2 and CO need to overcome a low energy barrier when entering the cavity and reach an energy…”

Section: ■ Results and Discussionmentioning

confidence: 99%

1 Host-guest Chemistry Meets Electrocatalysis: Cucurbit[6]uril on a Au Surface as Hybrid System in CO2 Reduction

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et al. 2019

Proceedings of the nanoGe Fall Meeting 2019

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The rational control of forming and stabilizing reaction intermediates to guide specific reaction pathways remains to be a major challenge in electrocatalysis. In this work, we report a surface active-site engineering approach for modulating electrocatalytic CO 2 reduction using the macrocycle cucurbit[6]uril (CB[6]). A pristine gold surface functionalized with CB[6] nanocavities was studied as a hybrid organic−inorganic model system that utilizes host−guest chemistry to influence the heterogeneous electrocatalytic reaction. The combination of surface-enhanced infrared absorption (SEIRA) spectroscopy and electrocatalytic experiments in conjunction with theoretical calculations supports capture and reduction of CO 2 inside the hydrophobic cavity of CB[6] on the gold surface in aqueous KHCO 3 at negative potentials. SEIRA spectroscopic experiments show that the decoration of gold with the supramolecular host CB[6] leads to an increased local CO 2 concentration close to the metal interface. Electrocatalytic CO 2 reduction on a CB[6]-coated gold electrode indicates differences in the specific interactions between CO 2 reduction intermediates within and outside the CB[6] molecular cavity, illustrated by a decrease in current density from CO generation, but almost invariant H 2 production compared to unfunctionalized gold. The presented methodology and mechanistic insight can guide future design of molecularly engineered catalytic environments through interfacial host−guest chemistry.

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“…This supramolecular sensor works at room temperature, while many semiconductor gas sensors require high temperature of 200-500°C, indicating that the supramolecular sensor operates with lower power consumption. Molecular hosts that can bind gas molecules [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] have been developed so far. A main difference between the nanocube and other molecular hosts is that the nanocube finely responds to the guest molecules and outputs a strong fluorescence signal.…”

Section: Discussionmentioning

confidence: 99%

Supramolecular fluorescence sensor for liquefied petroleum gas

et al. 2019

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Sensing systems of nonpolar gas molecules without functional groups such as natural gas and liquefied petroleum gas (LPG) remain difficult to develop because of lacking selective detection of such molecules over other gas molecules. Here we report a supramolecular fluorescence sensor for LPG using a 2-nm-sized cube-shaped molecular container i.e. a nanocube self-assembled from six molecules of gear-shaped amphiphiles (GSA) in water. The nanocube selectively encapsulates LPG, while it does not bind other gas molecules. Upon encapsulation of LPG in the nanocube, the fluorescence from the nanocube is enhanced by 3.9 times, which is caused by the restricted motion of the aromatic rings of GSA in the nanocube based on aggregation-induced emission. Besides the high selectivity, high sensitivity, quick response, high stability of the nanocube for LPG, and easy preparation of GSA satisfy the requirement for its practical use for an LPG sensor.

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Selectivity in Gas Adsorption by Molecular Cucurbit[6]uril

Cited by 54 publications

References 85 publications

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

1 Host-guest Chemistry Meets Electrocatalysis: Cucurbit[6]uril on a Au Surface as Hybrid System in CO2 Reduction

Supramolecular fluorescence sensor for liquefied petroleum gas

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