Computational Unravelling of the Role of Alkyl Groups on the Host‐Guest Complexation of Pillar[5]arenes with Neutral Dihalobutanes

Panneerselvam, Murugesan; Kumar, Madhu Deepan; Jaccob, Madhavan; Solomon, Rajadurai Vijay

doi:10.1002/slct.201702541

Cited by 19 publications

(11 citation statements)

References 42 publications

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“…Pillararene (in this instance 1,4-dimethoxypillar [5]arene) is afforded by reaction with boron trifluoride diethyl etherate in the presence of paraformaldehyde and can be fine-tunedbyi ncreasing ring expansion [37] and alteringt he functional groups at either rim. [38] Figure 5. Porous organic cage,CC3-R with tetrahedrally arranged windows.…”

Section: Metal-organic Polyhedramentioning

confidence: 99%

Molecularly Mixed Composite Membranes: Challenges and Opportunities

Zhu

O’Nolan

Lively

2019

Chemistry A European J

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The fabrication of porous molecules, such as metal–organic polyhedra (MOPs), porous organic cages (POCs) and others, has given rise to the potential for creating “solid solutions” of molecular fillers and polymers. Such solid solutions circumvent longstanding interface issues associated with mixed matrix membranes (MMMs), and are referred to as molecularly mixed composite membranes (MMCMs) to distinguish them from traditional two‐phase MMMs. Early investigations of MMCMs highlight the advantages of solid solutions over MMMs, including dispersion of the filler, anti‐plasticization of the polymer network, and removal of deleterious interfacial issues. However, the exact microscopic structure as well as the transport modality in this new class of membrane are not well understood. Moreover, there are clear engineering challenges that need to be addressed for MMCMs to transition into the field. In this Minireview, the authors outline several scientific and technological challenges associated with the aforementioned questions and their suggestions to tackle them.

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Section: Metal-organic Polyhedramentioning

confidence: 99%

Molecularly Mixed Composite Membranes: Challenges and Opportunities

Zhu

O’Nolan

Lively

2019

Chemistry A European J

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“…To this direction, complexation of neutral 1,4-dihalobutanes with different alkyl pillar[5]arenes were studied by Li and others . Computational investigations suggested that dispersive interactions accompanying guest penetration render large stability to such host–guest complexes . Noteworthy enough, EtP5 displays the strongest binding toward 1,4-diiodobutane than 1,4-difluorobutane.…”

Section: Introductionmentioning

confidence: 99%

Probing Binding of Ethylated Pillar[5]arene with Pentene and Chlorobutane Positional Isomers

Athare

Gejji

2019

J. Phys. Chem. A

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Host guest binding from alkyl-modified pillararene macrocycles has been of significant interest in a variety of applications in the domains of supramolecular chemistry. In this work, we analyze the selectivity in binding of the ethylated pillar[5]arene (EtP5) macrocycle with 1-pentene, cis and trans 2-pentene, and the 1- and 2-chlorobutane isomer guests employing the ωB97x-based density functional theory. EtP5 reveals stronger binding with 1-pentene the accompanying change of energy upon the complexation being 85.5 kJ mol–1 compared to 71.3 and 75.8 kJ mol–1 for the cis and trans-2-pentene isomers, respectively. The complexation of EtP5 with pentene isomers is governed by the interplay of CH···π, H–H, and O···H noncovalent interactions. The inferences on the guest binding rationalized through the quantum theory of atoms in molecules are in consonance with data on relative uptake of pentene isomers observed from the gas chromatography experiments reported earlier. A stronger binding of EtP5 with 1-pentene is borne out from a large C–H···π and H–H interactions. The chlorobutane isomers are held together within the EtP5 cavity via C–H···π as well as Cl···H interactions those prevail over the O–H···O hydrogen bonding in such complexes. The host–guest binding emerges with the signature in “frequency shifts” of the characteristic alkyl vibrations of the host and corroborated with the natural bond orbital analyses.

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“…The results obtained unambiguously indicate the formation of the 7/5-VT complex. The absence of cross peaks between 5-VT and aromatic protons of pillar [5]arene 7 indicates that the monomer is not in the macrocyclic cavity but in the pseudocavity of the macrocycle formed by fragments of substituents [62][63][64].…”

Section: Study Of the Interaction Of Pillar[5]arenes With Pvt And Pvte Polymersmentioning

confidence: 99%

Towards Universal Stimuli-Responsive Drug Delivery Systems: Pillar[5]arenes Synthesis and Self-Assembly into Nanocontainers with Tetrazole Polymers

et al. 2021

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In this work, we have proposed a novel universal stimulus-sensitive nanosized polymer system based on decasubstituted macrocyclic structures—pillar[5]arenes and tetrazole-containing polymers. Decasubstituted pillar[5]arenes containing a large, good leaving tosylate, and phthalimide groups were first synthesized and characterized. Pillar[5]arenes containing primary and tertiary amino groups, capable of interacting with tetrazole-containing polymers, were obtained with high yield by removing the tosylate and phthalimide protection. According to the fluorescence spectroscopy data, a dramatic fluorescence enhancement in the pillar[5]arene/fluorescein/polymer system was observed with decreasing pH from neutral (pH = 7) to acidic (pH = 5). This indicates the destruction of associates and the release of the dye at a pH close to 5. The presented results open a broad range of opportunities for the development of new universal stimulus-sensitive drug delivery systems containing macrocycles and nontoxic tetrazole-based polymers.

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Computational Unravelling of the Role of Alkyl Groups on the Host‐Guest Complexation of Pillar[5]arenes with Neutral Dihalobutanes

Cited by 19 publications

References 42 publications

Molecularly Mixed Composite Membranes: Challenges and Opportunities

Molecularly Mixed Composite Membranes: Challenges and Opportunities

Probing Binding of Ethylated Pillar[5]arene with Pentene and Chlorobutane Positional Isomers

Towards Universal Stimuli-Responsive Drug Delivery Systems: Pillar[5]arenes Synthesis and Self-Assembly into Nanocontainers with Tetrazole Polymers

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