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Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental-Computational Analysis of the Guest Inclusion Properties

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Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides : An Experimental-Computational Analysis of the Guest Inclusion Properties. / Twum, Kwaku; Rautiainen, J. Mikko; Yu, Shilin; Truong, Khai Nghi; Feder, Jordan; Rissanen, Kari; Puttreddy, Rakesh; Beyeh, Ngong Kodiah.

In: Crystal Growth and Design, Vol. 20, No. 4, 01.04.2020, p. 2367-2376.

Research output: Contribution to journalArticleScientificpeer-review

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Twum, K., Rautiainen, J. M., Yu, S., Truong, K. N., Feder, J., Rissanen, K., ... Beyeh, N. K. (2020). Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental-Computational Analysis of the Guest Inclusion Properties. Crystal Growth and Design, 20(4), 2367-2376. https://doi.org/10.1021/acs.cgd.9b01540

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Twum, Kwaku ; Rautiainen, J. Mikko ; Yu, Shilin ; Truong, Khai Nghi ; Feder, Jordan ; Rissanen, Kari ; Puttreddy, Rakesh ; Beyeh, Ngong Kodiah. / Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides : An Experimental-Computational Analysis of the Guest Inclusion Properties. In: Crystal Growth and Design. 2020 ; Vol. 20, No. 4. pp. 2367-2376.

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@article{ebc2cd9c5aa9436288e7fa18857a6db2,
title = "Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental-Computational Analysis of the Guest Inclusion Properties",
abstract = "The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using 1H NMR spectroscopy. Substitution of methylenesulfonate groups at 2-positions of resorcinol units resulted in an increase of cavity depth by ∼2.80 {\AA} and a narrow cavity portal compared to Calkyl-2-H-resorcinarenes. The effect of alkyl chain lengths on the endo-complexation, that is the ability to incorporate other than N-methyl chains inside the cavities, was investigated using ammonium cations of the type +NH2(R1)(R2), (R1 = Me, Et, Bu, R2 = Bu, Ph, Bz). The C-H···πinteractions between guests and hosts are the key driving forces for 14 out of 16 observed endo-complexes. In the case of the N-butyl-N-benzylammonium cation, the hydrogen bonding between -NH2 and sulfonate oxygens and the larger size hamper the N-butyl and N-benzyl groups from entering the host cavity. Association constants derived from isothermal calorimetry titrations confirm 1:1 host-guest complexes highlighting guest affinity, based on size and orientation. X-ray crystallographic analysis revealed two types of complexes viz. sodium-containing cocrystals, [(An)4 -·m(Bn)+·qNa+], and sodium-free, [(An)4 -·4(Bn)+]. Both types accommodate (Bn+) guests in their cavities. The N-methylated heterocycle guests and host form capsule-like structures in which the two halves were joined by O-Na coordination bonds and self-assembly into two-dimensional polymeric sheets. From the crystal structures, different conformations of methylenesulfonate groups with respect to cavity arising due to tetrahedral geometry of methylene linker were observed. Density functional theory (DFT) computations were used to analyze the effects of endo-guests on host conformations and to estimate the relative strengths of host-guest interactions.",
author = "Kwaku Twum and Rautiainen, {J. Mikko} and Shilin Yu and Truong, {Khai Nghi} and Jordan Feder and Kari Rissanen and Rakesh Puttreddy and Beyeh, {Ngong Kodiah}",
year = "2020",
month = "4",
day = "1",
doi = "10.1021/acs.cgd.9b01540",
language = "English",
volume = "20",
pages = "2367--2376",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "4",

}

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TY - JOUR

T1 - Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides

T2 - An Experimental-Computational Analysis of the Guest Inclusion Properties

AU - Twum, Kwaku

AU - Rautiainen, J. Mikko

AU - Yu, Shilin

AU - Truong, Khai Nghi

AU - Feder, Jordan

AU - Rissanen, Kari

AU - Puttreddy, Rakesh

AU - Beyeh, Ngong Kodiah

PY - 2020/4/1

Y1 - 2020/4/1

N2 - The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using 1H NMR spectroscopy. Substitution of methylenesulfonate groups at 2-positions of resorcinol units resulted in an increase of cavity depth by ∼2.80 Å and a narrow cavity portal compared to Calkyl-2-H-resorcinarenes. The effect of alkyl chain lengths on the endo-complexation, that is the ability to incorporate other than N-methyl chains inside the cavities, was investigated using ammonium cations of the type +NH2(R1)(R2), (R1 = Me, Et, Bu, R2 = Bu, Ph, Bz). The C-H···πinteractions between guests and hosts are the key driving forces for 14 out of 16 observed endo-complexes. In the case of the N-butyl-N-benzylammonium cation, the hydrogen bonding between -NH2 and sulfonate oxygens and the larger size hamper the N-butyl and N-benzyl groups from entering the host cavity. Association constants derived from isothermal calorimetry titrations confirm 1:1 host-guest complexes highlighting guest affinity, based on size and orientation. X-ray crystallographic analysis revealed two types of complexes viz. sodium-containing cocrystals, [(An)4 -·m(Bn)+·qNa+], and sodium-free, [(An)4 -·4(Bn)+]. Both types accommodate (Bn+) guests in their cavities. The N-methylated heterocycle guests and host form capsule-like structures in which the two halves were joined by O-Na coordination bonds and self-assembly into two-dimensional polymeric sheets. From the crystal structures, different conformations of methylenesulfonate groups with respect to cavity arising due to tetrahedral geometry of methylene linker were observed. Density functional theory (DFT) computations were used to analyze the effects of endo-guests on host conformations and to estimate the relative strengths of host-guest interactions.

AB - The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using 1H NMR spectroscopy. Substitution of methylenesulfonate groups at 2-positions of resorcinol units resulted in an increase of cavity depth by ∼2.80 Å and a narrow cavity portal compared to Calkyl-2-H-resorcinarenes. The effect of alkyl chain lengths on the endo-complexation, that is the ability to incorporate other than N-methyl chains inside the cavities, was investigated using ammonium cations of the type +NH2(R1)(R2), (R1 = Me, Et, Bu, R2 = Bu, Ph, Bz). The C-H···πinteractions between guests and hosts are the key driving forces for 14 out of 16 observed endo-complexes. In the case of the N-butyl-N-benzylammonium cation, the hydrogen bonding between -NH2 and sulfonate oxygens and the larger size hamper the N-butyl and N-benzyl groups from entering the host cavity. Association constants derived from isothermal calorimetry titrations confirm 1:1 host-guest complexes highlighting guest affinity, based on size and orientation. X-ray crystallographic analysis revealed two types of complexes viz. sodium-containing cocrystals, [(An)4 -·m(Bn)+·qNa+], and sodium-free, [(An)4 -·4(Bn)+]. Both types accommodate (Bn+) guests in their cavities. The N-methylated heterocycle guests and host form capsule-like structures in which the two halves were joined by O-Na coordination bonds and self-assembly into two-dimensional polymeric sheets. From the crystal structures, different conformations of methylenesulfonate groups with respect to cavity arising due to tetrahedral geometry of methylene linker were observed. Density functional theory (DFT) computations were used to analyze the effects of endo-guests on host conformations and to estimate the relative strengths of host-guest interactions.

U2 - 10.1021/acs.cgd.9b01540

DO - 10.1021/acs.cgd.9b01540

M3 - Article

VL - 20

SP - 2367

EP - 2376

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 4

ER -