AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds

David A. Leigh; Craig C. Robertson; Alexandra M. Z. Slawin; Patrick I. T. Thomson

doi:10.1021/ja404504m

AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds

David A. Leigh^*, Craig C. Robertson, Alexandra M. Z. Slawin, Patrick I. T. Thomson

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The X-ray crystal structure of a previously reported extremely strong quadruple NH center dot center dot center dot N AAAA-DDDD hydrogen-bond array [5.4] (K-a 1.5 x 10(6) M-1 in CH3CN; K-a > 3 x 10(12) M-1 in CH2Cl2) features four short linear hydrogen bonds. Changing the two benzimidazole groups of the DDDD unit to triazole groups replaces two of the NH center dot center dot center dot N hydrogen bonds with CH center dot center dot center dot N interactions (complex [5.6]), but only reduces the association constant in CH3CN by 2 orders of magnitude (K-a = 2.6 x 10(4) M-1 in CH3CN; K-a > 1 x 10(7) M-1 in CH2Cl2). Related complexes without the triazole groups range in K-a from 18 to 270 M-1 in CH3CN, suggesting that the CH center dot center dot center dot N interactions can be considered part of a strong AAAA-DDDD quadruple hydrogen-bonding array. The NH center dot center dot center dot N/CH center dot center dot center dot N AAAA-DDDD motif can be repeatedly switched "on" and "off" in CDCl3 through successive additions of acid and base.

Original language	English
Pages (from-to)	9939-9943
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	135
Issue number	26
DOIs	https://doi.org/10.1021/ja404504m
Publication status	Published - 3 Jul 2013

Keywords

Supramolecular polymers
Terminal alkynes
Association
Complexes
Chemistry
Cytosine
Modules
Azides

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10.1021/ja404504m

leigh2013jacs9939
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@article{90ab0f8f2a1b49459ae17ef101e4e4bf,

title = "AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds",

abstract = "The X-ray crystal structure of a previously reported extremely strong quadruple NH center dot center dot center dot N AAAA-DDDD hydrogen-bond array [5.4] (K-a 1.5 x 10(6) M-1 in CH3CN; K-a > 3 x 10(12) M-1 in CH2Cl2) features four short linear hydrogen bonds. Changing the two benzimidazole groups of the DDDD unit to triazole groups replaces two of the NH center dot center dot center dot N hydrogen bonds with CH center dot center dot center dot N interactions (complex [5.6]), but only reduces the association constant in CH3CN by 2 orders of magnitude (K-a = 2.6 x 10(4) M-1 in CH3CN; K-a > 1 x 10(7) M-1 in CH2Cl2). Related complexes without the triazole groups range in K-a from 18 to 270 M-1 in CH3CN, suggesting that the CH center dot center dot center dot N interactions can be considered part of a strong AAAA-DDDD quadruple hydrogen-bonding array. The NH center dot center dot center dot N/CH center dot center dot center dot N AAAA-DDDD motif can be repeatedly switched {"}on{"} and {"}off{"} in CDCl3 through successive additions of acid and base.",

keywords = "Supramolecular polymers, Terminal alkynes, Association, Complexes, Chemistry, Cytosine, Modules, Azides",

author = "Leigh, {David A.} and Robertson, {Craig C.} and Slawin, {Alexandra M. Z.} and Thomson, {Patrick I. T.}",

note = "This work is supported by funding from the EPSRC UK.",

year = "2013",

month = jul,

day = "3",

doi = "10.1021/ja404504m",

language = "English",

volume = "135",

pages = "9939--9943",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "26",

}

AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds. / Leigh, David A.; Robertson, Craig C.; Slawin, Alexandra M. Z. et al.
In: Journal of the American Chemical Society, Vol. 135, No. 26, 03.07.2013, p. 9939-9943.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds

AU - Leigh, David A.

AU - Robertson, Craig C.

AU - Slawin, Alexandra M. Z.

AU - Thomson, Patrick I. T.

N1 - This work is supported by funding from the EPSRC UK.

PY - 2013/7/3

Y1 - 2013/7/3

N2 - The X-ray crystal structure of a previously reported extremely strong quadruple NH center dot center dot center dot N AAAA-DDDD hydrogen-bond array [5.4] (K-a 1.5 x 10(6) M-1 in CH3CN; K-a > 3 x 10(12) M-1 in CH2Cl2) features four short linear hydrogen bonds. Changing the two benzimidazole groups of the DDDD unit to triazole groups replaces two of the NH center dot center dot center dot N hydrogen bonds with CH center dot center dot center dot N interactions (complex [5.6]), but only reduces the association constant in CH3CN by 2 orders of magnitude (K-a = 2.6 x 10(4) M-1 in CH3CN; K-a > 1 x 10(7) M-1 in CH2Cl2). Related complexes without the triazole groups range in K-a from 18 to 270 M-1 in CH3CN, suggesting that the CH center dot center dot center dot N interactions can be considered part of a strong AAAA-DDDD quadruple hydrogen-bonding array. The NH center dot center dot center dot N/CH center dot center dot center dot N AAAA-DDDD motif can be repeatedly switched "on" and "off" in CDCl3 through successive additions of acid and base.

AB - The X-ray crystal structure of a previously reported extremely strong quadruple NH center dot center dot center dot N AAAA-DDDD hydrogen-bond array [5.4] (K-a 1.5 x 10(6) M-1 in CH3CN; K-a > 3 x 10(12) M-1 in CH2Cl2) features four short linear hydrogen bonds. Changing the two benzimidazole groups of the DDDD unit to triazole groups replaces two of the NH center dot center dot center dot N hydrogen bonds with CH center dot center dot center dot N interactions (complex [5.6]), but only reduces the association constant in CH3CN by 2 orders of magnitude (K-a = 2.6 x 10(4) M-1 in CH3CN; K-a > 1 x 10(7) M-1 in CH2Cl2). Related complexes without the triazole groups range in K-a from 18 to 270 M-1 in CH3CN, suggesting that the CH center dot center dot center dot N interactions can be considered part of a strong AAAA-DDDD quadruple hydrogen-bonding array. The NH center dot center dot center dot N/CH center dot center dot center dot N AAAA-DDDD motif can be repeatedly switched "on" and "off" in CDCl3 through successive additions of acid and base.

KW - Supramolecular polymers

KW - Terminal alkynes

KW - Association

KW - Complexes

KW - Chemistry

KW - Cytosine

KW - Modules

KW - Azides

U2 - 10.1021/ja404504m

DO - 10.1021/ja404504m

M3 - Article

SN - 0002-7863

VL - 135

SP - 9939

EP - 9943

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 26

ER -

AAAA-DDDD Quadruple Hydrogen-Bond Arrays Featuring NH center dot center dot center dot N and CH center dot center dot center dot N Hydrogen Bonds

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Keywords

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