Fluorinated carboxylic acids as powerful building blocks for the formation of bimolecular monolayers

Pinfold, Harry; Greenland, Christopher; Pattison, Graham; Costantini, Giovanni

doi:10.1039/c9cc08361h

Cited by 12 publications

(6 citation statements)

References 40 publications

(46 reference statements)

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“…These two planar molecules are structural isomers differing in the positions of their pyridyl nitrogen atoms. The nitrogen atoms within such pyridyl groups have previously been shown to be effective halogen bond acceptor sites in networks formed under similar conditions to those used in this study. − Furthermore, we have previously demonstrated that 3TPTZ and 4TPTZ interact very favorably with fluorinated carboxylic acids, like 4BTFBA, via strong O–H···N(pyridyl) interactions . It should also be noted that despite their different structures, from an electrostatic perspective, the ability of the N(pyridyl) sites of 3TPTZ and 4TPTZ to act as halogen/hydrogen bond acceptors is essentially the same (see the Supporting Information, section 3).…”

Section: Resultssupporting

confidence: 59%

Determining the Relative Structural Relevance of Halogen and Hydrogen Bonds in Self-Assembled Monolayers

et al. 2021

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Although hydrogen bonds have long been established as a highly effective intermolecular interaction for controlling the formation of self-assembled monolayers, the potential utility of the closely related halogen bonds has only recently emerged. The synergistic use of both halogen and hydrogen bonds provides a unique, multitiered strategy toward controlling the morphology of self-assembled structures. However, the interplay between these two interactions within monolayer systems has been little studied. Here, we have systematically investigated this interplay in self-assembled monolayers formed at the solid–liquid interface, with a specific attention on determining the structural relevance of the two interactions in the formation of 2D supramolecular structures. A single molecule that can simultaneously act as both a halogen and a hydrogen bond donor was paired with molecules that are effective acceptors for both of these interactions. The bimolecular networks that result from these pairings were studied by using scanning tunneling microscopy coupled with density functional theory calculations. Additional measurements on similar networks formed by using structural analogues in which halogen-bonding interactions are no longer possible give significant insight into the structure-determining role of these interactions. We find that in some monolayer systems the halogen bonds serve no significant structure-determining role, and the assembly is dominated by hydrogen bonding; however, in other systems, effective cooperation between the two interactions is observed. This study gives clear insight into the synergistic and competitive balance between halogen and hydrogen bonds in self-assembled monolayers. This information is expected to be of considerable value for the future design of monolayer systems using both halogen and hydrogen bonds.

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Section: Resultssupporting

confidence: 59%

Determining the Relative Structural Relevance of Halogen and Hydrogen Bonds in Self-Assembled Monolayers

et al. 2021

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“…Fluorinated carboxylic acids are an important structural component widely found in pharmaceuticals and bioactive compounds, 51 but the defluorinative electrocarboxylation of fluoroalkenes has rarely been reported due to the thermodynamic and kinetic stability of C–F bonds. In 2020, Zhou and colleagues disclosed a facile and economical direct defluorinative carboxylation of gem -difluoroalkenes with CO 2 , in an undivided cell equipped with a Pt plate as a cathode and nickel as an anode at room temperature at a constant current of 8.0 mA cm −2 with 6.7 F mol −1 (Scheme 25).…”

Section: Direct Electroreductionmentioning

confidence: 99%

Recent advances in the electrochemically mediated chemical transformation of carbon dioxide

Shi

2022

Chem. Commun.

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“…Medicinal chemists who are making oxygen to fluorine bioisosteric replacements need to understand the effects this replacement will have on the physicochemical properties of a molecule, particularly lipophilicity because of the key role it plays in biodistribution, metabolism, and binding. As part of our interest in the chemistry of fluorinated aromatic compounds, − in this paper, we will describe how structural features in a drug-like molecule may affect the change in lipophilicity on transformation of an aromatic hydroxy or methoxy group to a fluorine atom.…”

Section: Introductionmentioning

confidence: 99%

Effects of Replacing Oxygenated Functionality with Fluorine on Lipophilicity

Glyn

Pattison

2021

J. Med. Chem.

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The replacement of oxygenated functionality (hydroxy and alkoxy) with a fluorine atom is a commonly used bioisosteric replacement in medicinal chemistry. In this paper, we use molecular matched-pair analysis to better understand the effects of this replacement on lipophilicity. It seems that the reduced log P of the oxygenated compound is normally dominant in determining the size of this difference. We observe that the presence of additional electron-donating groups on an aromatic ring generally increases the difference in lipophilicity between an oxygenated compound and its fluorinated analogue, while electron-withdrawing groups lead to smaller differences. Ortho-substituted compounds generally display a reduced difference in log P compared to para- and meta-substituted compounds, particularly if an ortho-substituent can form an intramolecular hydrogen bond. Hydrogen-bond acceptors remote to an aromatic ring containing fluorine/oxygen can also reduce the difference in log P between oxygen- and fluorine-substituted compounds.

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Fluorinated carboxylic acids as powerful building blocks for the formation of bimolecular monolayers

Abstract: Fluorination transforms a simple carboxylic acid into a highly effective building block for the formation of bimolecular monolayers.

Cited by 12 publications

References 40 publications

Determining the Relative Structural Relevance of Halogen and Hydrogen Bonds in Self-Assembled Monolayers

Determining the Relative Structural Relevance of Halogen and Hydrogen Bonds in Self-Assembled Monolayers

Recent advances in the electrochemically mediated chemical transformation of carbon dioxide

Effects of Replacing Oxygenated Functionality with Fluorine on Lipophilicity

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