Controlling “like–likes–like” charge attraction in hydroxy-functionalized ionic liquids by polarizability of the cations, interaction strength of the anions and varying alkyl chain length

2020 ◽  
Vol 22 (5) ◽  
pp. 2763-2774 ◽  
Author(s):  
Thomas Niemann ◽  
Dzmitry H. Zaitsau ◽  
Anne Strate ◽  
Peter Stange ◽  
Ralf Ludwig
Keyword(s):  
Hydrogen Bonding ◽  
Ionic Liquids ◽  
Chain Length ◽  
Alkyl Chain ◽  
Cluster Formation ◽  
Interaction Strength ◽  
Alkyl Chain Length ◽  
Molecular Parameters

Like–likes–like charge attraction via hydrogen bonding: three molecular parameters control the cationic cluster formation in hydroxy-functionalized ionic liquids.

scholarly journals Clusters of Hydroxyl-Functionalized Cations Stabilized by Cooperative Hydrogen Bonds: The Role of Polarizability and Alkyl Chain Length

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 4972
Author(s):  
Jule Philipp ◽  
Ralf Ludwig
Keyword(s):  
Hydrogen Bonding ◽  
Ionic Liquids ◽  
Hydrogen Bonds ◽  
Functional Groups ◽  
Chain Length ◽  
Alkyl Chain ◽  
Kinetic Stability ◽  
Alkyl Chain Length ◽  
Coupling Constants ◽  
Imidazolium Cations

We explore quantum chemical calculations for studying clusters of hydroxyl-functionalized cations kinetically stabilized by hydrogen bonding despite strongly repulsive electrostatic forces. In a comprehensive study, we calculate clusters of ammonium, piperidinium, pyrrolidinium, imidazolium, pyridinium, and imidazolium cations, which are prominent constituents of ionic liquids. All cations are decorated with hydroxy-alkyl chains allowing H-bond formation between ions of like charge. The cluster topologies comprise linear and cyclic clusters up to the size of hexamers. The ring structures exhibit cooperative hydrogen bonds opposing the repulsive Coulomb forces and leading to kinetic stability of the clusters. We discuss the importance of hydrogen bonding and dispersion forces for the stability of the differently sized clusters. We find the largest clusters when hydrogen bonding is maximized in cyclic topologies and dispersion interaction is properly taken into account. The kinetic stability of the clusters with short-chained cations is studied for the different types of cations ranging from hard to polarizable or exhibiting additional functional groups such as the acidic C(2)-H position in the imidazolium-based cation. Increasing the alkyl chain length, the cation effect diminishes and the kinetic stability is exclusively governed by the alkyl chain tether increasing the distance between the positively charged rings of the cations. With adding the counterion tetrafluoroborate (BF4−) to the cationic clusters, the binding energies immediately switch from strongly positive to strongly negative. In the neutral clusters, the OH functional groups of the cations can interact either with other cations or with the anions. The hexamer cluster with the cyclic H-bond motive and “released” anions is almost as stable as the hexamer built by H-bonded ion pairs exclusively, which is in accord with recent IR spectra of similar ionic liquids detecting both types of hydrogen bonding. For the cationic and neutral clusters, we discuss geometric and spectroscopic properties as sensitive probes of opposite- and like-charge interaction. Finally, we show that NMR proton chemical shifts and deuteron quadrupole coupling constants can be related to each other, allowing to predict properties which are not easily accessible by experiment.

Spectroscopic Study on Imidazolium-Based Ionic Liquids: Effect of Alkyl Chain Length and Anion

2012 ◽  
Vol 116 (11) ◽  
pp. 3512-3518 ◽  
Author(s):  
Enrico Binetti ◽  
Annamaria Panniello ◽  
Leonardo Triggiani ◽  
Raffaele Tommasi ◽  
Angela Agostiano ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Spectroscopic Study ◽  
Chain Length ◽  
Alkyl Chain ◽  
Alkyl Chain Length

Densities and refractive indices of imidazolium- and phosphonium-based ionic liquids: Effect of temperature, alkyl chain length, and anion

2009 ◽  
Vol 41 (6) ◽  
pp. 790-798 ◽  
Author(s):  
M. Tariq ◽  
P.A.S. Forte ◽  
M.F. Costa Gomes ◽  
J.N. Canongia Lopes ◽  
L.P.N. Rebelo
Keyword(s):  
Ionic Liquids ◽  
Chain Length ◽  
Alkyl Chain ◽  
Alkyl Chain Length ◽  
Effect Of Temperature ◽  
Refractive Indices

Protic Ionic Liquids Based on the Alkyl-Imidazolium Cation: Effect of the Alkyl Chain Length on Structure and Dynamics

2019 ◽  
Vol 123 (18) ◽  
pp. 4044-4054 ◽  
Author(s):  
Iqbaal Abdurrokhman ◽  
Khalid Elamin ◽  
Olesia Danyliv ◽  
Mohammad Hasani ◽  
Jan Swenson ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Chain Length ◽  
Alkyl Chain ◽  
Alkyl Chain Length ◽  
Protic Ionic Liquids ◽  
Imidazolium Cation ◽  
Structure And Dynamics ◽  
Cation Effect
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