Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen‐bonded supramolecular anions [CnF2 n+1‐I⋅⋅⋅I⋅⋅⋅I‐CnF2 n+1]− are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen‐bonded liquid crystals, and 2) imidazolium‐based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.

thick fi lm to achieve signifi cant durability and, therefore, requires a relatively large amount of fl uoropolymer. Alternative approaches, such as chemical grafting of fl uoropolymers by radical methods through irradiation, [ 6−8 ] plasma, [ 9−12 ] or direct fl uorination with fl uorine gas, [ 1,2,13 ] require only moderate amounts of fl uorinated surface modifi ers but are much more aggressive and, in some cases, potentially hazardous.Other possibilities involve functionalization with fl uorinated molecules/ polymers consisting of specifi c chemical moieties that are able to bind either covalently or noncovalently to the polymer surface. [ 4,5,14,15 ] However, to achieve sufficiently stable bonding, this general strategy requires the presence of reactive hydrophilic sites, typically OH groups, which are not typically observed on the surfaces of apolar, hydrophobic polymers, such as polyolefi ns, and need to be introduced via oxidizing pretreatments that are usually either energy-intensive or not environmentally friendly. [ 16−19 ] Expanding on this strategy, we present an effi cient, rapid, and more environmentally friendly method to perform the fl uorocarbon coating of hydrophobic polymer surfaces. The method is based on the use of hydrophobins, i.e., amphiphilic surface-active proteins, as a nanosized primer layer that adheres to the hydrophobic polymer surface, making the surface hydrophilic and preparing it for the subsequent binding of a fl uoropolymer containing ionic moieties.Hydrophobins are a class of nontoxic, surface-active, and fi lm-forming proteins that are produced by fi lamentous A new and simple method is presented to fl uorinate the surfaces of poorly reactive hydrophobic polymers in a more environmentally friendly way using the protein hydrophobin (HFBII) as a nanosized primer layer. In particular, HFBII, via electrostatic interactions, enables the otherwise ineffi cient binding of a phosphate-terminated perfl uoropolyether onto polystyrene, polypropylene, and low-density polyethylene surfaces. The binding between HFBII and the perfl uoropolyether depends signifi cantly on the environmental pH, reaching the maximum stability at pH 4. Upon treatment, the polymeric surfaces mostly retain their hydrophobic character but also acquire remarkable oil repellency, which is not observed in the absence of the protein primer. The functionalization proceeds rapidly and spontaneously at room temperature in aqueous solutions without requiring energy-intensive procedures, such as plasma or irradiation treatments.

Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen-bonded supramolecular anions [C n F 2n+1 -I···I···I-C n F 2n+1 ]À are reported. The material system is unique in many ways,demonstrating for the first time 1) ionic, halogen-bonded liquid crystals,and 2) imidazolium-based ionic liquid crystals in whicht he occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.Ionic liquids are often defined as salts with melting points below 100 8 8C. Ionic liquids have several unique characteristics,such as high ionic conductivity,low volatility,and alack of flammability,o na ccount of which they are investigated extensively as new materials for electrochemical devices and as green solvents for materials synthesis and characterization. [1][2][3][4][5] Thep roperties of imidazolium-based ionic liquids are highly sensitive to the nature of the counteranion and can be tailored further through chemical modification of the organic cation. In particular, upon substituting the cation with long alkyl chain(s), some ionic liquids may exhibit liquid-crystalline properties,c ombining the attractive features of liquid crystals and ionic liquids. [6][7][8][9] Thea nisotropic conductivity of ionic liquid crystals,h ereinafter referred to as ILCs,i so f particular interest as it can find application in molecular electronics [10,11] or in dye-sensitized solar cells. [12][13][14] In order to realize the potential of ILCs,t here is high demand for novel types of ionic mesogens with tailored physical and/or chemical properties.H erein, we present as trategy for obtaining an ew type of ILCs,i nw hich the liquid crystallinity is enabled by the formation of supramolecular, halogen-bonded trimeric anions containing 1-iodoperfluoroalkane units,w hich encode calamitic mesomorphism. Thes upramolecular, halogen-bonded CÀI···I À ···IÀCs ynthon acts here as am esogenic core driving mesophase formation, which is,tosome extent, independent of the alkyl chain length of the imidazolium cation. Thes egregation of the perfluorocarbon chains (fluorophobic effect) [15][16][17] promotes the selforganization of the obtained ILCs.T hese unconventional superfluorinated ILCs (Scheme 1) exhibit liquid crystallinity even at room temperature. [18] In the conventional design, calamitic liquid crystals normally consist of af airly rigid core functionalized with one or more flexible alkyl or alkoxy chains. [19,20] An archetypical ILC comprises a1 -alkyl-3-methylimidazolium cation as amesogenic core [6] and for mesophase formation to occur, the length of the alkyl chain attached to the imidazolium core is of critical importance;i th as been claimed that at least ad odecyl chain is required for the system to exhibit liquid crystallinity. [21,22] Typically,l amellar mesophases are formed, driven largely by attractive,electrostatic interactions between charged species,which separate from the apolar alkyl tails. [23] However,although the imidazolium cation plays akey role in defining the mesomorphism...