We report on molecular and local orientational order of a series of imidazolium-based ionic liquid crystals exhibiting layered smectic A mesophase. Materials constituting of 1-dodecyl-3-methylimidazolium cation, and different counter-ions, were investigated. We apply two-dimensional 13C-1H dipolar NMR spectroscopy to quantify orientational order of C-H bonds of the organic cation. The experimental data supported the structural model of the interdigitated chains aligned with the smectic layer normal. Molecular order parameter S was found to increase in the anion sequence BF4− < I− < Br− < Cl−. This trend correlates well with ionic radius, negative charge delocalization, and hydrogen-bonding properties of the anions.

Aggregation behavior of a series of neat 1-ethyl 3-methylimidazolium alkyl sulfate (alkyl = ethyl, butyl, hexyl, and octyl) ionic liquids has been investigated through combined time-resolved fluorescence spectroscopy, 1-D and 2-D NMR spectroscopy, and fluorescence correlation spectroscopy (FCS). Interestingly, experimentally measured rotational relaxation times (τr) for ethyl, butyl, hexyl and octyl systems are measured to be 2.25, 1.64, 1.36, and 1.32 times higher than the estimated (from Stokes-Einstein-Debye theory) values for the same respective systems. This indicates that the emitting species is not the monomeric imidazolium moiety rather an associated species, and volume of the rotating fluorescing species decreases even though the length of the alkyl moiety on the anions is increased. The shift in the (1)H proton signal as well as a change in the width of the same signal upon dilution of the neat ionic liquids indicates that ionic liquids exist in the aggregated form. Further investigation through the 2D-ROESY experiment shows that interaction between imidazolium and sulfate is relatively stronger in the ethyl system than that of the longer octyl system. FCS measurements independently show that the hydrodynamic volume decreases with an increase in the anion chain length. The NMR and FCS results are consistent with the findings of the fluorescence anisotropy study.

Water-enhanced hydrogen-bonding network in ionic sublayer supports the formation of a thermodynamically stable smectic phase of less-ordered molecules.

Analysis of time-resolved fluorescence anisotropy data in light of the Stokes-Einstein-Debye hydrodynamic description reveals significant decoupling of rotational motion of the solute and the viscosity of the medium for a hydroxyl-functionalized ionic liquid (IL). This behavior and NMR experiments indicate that the hydroxyl-functionalized IL is more heterogeneous than other structurally similar ILs. Considering that recent theoretical investigations have demonstrated that the jump dynamics and hydrogen-bond fluctuations are closely related in viscous media, in such a case the hydrodynamic description can provide inconsistent results, and the present inapplicability of the hydrodynamics description in explaining solute rotation in a viscous hydroxyl-functionalized IL perhaps provides experimental support to the role of orientational jumps and hydrogen bond formation in that event.

The rotational diffusion of two organic solutes, 4-(azitidine-1-yl)-7-nitrobenzo[1,2,5]oxadi-azole (ANBD) and 7-nitrobenzo[1,2,5]oxadiazole-4-amine (HNBD), has been examined in 1-ethyl-3-methylimidazolium alkyl sulfate (alkyl = ethyl, hexyl and octyl) ionic liquids with the aim of understanding intermolecular interactions among solute and solvent molecules. Solute-solvent interaction has also been investigated by employing fluorescence, NMR and fluorescence correlation spectroscopy (FCS). The ionic liquids (ILs) having a fixed cationic moiety are chosen to monitor the roles of the alkyl chain length as well as the solute-anion (sulfate) interactions in the rotational diffusion of the solutes in the given ILs. In the present study, two chemically distinguishable solutes with structural similarity in their fluorophore unit are employed so that the difference in the rotational behavior of the solutes, if any, can be correlated with the solute-solvent interactions, and not with other factors like the size of the solutes etc. The steady state absorption and emission data indicate that HNBD and ANBD exist in different microenvironments in both ILs. The rotational diffusion data for both the solutes have been analyzed in light of hydrodynamic and quasi hydrodynamic theories. Interestingly, the rotational dynamics of ANBD is observed to be relatively fast and shows slip hydrodynamics, whereas HNBD exhibits hindered rotation with superstick behavior. The hindered rotation of HNBD as compared to that of ANBD in both ILs has been explained by considering the strong hydrogen bonding interactions between the two N-H groups of HNBD and sulfate anions of ILs. The faster rotation of ANBD with the increasing anion chain length has been explained by invoking quasi hydrodynamic theory. The presence of a specific hydrogen bonding interaction between solute (HNBD) and solvent (ILs) molecules has been confirmed by (1)H-NMR experiments. FCS measurements have independently demonstrated the relatively strong association of HNBD with the present ILs as compared to that of ANBD.

Ionic liquid crystals (ILCs) present a new class of non-molecular soft materials with a unique combination of high ionic conductivity and anisotropy of physicochemical properties. Symmetrically-substituted long-chain imidazolium-based mesogenic ionic liquids exhibiting a smectic liquid crystalline phase were investigated by solid state NMR spectroscopy and computational methods. The aim of the study was to reveal the correlation between cation size and structure, local dynamics, and orientational order in the layered mesophase. The obtained experimental data are consistent with the model of a rod-shaped cation with the two chains aligned in opposite directions outward from the imidazolium core. The alignment of the core plane to the phase director and the restricted conformations of the chain segments were determined and compared to those in single-chain counterparts. The orientational order parameter S~0.5–0.6 of double-chain ionic liquid crystals is higher than that of corresponding single-chain analogues. This is compatible with the enhanced contribution of van der Waals forces to the stabilization of smectic layers. Increased orientational order for the material with Br− counterions, which exhibit a smaller ionic radius and higher ability to form hydrogen bonds as compared to that of BF4−, also indicated a non-negligible influence of electrostatic and hydrogen bonding interactions. The enhanced rod-shape character and higher orientational order of symmetrically-substituted ILCs can offer additional opportunities in the design of self-assembling non-molecular materials.

With an aim to understand the intermolecular/particle interaction and the optical properties of the inorganic-organic hybrid nanostructured materials, Förster resonance energy transfer (FRET) between negatively charged CdS quantum dots (donor) and positively charged Oxazine 170 perchlorate (acceptor) has been investigated by employing steady-state and time-resolved fluorescence spectroscopy. Investigations revealed that size-dependent changes in the FRET efficiency of different QD-dye FRET pairs occurred mainly due to the electrostatic effects. Interestingly, the present study also reveals that at a higher concentration of dye molecules, aggregation occurs on the QD surface and the quenching of dye fluorescence occurs due to homo-FRET process. The homo-FRET process in this case has been established by exploiting steady-state fluorescence anisotropy measurements. The feasibility of aggregate formation and the homo-FRET interaction between the dye molecules has also been demonstrated through quantum mechanical calculations.

With an aim to understand the behavior in terms of the intermolecular interactions, structure and dynamics of dicationic and monocationic ionic liquids (ILs), two imidazolium-based dicationic ionic liquids (DILs), 1,8-bis-(3-methylimidazolium-1-yl)octane bis-(trifluoromethylsulfonyl)amide ([C(mim)][NTf]), 1,9-bis-(3-methylimidazolium-1-yl)nonane bis-(trifluoromethylsulfonyl)amide ([C(mim)][NTf]), and one monocationic ionic liquid (MIL), 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide ([C(mim)][NTf]), have been investigated through combined fluorescence, electron paramagnetic resonance (EPR), NMR and fluorescence correlation spectroscopy (FCS). The DILs were synthesized by following a standard synthetic protocol and subsequently characterized by different analytical techniques. Steady state absorption, emission and EPR spectroscopic data reveal that DILs are less polar compared to MIL. The polarities of the DILs and MIL were found to be close to those of acetonitrile and short chain alcohols, respectively. The excitation wavelength dependent emission data reveals that DILs are more micro-heterogeneous in nature than MIL. The rotational diffusion of two organic solutes, perylene and 8-methoxypyrene-1,3,6-sulfonate (MPTS), were examined in the DILs and MIL. The rotational diffusion data for perylene and MPTS were analyzed in light of the Stokes-Einstein-Debye (SED) hydrodynamic theory. The rotation of perylene in the DILs was observed to be relatively faster to that in the MIL, and it goes beyond the limit predicted by the SED theory. In order to explain the rotational motion of perylene in DILs, the data was analyzed further by invoking quasi-hydrodynamic theory. The observed rotational behavior of perylene has been explained by considering the fact that perylene is located in the nonpolar region of ILs, and larger solvent molecules (DILs) induce a lower friction to the rotating solute. Interestingly, unlike perylene, rotations of MPTS in both of the ILs were observed to be much hindered indicating a relatively stronger MPTS-IL interaction than perylene-IL interaction. More interestingly, rotation of MPTS was observed to be faster in the DILs than that in the MIL despite the fact that DILs are more viscous than MILs. Relatively faster rotation of MPTS in DILs has been explained by resorting to NMR and FCS studies. The outcomes of the NMR and FCS studies revealed that DILs in the experimental condition exist in their folded form and because of this structural restriction of DILs it becomes difficult for the bulky MPTS to make stronger hydrogen bonding interactions with DILs, which eventually makes the rotation of MPTS in DILs faster. Essentially, the outcomes of all of these studies have demonstrated that the behavior of DILs is quite different to that of the usual MILs.