Electronic Structure, NMR, SpinâSpin Coupling, and Noncovalent

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Electronic Structure, NMR, Spin-Spin Coupling and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids Soniya S Rao, and Shridhar P. Gejji J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.6b03985 • Publication Date (Web): 23 Jun 2016 Downloaded from http://pubs.acs.org on June 27, 2016

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The Journal of Physical Chemistry

Electronic Structure, NMR, Spin-spin Coupling and Noncovalent Interactions in Aromatic Amino Acid based Ionic Liquids. Soniya S. Rao and Shridhar P. Gejji* Department of Chemistry, Savitribai Phule Pune University, Pune 411 007, India.

Corresponding author: [email protected] Fax No.: +91-20-225691728 Telephone No.: +91 020 25601225

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Abstract Non-covalent interactions accompanying phenylalanine (Phe), tryptophan (Trp) and tyrosine (Tyr) amino acidsbased ionic liquids (AAILs) composed of 1-methyl-3-butyl-imidazole and its methyl substituted derivative as cations have been analyzed employing the dispersion corrected density functional theory. It has been shown that cation-anion binding in such bioionic ILs is primarily facilitated through hydrogen bonding in addition to lp---π and CH---π interactions those arise from aromatic moieties and can be probed through 1H and

13C

NMR spectra obtained from the gauge

independent atomic orbital method. Characteristic NMR spin-spin coupling constants across hydrogen bonds of the ion pair structures viz., Fermi contact, spin-orbit and spin-dipole terms, are strongly dependent on the mutual orientation of cation with the amino acid anion. The spin-spin coupling mechanism transmits spin polarization via electric field effect originating from lp---π interactions whereas the electron delocalization from the lone pair of the carbonyl oxygen to the antibonding C-H orbital is facilitated by hydrogen bonding. It has been demonstrated that indirect spin-spin coupling constants across the hydrogen bonds correlate linearly with hydrogen bond distances. The binding energies and dissected nucleus independent chemical shifts (NICS) document the mutual reduction of aromaticity of hydrogen bonded ion pairs consequent to localization of π-character. The nature and type of such noncovalent interactions governing the inplane and out-of-plane NICS components provide a measure of diatropic and paratropic currents for the aromatic rings of varying size in AAILs. Besides the direction of frequency shifts of characteristic C=O and NH stretching vibrations in the calculated vibrational spectra has been rationalized.

Key words:

Aromatic amino acid ionic liquids, NMR, NICS, Spin-spin coupling, Noncovalent

interactions.


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Graphical Abstract



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1. Introduction Room temperature ionic liquids (RTILs) exclusively composed of organic cations and organic/inorganic anions exhibit liquidus behavior with melting points well below 100oC and find ubiquitous applications owing to their characteristic properties such as nonvolatility, high viscosity, high ion conductivity, thermal and chemical stability.1,2 Naturally occurring carboxylate salts,3,4 amino acids,5-9 and sugar derivatives

10-12

have been explored as economical and clean precursors

for the synthesis of ILs. Early works of Fukumoto and Ohno13 on the 1-ethyl-3-methylimidazolium [Emim] and natural amino acids have led to a new class of amino acids ionic liquids (AAILs). Amino acids comprising of both amino- and carboxyl-groups with a chiral center and varying alkyl side chains have been harnessed for designing and synthesis of novel functional materials.14,15AAILs are liquids at ambient or far below ambient temperatures and serve as suitable media alternative to volatile organic solvents in a variety of chemical reactions. The zwitterionic amino acids allows their use as either cation or anion that facilitates multitudes of combinations for ILs.16-19 AAILs have been employed as chiral solvents or reactants for dissolution and stabilization of cellulose, nucleic acids, carbohydrates and other species of primary biological importance.20-25 On the theoretical front, molecular dynamics (MD) simulations on the ILs composed of deprotonated amino acid anions and choline cation revealed that their formation is facilitated through proton transfer involving the hydrogen bond effectively neutralizing cation and anion.26 Fileti and coworkers27 carried out atomistic force field simuations to determine shear viscosities and cluster compositions of imidazolium and amino acid salts containing alanine, methionine and tryptophan anions in aqueous solutions and further demonstrated how the structural change of amino acid modulates the dispersion of AAILs in water for varying concentrations. A molecular level understanding of noncovalent interactions encompassing hydrogen bonding, steric repulsion, aromatic ring stacking and electrostatic interactions should prove useful 4 ACS Paragon Plus Environment

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for designing of task specific ILs. To this direction interactions arising from aromatic rings or πstacking have received significant attention in the recent years.28-30 The origin of highly directional electrostatic attractions (with possible induction and dispersive contributions) between rings involving positive electrostatic potential region on the molecular surface of aromatic or nonaromatic moieties was discussed in terms of π-hole interactions by Politzer et al.31-33 Consequent anion/lone-pair-π or π-π interactions are usually referred as π-hole bonds. Further Hunt and coworkers described π-π interactions in imidazolium based ILs through energetic landscapes of π+-π+ stacked motifs, hydrogen bonding and anion-π+ interactions.29 Dias et al. examined solubilities of aromatic molecules, in particular those of benzene and its fluorinated derivatives in [Emim][NTf2] based ILs, using the NMR spectroscopy experiments combined with MD simulations.34 The solubilities of aromatic molecules in ILs further are shown to be dependent on diamagnetic characteristics of the aromatic ring. The aromatic amino acids phenylalanine ([Phe]), tryptophan ([Trp]) and tyrosine ([Try]) form primary constituents of biomolecules, are fluorescent aromatic chromophores which are used as probe to unravel protein structure environment from fluorescence and NMR experiments.34-38 It has also been shown that reaction between tryptophan and [Bmim][PF6] based ILs occurs via the proton transfer.39 Despite of afore mentioned works which concerns with the interaction of amino acids or aromatic moieties with ILs, attempts to exclusively explore aromatic AAILs as storage media for stabilizing bimolecules are rather scanty. With this perspective a more complete picture of noncovalent interactions involving Aromatic AAILs should prove pivotal for rational design of task specific ILs in a myriad of chemical applications. The present work precisely focuses on analyzing underlying noncovalent interactions accompanying aromatic AAILs composed of [Phe], [Trp] and [Tyr] anions with 1-methyl-3butylimidazolium cation [Bmim] and its substituted methyl derivative [MBmim] employing the dispersion corrected density functional theoretic calculations. It would be intriguing to understand how aromatic rings in the cation and anion render different noncovalent interactions in turn



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affecting structure and spectral characteristics of pure ILs. The following questions have been addressed. How methyl substitution on the imidazolium cation influences the ion-pair structures? How interactions arising from π-cloud of the aromatic rings and inter- as well as intramolecular hydrogen bonding govern the local aromaticities in these aromatic AAILs? How such interactions reflect in spin-spin coupling constants, NMR and vibrational spectra? The computational method is outlined below.

2. Methodology The atomic numbering scheme for [Bmim] cation and amino acid anions (AA) (AA= Phe, Trp and Tyr) is shown in Fig. 1. The initial structures of ion pairs were generated by carrying out appropriate transformations combining the rotation and translation of [Bmim+] and [AA−] around the minima and saddle points in the molecular electrostatic potential (ESP) topography40-42 followed by subsequent optimizations employing the GAUSSIAN-09 program.43 The structures thus derived were subjected to density functional calculations based on Becke’s three parameter exchange combined with the correlation functional due to Lee, Yang and Parr (B3LYP).44,45 The internally stored 6-311G++(d,p) basis with diffuse functions added to heavy atoms and hydrogens were used. Optimized ion pair conformers destabilized upto 5 kJ mol−1 higher relative to the lowest energy conformer, having qualitatively different binding patterns were subjected to optimizations employing the hybrid meta-GGA (generalized gradient approximation) exchange correlation M052X functional subsequently.46-51 Binding energies of [Bmim][AA] were obtained by subtracting the sum of energies of individual cations and anions making up the ion pairs in their free state (isolated) from those of the ion pair systems. Stationary point structures obtained were confirmed to be local minima on the multivariate potential energy surface since of all the normal vibration frequencies turned out to be real. The potential energy distribution (PED) was derived, and the normal modes were assigned through visualization of displacement of atoms around their 6 ACS Paragon Plus Environment

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equilibrium (mean) positions using the GAUSSVIEW-5 program.52 To delve into underlying molecular interactions and their manifestation in vibrational spectral characteristics we use the quantum theory of atoms in molecule (QTAIM)53,54 approach employing the AIMAll software.55 The underlying noncovalent interactions are further deciphered in terms of the bond critical points (bcp) in molecular electron density topography, its Laplacian ( ∇ 2 ρ ) and the corresponding reduced

density gradients (RDG) defined through

∇ρ(r)

1 2

2(3π )

1 3

4

ρ(r)

within QTAIM model.56 The NCI-RDG

3

isosurfaces were obtained employing a uniform spatial grid with a step size of 0.1 a.u. The δH parameters in 1H NMR spectra were calculated by subtracting the nuclear magnetic shielding tensors of protons in the cation, anion and ion pair complexes from those in tetramethylsilane (reference) using the gauge-independent atomic orbital (GIAO) method57,58within the framework of M05-2x based density functional theory. Further the nucleus independent chemical shifts (NICS) were derived using the GIAO method.59,60 For nonplanar systems studied in the present work the local aromaticities were gauged from the NICS profiles. The ring critical points (rcp) within the MED topography were located. This was followed by identifying the points upto 3 Å both above as well as below the aromatic ring with a step size of 0.5 Å along the unit normal vector perpendicular to the ring plane with rcp as origin. The magnetic shielding tensors were computed at these points. To explain the frequency shifts of characteristic vibrations in the calculated vibrational spectra natural bond orbital (NBO) analysis were carried out.61

3. Results and Discussion 3.1 Structure and Noncovalent Interactions It is known that the ion pair refers to the smallest representative unit of ILs that simulates the structural and binding features and widely have been employed to model their physicochemical



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properties and liquidus behavior.62,63 The isolated anions were used to generate initial ion pair structures employing the ESP topography of the anion. The optimized lowest energy structures of [Bmim][AA] and [MBmim][AA] using the M05-2x/6-311++G(d,p) level of theory are shown in Figs. 2 and 3. As shown in Fig. 2 the acidic H1 proton of the [Bmim] cation facilitates bi-furcated C=O---H hydrogen bonds with carboxylate oxygens O1 and O2 of the anion rendering T-shaped structure to the conformer. The [Bmim][Phe] conformer possesses C-H---O interactions (corresponding bond distances being 2.004 Å and 2.288 Å) from alkyl group of the [Bmim] cation in addition to bifurcated hydrogen bonds from the H1 proton of imidazole ring as shown in Fig 2(a). These inferences can be extended to explain the stabilities of [Bmim][Trp] and [Bmim][Tyr] ion-pairs. Selected geometrical parameters including the hydrogen bond distances in [Bmim][AA] ion-pairs are compared with the free ions in Table 1. The C1-H1---O interactions engender an elongation up to 0.06 Å for C1H1 bond in the [Bmim][Tyr] ion-pair. The C=N bonds from the imidazole ring are contracted by ~0.1 Å compared to the free cation. A shortening of ~0.06 Å for the N3-H12 bond was further predicted for [Bmim][Phe] and [Bmim][Trp] ion-pairs. The carbonyl bond distances are elongated up to 0.009 Å in these ion-pairs. The bi-furcated hydrogen bond distances range from 1.990 Å to 2.497 Å in [Bmim][Trp] and [Bmim][Tyr] ion pairs. Generally bond angle parameters of the anion do not vary significantly on interaction with the [Bmim] cation, the only exception being the 0) ones. These interactions are described in terms of attractive, repulsive steric and weak dispersive components. The elegance of NCI method lies in elucidating such interactions in real-space and as graphical representations. The position, strength and type of an interactions shown as RDG isosurface are represented on a blue–green–red (BGR) scale according to the values and sign of (λ2)ρ located in between −0.05 a.u to +0.05 a.u. Regions with positive (λ2)ρ, the area are portrayed as red indicate strong repulsive non-bonded overlap, the attractive interactions displayed in blue and the green regions refer to electrostatic interactions. NCI surfaces in [Bmim][Phe] and [MBmim][Phe] ion pairs are shown in Fig. 6. As shown in Fig. 6(a) the green regions between the [Bmim][Phe] ion pair stem from hydrogen bonding interactions. The green isosurface indicate weak attractive interactions between H7, H9, and H11 protons of the alkyl chain with the anion. As suggested earlier66,68 the hydrogen bond is considered to be composed of components representing covalent as well as electrostatic and van der Waals interactions to a varying degree. The presence of donor/acceptor groups or alternatively substitution of the electron donating or withdrawing groups engenders mutual existence of hydrogen bond along with other noncovalent interactions possibly encompassing the van der Waals interactions as well.69 Consequently the [MBmim][Phe] ion pair that facilitates additional lp--π and hydrogen bonding interactions those emerge with isosurfaces between imidazole ring and 12 ACS Paragon Plus Environment

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the carboxylate group shown as green implying weaker hydrogen bonding interactions in conjuction with the lp---π interactions; the latter being dominant. Thus the underlying cation anion binding stem from the electrostatic and van der Waal type of interactions (cf. Fig. 6 (c). Furthermore distinct NCI surface between the phenyl ring and terminal methyl group of the cation further suggests the presence of CH---π interactions. The red regions as shown in figure arise as a result of depletion of electron density which is counterbalanced by steric contributions. As an alternate perspective to real-space NCI isosurface for cation-anion binding the reduced gradient of density is plotted as a function of electron density multiplied by the sign of λ2. The NCI plot of [Bmim][Phe] ion-pair shown in Fig. 6(b) reveals spikes around±0.010 a.u consequent to strong bifurcated hydrogen bonding. The reduced gradient at low electron density values show deep spikes around ±0.020 a.u on the abscissa implying the presence of attractive interactions with the alkyl protons. NCI plot of [MBmim][Phe] has been portrayed in Fig. 6 (d). The region between ±0.005 a.u shows the appearance of new spikes which refers to lp---π interactions. As a result narrowing of the region separating low and high electron densities in vicinity of 0.00 a.u can be observed. The NCI plots of [Bmim] and [MBmim] AAILs portrayed in Fig. S2 of the supporting information corroborate these conclusions. To delve further into the sensitive dependence of many body effects on cation-anion binding and accompanying molecular interactions we carried out the energy decomposition analyses (EDA). EDA gives contributions from steric (electrostatic + exchange terms, ΔEsteric), orbital (ΔEorb) and dispersion (ΔEdisp) energy to overall binding energy (ΔEtotal) etc and provide insights for charge distributions in these noncovalent bonded systems. Fig. 7 illustrates the contributions toward the cation anion binding constituting the ion pair in the form of a histogram. The methyl substitution strongly influences the molecular interactions as a result of contributions from noncovalent components to the ion pair. The underlying interactions in [MBmim] ion pairs are dominated by dispersion effects and are simulated well via the inclusion of the M0x exchange 13 ACS Paragon Plus Environment


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correlation functionals those incorporate a large set of parameters.46 The parallel displaced stacked [MBmim][AA] structures can be distinguished those for [Bmim][AA] ion pairs. In other words, the interplay of electrostatic/dispersive effects from the π-cloud and hydrogen bonding interactions dictate structural characteristics of aromatic AAILs. The hydrogen bonding and lp--π interactions with large electrostatic and polarization components, are further rationalized in terms of dispersive contributions. The electron donating methyl substituent in the [MBmim] ion pair enhances the donor-acceptor ability and exhibits comparable binding strengths to its unsubstituted analogs. It should be discernible that [MBmim][Trp] ion pair void of CH---π interactions emerge with relatively less dispersion contributions as evidenced from the histogram.

3.2 1H and 13C NMR The cation-anion binding can be monitored through 1H NMR experiments. GIAO computed δH and δC values of the individual cation or anion and those in the ion pair from the M05-2x/ 631++G(d,p) theory are summarized in Table 3. The accurate determination of NMR parameters is a challenging task and requires simulation of electron correlation and extended basis set.71,72 The NMR shielding constants, interaction energies and spin-spin coupling constants (SSCCs) are sensitive to choice of the basis set. It has further been known that for noncovalently bonded systems the shielding constants and NMR parameters for example, indirect or direct nuclear SSCCs are critically dependent on the electronic structure and their computations requires

good

description of core as well as diffuse orbitals.73-75 It should be remarked here that the density functional theoretic calculations incorporating the dispersion corrected M05-2x or related functionals combined with the Huzinaga and further extended correlated basis set have been carried out for water clusters and clatherates.76,77 Deriving the electronic structure and NMR spectral characteristics with such level of theory become computationally demanding for large molecular systems. As an alternative M05-2x/6-311++G(d,p) level of theory have widely been


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employed to derive the NMR parameters in the recent literature

78-85

and accordingly the M05-

2x/6-311++G(d,p) approach has been identified to be economical and convenient in terms of quality to cost ratio for obtaining the NMR chemical shifts. We therefore employ this level of theory for deriving NMR characteristics of aromatic AAILs studied in this work. The protons in the [Bmim] cation can be classified as: the methine proton H1; aromatic H2 and H3 protons on imidazole ring and those of methyl or butyl group. The H1 proton from the bifurcated hydrogen bonds reveals a large deshielding (~4.9 ppm) compared to cation in the [Bmim][Phe] ion pair. The alkyl protons participating in C-H---O interaction fall in the range of 2.6 ppm to 4.9 ppm and can be distinguished from the non-interacting protons. These inferences are borne out for the [Bmim][Trp] as well as [Bmim][Tyr] ion pairs. The amide Hb protons on the anion emerge with downfield NMR signals owing to intramolecular hydrogen bonding and follows the order: [Bmim][Trp] (2.6 ppm) > [Bmim][Tyr] (2.4 ppm) > [Bmim][Phe] (1.5 ppm). A large deshielding for [Bmim][Phe] points to stronger intramolecular hydrogen bonding. The signals near 7.2 to 8.4 ppm arise from protons occupying diamagnetic positions in close vicinity of the aromatic ring of the anion(s) are attributed to ring current effects. The shielding/deshielding effects within the ion pair can be probed using the 13C NMR data reported in Table 4. The C1, C2 and C3 carbon atoms of imidazole ring penetrate deep inside diamagnetic zone of the [Bmim] cation, while aliphatic carbons place farther from the ring experience a large paramagnetic influence. The C1 carbon shows signal at 152 ppm in the isolated [Bmim] cation that corresponds to the ~169 ppm signal for the [Phe] ion pair. Similar conclusions are drawn for [Bmim][Trp] and [Bmim][Tyr] ion pairs. The polar network accompanying the ILs is influenced strongly by substitution at the (most reactive) H1 proton and has profound influence on the structure and NMR spectra of ion pairs. The substituent (the functional group) at this site introduces lp---π or CH---π interactions in addition to 15 ACS Paragon Plus Environment


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hydrogen bonding. The downfield signals at 9.7 ppm and 8.4 ppm assigned to H2 and H3 protons on imidazole ring in the [MBmim][Phe] ion pair. Further protons participating in inter as well as intramolecular hydrogen bonding interactions emerge with downfield signals. Subsequently orientations of phenyl ring and carboxylate group of the anion relative to the imidazole ring influence magnetic shielding largely and appear as distinct paramagnetic zones for imidazole and phenyl rings. This is accompanied by deshielded signals for C1 in the [MBmim] ion pairs. Moreover, deshielding of

13C

signals in the anion was attributed to lp---π interactions and follows the order:

[MBmim][Phe] (206 ppm) > [MBmim][Trp] (205 ppm) > [MBmim][Tyr] (200 ppm). The CH---π interactions in the [MBmim][Phe] and [MBmim][Tyr] engender downfield signals for aromatic carbons of the anion as opposed to those in the [MBmim][Trp] ion pair. Thus, the methyl substitution gives rise to paratropic ring currents to the aromatic ring facilitating different noncovalent interactions with their direction being strongly dependent on the π-conjugation. Lastly 15N

chemical shifts reported in Table S2 of the supporting information turned out to be nearly the

same for [Bmim] and [MBmim] substituted ion pairs.

3.3 Spin-spin Coupling Constants The direct and indirect spin-spin coupling constants in NMR spectra provide better understanding of the electronic structure and in turn, the molecular interactions.86,87 Calculated spin-spin coupling constants (SSCCs) are formulated using the Ramsey nonrelativistic theory having contributions from the Fermi contact (FC), spin-dipole (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO) components reported in Table 5. For the purpose of decoding the spin–spin coupling mechanism FC, SD, DSO, and PSO coupling is discussed in details. NMR chemical shifts or SSCCs sensitively depend on the structure of a molecule.88 A knowledge of SSCCs across hydrogen bonds and their characteristics enable one to unravel the noncovalent interactions accompanying


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the ILs which subsequently can be explored for modeling of physicochemical properties in task specific ILs. The inferences drawn from indirect coupling constants across C1’=O---H1-C1 hydrogen bond in [Bmim] and [MBmim] ion pairs are outlined below. Intermolecular equilibrium C1’-C1 distances, total coupling constant (J(C1’,C1)) and contributions from other components to J(C1’,C1) are reported in Table 5. The total SSCC in the [Bmim][Phe] ion pair turned out to be -0.7 Hz. Likewise [Bmim][Trp], [Bmim][Tyr] and [MBmim][Trp] ion pairs exhibit qualitatively similar J(C1’,C1) values in terms of sign and their magnitudes with values -0.05 to -0.7 Hz range. On the other hand, the parallel displaced stacked [MBmim][Phe] and [MBmim][Tyr] ion pairs reveal the total SSCCs values which are> 0. Change in sign of J from nehative to positive and can be attributed to the induced spin polarization. The J(C1’,C1) in the [MBmim][Phe] turns out to be 0.01 Hz. which is nearly ten times smaller compared to 0.1 Hz for [MBmim][Tyr] ion pair. It may therefore, be conjectured that CH---π interactions from rear end of the anion engender large C1’-C1 separations subsequent to mutual orientation of imidazole and carboxylate groups. The histogram displayed in Fig. 8, shows the FC term contributes largely to total SSCC parameters. To elucidate further the nature of hydrogen bond the indirect SSCCS for the across both intermolecular C=O---H-C as well as intramolecular N-H---O=C hydrogen bonds were obtained (cf. Table 6). The relative contributions of various components to J(O,H) for the [Bmim][Phe] ion pair are also reported. As pointed out earlier the total SSCCs shows sensitive dependence on the cation anion intermolecular separation and their mutual orientation. Accordingly the relatively shorter separations of the bifurcated hydrogen bonds engender relatively high SSCCs (~2.7 Hz) which suggest predominant electrostatic interactions. On the contrary the hydrogen bonding interactions srising from the alkyl chain on the cation reveal distances leading to negative J values (in the range of -0.02 Hz. to -0.7 Hz) and thus covalent nature of the hydrogen bond can be inferred.



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The reciprocal relation describing the dependence of covalent character of intermolecular hydrogen bonding distances on the SSCCs can readily be noticed. The dominance of strongly distance dependent FC term toward total SSCC values across the hydrogen bond is found to be sensitive to the interatomic distance, s-character of the atomic hybrids involved in the bond and lastly on the extent of induction of spin density transmitted through the nuclear spin magnetic moment. As evident from Table 6, the total J across C1’-H1---O1-C1 turns out to be a small negative (-0.4 Hz.) where the PSO contributions dominate. As compared to this the corresponding J value for the C1’-H1---O2-C1 turns out to be ~2.3 Å with dominant FC component. The total J(O,H) is negative for symmetric hydrogen bonds and positive for asymmetric hydrogen bonds. It may therefore, be concluded that O1 centers render large contributions to lp---π interactions through increased proton shared character to the cation. Moreover, the negative magnetogyric ratio of O1 or O2 engendering opposite signs for J(O,H) and K(O,H) suggests asymmetric (conventional) hydrogen bond those provide stability to the ILs. The variation of total J(O,H) as a function of O---H distances is portrayed in Fig. 9(a). The intramolecular N-H---O interactions are also transparent from Fig. 9 (b). In brief both FC and PSO mechanisms govern indirect J(H---O) parameters consequent to either hydrogen bonding or π-interactions responsible for strong deshielding of the imidazolium protons in these systems. As far as direct coupling constants are concerned, the one bond J(C,O) coupling constant serve as a probe to understand the nature of hydrogen as well as other noncovalent interactions accompanying ILs. The carboxylate oxygens pointing toward C=N bond of the imidazole ring bring about lp---π interactions and accordingly separation of C=N midpoint and carbonyl oxygen of the anion turns out to be ~2.9 Å. Noteworthy enough, the lone pair of carbonyl oxygens facilitating such interactions have dominant contributions from the PSO component corresponding to C1’=O1 (PSO1) and C1’=O2 (PSO2) (cf. Table 7). On the other hand, the magnitude of DSO was predicted to be merely -0.17 Hz. with the corresponding FC components being 7.283 and 5.156 Hz., respectively. 18 ACS Paragon Plus Environment

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A delicate balance of these components in conjunction with the relatively small SD term plays an important role in determining the total coupling constant. Higher PSO contributions toward total J imply relatively large lp---π contributions that brings about cation anion binding. A comparison of [Bmim] and [MBmim] ion pairs reveals total J(C1,O2) (J2) for the intermolecular hydrogen bond to be large. An increase of J2 parameters across C1=O2---H1-C1’ hydrogen bond concomitantly reflects in elongation of the C1=O2 bond. Contrary to this, a decrease of J(C1,O1) (J1) was observed for the methyl substituted ion pair systems owing to lp---π interactions. These arguments further can be extended to rest of the ion pairs and the corresponding parameters are summarized in Table S3 of the supporting information.

3.4 Nucleus Independent Chemical Shifts The magnetic field of a nucleus locally induces a magnetic moment in the electronic system, which results from either increase/decrease of polarizabilities or by inducing orbital ring currents. The electronic motion in a many body electron system is coupled with electrostatic Coulombic interactions. Thus, the locally induced electronic magnetic moment has a profound influence on the electronic structure of a molecule/ion pair and the effect of applied magnetic field on ring currents intrinsically can be correlated to π-electron delocalization, which has been quantified through NICS describing the "local aromaticity" in a polycyclic molecule. The π-cloud contributions of the aromatic rings can be accessed through the standard NICS(1)zz parameters and accordingly the NICS profiles are usually derived by scanning over the distances in the range from 0 to 3 Å. The isotropic NICS parameters are resolved into the in-plane and out-of-plane components. In the present work NICS profiles of imidazole ring of the cation along with those for the phenyl and pyrrole rings of the AA anion were derived independently. The NICS scans for imidazole and phenyl rings in [Bmim][Phe] ion pairs are shown in Figs. 10 (a) and 10 (b). Aromatic molecules are controlled by the in-plane and out-of-plane 19 ACS Paragon Plus Environment


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components of the magnetic tensors.89 Both imidazole and phenyl rings show the in-plane components profiles which are similar. The in-plane contribution to the isotropic NICS for imidazole ring reveals the minimum near -19.7 ppm at 1 Å whereas the corresponding minimum (-9.7 ppm) of the phenyl ring was located near 0.5 Å. The shifts are negative throughout the distance range considered. The out-of-plane components of chemical shifts of the imidazole ring are observed to be relatively less diatropic compared to the phenyl ring. NICS scans of these components of imidazole and phenyl rings in the [Bmim][Trp] ion pair are depicted in Fig. 10 (c) and (d). The imidazole ring NICS profiles in [Bmim][Trp] and [Bmim][Phe] are qualitatively similar. As far as the out of plane components are concerned they exhibit a minimum corresponding to phenyl rings whereas that for the imidazole ring steadily increases to maximum in the NICS profiles shown. Thus a complimentary behavior of the in-plane and out-of-plane component can be noticed. Interestingly the in-plane components of the phenyl ring engender diatropic shifts up to 2 Å beyond which a slight paratropic behavior can be observed (cf. Fig 10 (d)). NICS components for pyrrole ring in [Trp] shows qualitatively similar behavior to the phenyl ring. A comparison of out-of-plane NICS components and the isotropic values above the center of imidazole ring show unconvincing shallow minima for [Bmim][Phe] and [Bmim][Trp], which was not observed for the [Bmim][Tyr] system (cf. Fig. 10 (e)) owing to the presence of the lp---π interactions. The in-plane components in [Bmim][Tyr] system for phenyl ring reveal the deepest minimum near -25 ppm at 1 Å as shown in Fig. 10 (f). The relatively electron-deficient oxygen atoms in [Bmim][Tyr] ion pair are evident from residual NBO charges, which further corroborate these inferences (cf. Table S1 of the supporting information). Table 8 show NICS(0) values of the imidazole ring correlate well to ion pair binding energies and follows the hierarchy: [Phe] > [Tyr] > [Trp]. The substitution of an electron donating group significantly affects the orientation and binding patterns of the ion pair. It has earlier been recognized that the negative charge significantly influences the paratropic behavior 90 and emerge as signature for aromatic π-hole interactions. NICS


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components for [MBmim] aion pairs have been shown in Fig. 11 (a) through Fig. 11 (f). The [MBmim][Phe] ion pair underlines diatropic nature of the imidazole NICSzz below 1.0 Å and beyond 2 Å as shown in Fig. 11(a). On the other hand, the region from 1 Å to 2 Å reveals paratropic behavior and shows the maximum near 1.5 Å. The imidazole ring of [MBmim][Tyr] is qualitatively similar to aromatic NICS scan with its minimum being -13.9 ppm at 1 Å. Resolving the isotropic chemicals shifts as in-plane and out-of-plane contributions of the phenyl ring points to their distinct behavior. A comparison of NICS components indicate relatively strong diamagnetic currents in phenyl rings at longer distances within [MBmim][Phe] and [MBmim][Tyr] ion pairs can be attributed to CH---π interactions. It has been recognized that substitution on aromatic ring alters the charge distribution in the π-cloud and the diatropic effect can be experienced at different distances from the plane of the ring. The general shape of the NICSzz scan plots for [Bmim], [MBmim] ion pairs with varying anions for imidazole and phenyl rings are depicted in Fig.12 (a) and (b). The computed NICS(1)zz values of -24.9 ppm for the methyl-imidazole ring in the isolated [MBmim] cation become less negative (diatropic) upon interaction with the AA anion viz., -0.4 ppm in [MBmim][Phe], -0.2 ppm in [MBmim][Trp] and -13.9 in [MBmim][Tyr] consequent to C-H---O as well as N-H---O hydrogen bonding interactions in these ion pairs. The hydrogen bond induced decreased aromatic sextet character of the rings involved, hence can be inferred. A significant reduction of aromaticity was noticed for the [MBmim] ion pairs than their unsubstituted analogues. As shown in the figure the out-of-plane components for [Bmim][Phe] and [Bmim][Trp] are qualitatively similar to those for the isolated cation or their [MBmim] analogues. A complimentary feature for the imidazole ring participating in in the lp---π interactions can be observed for [Tyr] anion based systems. NICS scan for the phenyl rings herein are shown in Fig. 12 (b). The out-of-plane components of the phenyl rings in these ion pairs, except those predicted for the [MBmim][AA] (AA=Phe, Tyr), are qualitatively similar to their respective isolated anions. The [MBmim][AA] (AA=Phe, Tyr) ion pairs 21 ACS Paragon Plus Environment


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possess CH---π interactions. Further the NICS(1)zz parameters data given in Table 8 suggests the phenyl and pyrrole rings of [MBmim][Trp] ion pair have large aromatic character compared to their unsubstituted counterpart.

3.5 Infrared spectra Intermolecular hydrogen bonding between donor-acceptor complexes, for example ionpairs or composites induces structural changes, show their signatures in characteristic vibration frequency shifts compared to their constituents. Cation-anion binding can be probed through normal coordinate analysis. The formation of ion pairs engenders a down-shift (red shift) in the vibrational frequency of carbonyl stretching compared to the isolated cation of the ion pair. As opposed to this, a shift toward higher wave-number (blue shift) can be characterized in terms of bond contraction accompanied by diminutive IR intensity arising from the negative dipole moment derivative with respect to stretching coordinate. Underlying molecular interactions are probed subsequently through the normal vibration analysis based on the potential energy distribution computed for each ion-pair. Calculated vibrational spectra portraying the molar absorption coefficient (or, molar absorptivity in units of 0.1 m2 mol-1) versus the frequency (in cm−1) of [Bmim][AA] and [MBmim][AA] systems are depicted in Fig. 13 and Fig. S3 of the supporting information. The spectra of the [Phe] (anion), [Bmim] and the ion-pair are marked as blue, red and black (on line version), respectively, in Fig. 13 (a). The following inferences may be drawn. The region 3700-2900 cm−1 shows the ion pair formation is accompanied by a frequency upshift of 48 cm−1 for the N-H stretching vibration in the free anion (3574 cm−1). As may be noted, the 3305 cm−1 bandassigned to C1-H1 stretching of the free cation appears as an intense band at 3239 cm−1 in the ion pair. The aromatic CH stretch for the phenyl moiety occurs in the 3253 to 3239 cm−1 range whereas the imidazole ring vibrations are noticed in the 3353-3335 cm−1 region. The most intense carbonyl stretching of the anion assigned to the 1713 cm−1 vibration shifts to 1677 cm−1 with


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diminutive intensity. On the other hand, C=N stretching (1647 cm−1) from imidazole ring of the cation emerges with a downshift of 19 cm−1 with the enhanced intensity accomanying the ion-pair formation. The 1468 cm−1 vibrations in the ion-pair arising from [Bmim] and [Phe] respectively, invoke a strong coupling from C2C1H1 deformation and NH2 rocking. Analyses of vibration spectra of [Trp] and [Tyr] ion-pairs with [Bmim] lead to similar inferences. Selected normal vibrations are summarized in Table S4 of the supporting information. Similar inferences are drawn for the [MBmim] based ion pairs with methyl vibrations appearing in the range of 3205-3071 cm−1 as shown in Fig. 13 (b). The low frequency aromatic ring liberation modes usually invoke strong coupling of twisting or bending coordinates from the bulky cation and anion. As shown in Fig. 13 (a), the Raman active inter-ionic vibrations in aromatic AAILs appear below 200 cm−1. The aromatic ring liberation modes in the neutral [Bmim][Phe] ion pair was predicted near 80 cm-1 compared to the 65 cm−1 vibration of the charged aromatic ring in the isolated [Bmim]+ cation. Moreover the correponding vibration in respective [Bmim][Trp] and [Bmim][Tyr] ion pairs assigned to 56 cm−1 and 51 cm−1 bands also stem from strong inter-ionic interactions. These inferences are consonance with those drawn earlier for the [MBmim][AA] ion pairs. The direction of frequency shifts further is rationalized through natural bond orbital analysis. An increase of antibonding π* (C=O) natural orbital population accompanying the [Bmim][AA] ion pair formation relative to the free anion thus explains the red (down) shift of the corresponding vibration. A large change in the [Bmim][Tyr] ion pair is consistent with a large frequency shift (nearly ~29cm−1) of the carbonyl vibration. As opposed to this, wavenumber upshift of the NH stretching in such ion pairs can be rationalized from a decrease of population in the corresponding σ*(NH) natural orbitals.



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4. Conclusions Structure, binding energies and noncovalent interactions in [Bmim][AA] and [MBmim][AA] (AA= [Phe], [Trp] and [Tyr] have been analyzed. [Bmim] based ILs attain T-shaped structures owing to bifurcated hydrogen bonding from the most reactive proton of the cation and AA anion. The methyl substitution on cation renders electron-deficient π holes leading to lp---π interactions with concomitant CH---π interactions from phenyl ring of the anion engendering parallel displaced stacked structures for the [MBmim][Phe] and [MBmim][Tyr] ion pairs. On the other hand, the [MBmim][Trp] ion pair void of CH---π interactions shows T-shaped structure. Displaced parallel structures of [MBmim] ion pairs have dominant dispersion components contrary to T-shaped structure wherein the electrostatic contributions prevail. The ramifications of these interactions to 1H

NMR spectra manifest in strong deshielded signals as a result of an effective induction of

paramagnetic current density by the external magnetic field. Isotropic chemicals shifts resolved into in-plane and out-of-plane NICS components corresponding to phenyl and imidazole rings are indicative of diamagnetic and paramagnetic ring currents consequent to underlying noncovalent interactions. Thus hydrogen bond induced reduction in aromaticity for the ion pairs can be deciphered. Furthermore, the spin-spin coupling constants serve as “fingerprint” for hydrogen bonding interactions with FC components contributing largely to total SSCCs. On the other hand, lp--π interactions have dominant PSO components. The present work demonstrates that the cation anion separations turn out to be a crucial in the determination of indirect coupling constants. The direction of frequency shifts of characteristic C=O and N-H stretching in the vibrational spectra accompanying the ion pair formation has further been rationalized.


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Acknowledgements S. P. G. acknowledges the support from the Board of Research in Nuclear Sciences (BRNS) India through the research project 37(2)/14/11/2015-BRNS. S. S. R. is grateful to University Grants Commission, New Delhi for award of the meritorious research fellowship. Authors thank the Centre for Development of Advanced Computing (CDAC), Pune for providing National Param Supercomputing Facility.

Supporting Information Optimized geometries, Spin-spin Coupling Constants, net atomic charges in ion-pairs, vibrational frequencies for ion-pairs.



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35 Table 1. Selected bond distances (in Å) of [Bmim]+, [MBmim]+ cations, [AA]− anions (AA= Phe, Trp, Tyr) along with respective ion pairs.

C1-H1 C1-H3 C1-N1 C1’=O1 C1’=O2 N1’-Ha N1’C2’C1’O1 C1H1O1C1’ C1N1O2C1’

Bmim 1.076 1.330

MBmim

Phe

Trp

Tyr

1.090 1.337 1.249 1.246 1.018 11.52

1.249 1.245 1.018 10.37

1.250 1.246 1.018 -5.9

[Bmim][Phe] 1.081

[Bmim][Trp] 1.081

[Bmim][Tyr] 1.082

1.329 1.258 1.252 1.013 -26.08 -77.23

1.329 1.258 1.252 1.014 -17.44 -76.02

1.329 1.257 1.252 1.012 -19.98 -75.43

[MBmim][Phe]

[MBmim][Trp]

[MBmim][Tyr]

1.090 1.334 1.250 1.258 1.014 13.13

1.089 1.335 1.256 1.253 1.014 4.10

1.091 1.336 1.254 1.251 1.012 -35.34

-100.29

-138.39

30.24



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36 Table 2: Inter-molecular distances, corresponding ρbcp and Laplacian ∇ 2 ρ parameters (in a.u) in (a) [Bmim][AA] and (b) [MBmim][AA] ion pairs.

(a)

(b)

O1---H1 O2---H1 O1---H6 O2---H7 N1’---H9 N1’---H13 O2---Ha

O1---H6 O1---H16 O2---H16 O2---H9 O2---H7

r 2.004 2.288 2.211 2.386 2.740 2.809

[Bmim][Phe] ρbcp ∇2ρ 0.0179 0.0685 0.0257 0.0961 0.0155 0.0570 0.0124 0.0424 0.0072 0.0195 0.0068 0.0174

r 2.292 2.013 2.208 2.392 2.802 2.117

[Bmim][Trp] ρbcp ∇2ρ 0.0180 0.0687 0.0253 0.0950 0.0156 0.0576 0.0123 0.0423 0.0060 0.0172 0.0224

[MBmim][Trp] r ρbcp ∇2ρ 2.340 0.0142 0.0459 2.115 0.0189 0.0736

2.378

2.217 2.132

0.0390

0.0156 0.0222

[Bmim][Tyr] ρbcp ∇2ρ 0.0179 0.0687 0.0263 0.0983 0.0119 0.0405 0.0153 0.0556 0.0069 0.0185

0.0970

[MBmim][Phe] r ρbcp ∇2ρ 2.218 0.0162 0.0517 2.258 0.0150 0.0498 0.0127

r 2.291 1.990 2.409 2.223 2.771

0.0620 0.0924

[MBmim][Tyr] r ρbcp ∇2ρ 2.453 0.0131 0.0461 2.497 0.0109 0.0357 2.161 0.0178 0.0660 2.460 0.0122 0.0461 2.473 0.0107 0.0364


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37 Table 3: 1H NMR in [Bmim][AA] and [MBmim][AA] ion pairs.

δH

Bmim

H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 H17 H18 Ha Hb Hc Hd He Hf Hg Hh Hi Hj Hk

8.0 7.8 7.9 3.9 3.9 3.8 4.1 4.2 1.8 2.0 1.4 1.4 1.0 1.5 1.0

MBmim

Phe

Trp

Tyr

7.9 7.5 4.0 4.0 4.1 4.0 4.0 2.1 2.1 1.6 1.6 1.4 2.0 1.4 2.8 2.8 3.2 -0.7 3.5 2.8 4.6 2.2 8.0 7.6 7.5 7.9 10.0

-0.7 3.8 3.0 4.2 2.3 8.5 7.6 7.6 7.6 8.9 7.0

-0.4 3.7 2.5 3.8 2.1 7.9 6.8 7.4 8.6 3.3

[Bmim][Phe]

[Bmim][Trp]

[Bmim][Tyr]

12.9 7.1 7.1 3.3 3.4 6.4 5.3 3.5 2.6 1.2 1.5 1.0 1.7 0.9 0.5

12.7 7.2 7.1 3.3 3.5 6.4 5.4 3.6 2.4 1.5 1.5 1.0 2.2 1.0 0.7

12.8 7.1 7.0 3.4 3.2 6.2 5.2 3.5 2.8 1.3 1.7 1.0 2.4 1.2 0.7

0.4 1.5 3.1 3.3 2.2 8.2 8.1 8.0 8.0 7.9

2.6 0.9 3.8 2.6 3.3 8.4 8.1 8.0 8.0 7.4 7.3

2.4 0.1 3.2 2.2 3.6 7.7 7.2 7.4 8.1 3.8

[MBmim][Phe]

[MBmim][Trp]

[MBmim][Tyr]

9.7 8.1 7.9 7.8 7.7 7.1 7.1 6.9 4.6 4.0 3.7 3.5 3.4 3.2 2.8 2.8 2.7 0.0 -0.5 0.2 0.8 0.4 2.4 2.0 1.5 1.4 0.8

8.4 8.2 8.1 7.8 7.6 7.5 7.1 6.9 6.0 5.7 4.4 3.8 3.7 3.3 3.3 3.2 3.1 0.9 0.0 0.9 1.3 1.3 2.3 2.8 1.7 1.7 1.6 1.6

8.0 7.7 7.5 7.3 7.2 7.1 5.5 4.9 4.7 3.7 3.5 3.4 3.2 3.2 3.1 2.8 2.6 1.1 0.8 1.1 1.2 1.8 1.8 1.9 2.0 2.1 0.1



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38 Table 4: 13C NMR in [Bmim][AA] and [MBmim][AA] ion pairs.

δC C1 C2 C3 C4 C5 C6 C7 C8 C9 C1’ C2’ C3’ C4’ C5’ C6’ C7’ C8’ C9’ C10’ C11’

Bmim 152.4 144.8 145.3 39.5 59.2 41.2 23.4 14.6

MBmim 166.7 139.5 144.3 39.8 55.8 34.1 23.9 16.8 12.2

Phe

Trp

Tyr

196.7 61.7 48.9 178.6 153.3 147.2 142.9 150.1 156.2

196.5 61.9 36.4 146.2 154.6 142.2 137.1 139.2 127.5 156.9 146.2

194.2 66.3 52.2 170.6 153.4 129.4 174.9 132.8 158.8

[Bmim][Phe] 168.7 137.5 140.1 38.3 56.3 38.5 24.1 14.0

[Bmim][Trp] 166.8 137.5 140.1 38.6 23.1 39.0 23.1 15.0

[Bmim][Tyr] 168.5 136.8 139.9 38.0 57.3 38.9 24.7 14.4

204.6 66.8 52.2 170.5 153.2 152.1 147.5 151.7 153.9

205.8 60.9 39.9 139.1 152.5 140.0 139.9 144.0 130.2 158.4 139.3

203.2 66.1 48.1 161.6 152.1 133.0 178.0 135.2 156.7

[MBmim][Phe] 174.4 136.4 141.0 40.1 56.2 36.7 24.9 14.8 12.8 205.6 67.1 46.4 173.8 153.2 149.9 146.9 152.1 154.6

[MBmim][Trp] 173.1 138.1 137.8 38.7 55.6 38.1 23.0 15.5 17.9 205.0 61.0 37.0 136.1 152.7 140.0 139.4 141.6 130.0 158.1 143.6

[MBmim][Tyr] 170.6 135.8 143.5 39.0 54.3 36.8 23.0 15.0 18.4 200.0 65.3 47.5 162.0 153.0 132.8 178.1 136.0 155.8


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39

Table 5: Calculated intermolecular spin-spin coupling constants J( C1’,C1)across the C1’O1H1C1 dihedral angle in [Bmim][AA] and [MBmim][AA] ion pairs.

[Bmim][Phe]

PSO -0.137

DSO 0.115

FC -0.661

SD -0.002

J( C1’,C1) -0.684

Distance(C1’-C1) 3.023

[Bmim][Trp]

-0.136

0.116

-0.661

-0.002

-0.684

3.095

[Bmim][Tyr]

-0.136

0.116

-0.682

-0.001

-0.703

3.015

[MBmim][Phe]

-0.055

0.070

-0.003

-0.010

0.002

3.318

[MBmim][Trp]

-0.108

0.088

-0.011

-0.019

-0.051

3.224

[MBmim][Tyr]

-0.103

0.141

0.056

-0.011

0.083

3.044



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40 Table 6: Spin-spin coupling constants for J(O,H)for inter- as well as intramolecular hydrogen bonding in (a) [Bmim][Phe] and (b) [MBmim][Phe] ion pairs. See text for details.

(a)

O1---H1 O2---H1 O1---H6 O2---H7 N1’---H9 N1’---H13 O2---Ha

(b)

O1---H6 O1---H16 O2---H6 O2---H7 O1---Ha O2---Hd

distances 2.004 2.288 2.211 2.386 2.740 2.809 2.242 distances 2.218 2.257 2.677 2.378 2.325 2.269

FC -0.61 2.46 2.48 0.70 -0.19 -0.06 1.11 FC 1.66 1.12 -0.22 0.31 1.05 0.38

SD -0.03 -0.05 -0.09 -0.07 0.01 0.01 0.09 SD -0.21 0.08 -0.01 0.03 0.09 0.09

PSO 0.49 0.83 0.65 0.38 -0.17 -0.14 0.56 PSO 0.62 0.33 0.36 0.48 0.55 0.55

DSO -0.37 -0.54 -0.48 -0.45 0.19 0.16 -0.41 DSO -0.46 -0.44 -0.30 -0.51 -0.35 -0.40

Total J -0.46 2.69 2.56 0.70 -0.16 -0.02 1.35 Total J 1.61 0.11 -0.16 0.32 1.39 0.64


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41 Table 7: Direct spin-spin coupling constants for J(C1’,O1) (J1) and J(C1’,O2) (J2) in [Bmim][AA] and [MBmim][AA] ion pairs. See text for details.

[Bmim][Phe] [Bmim][Trp] [Bmim][Tyr] [MBmim][Phe] [MBmim][Trp] [MBmim][Tyr]

PSO1 13.90 14.00 13.87 14.25 13.93 13.81

PSO2 14.14 13.81 14.02 13.71 13.65 14.03

DSO1 -0.176 -0.176 -0.174 -0.166 -0.177 -0.182

DSO2 -0.170 0.663 -0.171 -0.185 -0.174 -0.174

FC1 7.28 7.20 7.25 5.41 5.42 6.07

FC2 5.15 0.24 5.19 7.10 5.78 5.07

SD1 -0.26 -0.27 -2.27 -0.46 -0.14 -0.29

SD2 -0.35 -0.08 -0.35 -0.19 -0.31 -0.34

D1 1.258 1.258 1.258 1.259 1.256 1.255

D2 1.252 1.252 1.253 1.250 1.253 1.252

J1 20.74 20.52 20.68 20.43 18.95 19.42

J2 18.78 18.31 18.68 19.04 18.86 18.58



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42 Table 8: NICS parameters, ρrcp and ∇2ρ, (in a.u) for imidazole and phenol rings in [Bmim][AA] and [MBmim][AA].

[Bmim][Phe] [Bmim][Trp] [Bmim][Tyr] [MBmim][Phe] [MBmim][Trp] [MBmim][Tyr]

Imidazole Phenyl Imidazole Phenyl Pyrol Imidazole Phenyl Imidazole Phenyl Imidazole Phenyl Pyrol Imidazole Phenyl

NICS(0) -13.47 -7.35 -13.95 -9.02 -11.66 -13.58 -8.87 -12.99 -7.53 -13.14 -9.00 -11.93 -12.78 -8.78

NICS(1) -10.57 -10.17 -10.27 -10.95 -9.20 -9.31 -9.85 -8.98 -10.27 -8.82 -10.59 -9.98 -10.55 -9.83

NICS(0)zz -6.54 -5.11 -7.71 -9.23 -9.92 -8.40 -11.45 -7.87 -5.10 -11.05 -11.00 -9.01 -8.55 -7.55

NICS(1)zz -8.00 -6.15 -7.40 -14.79 -10.69 -5.46 -23.45 -0.41 -4.57 -0.21 -20.66 -18.13 -13.95 -5.21

ρrcp 0.056 0.023 0.056 0.022 0.051 0.056 0.023 0.056 0.023 0.056 0.022 0.050 0.0561 0.023

∇2ρ 0.418 0.164 0.418 0.016 0.351 0.418 0.007 0.414 0.164 0.415 0.159 0.351 0.416 0.162


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43

Figure Captions Figure 1.

Structures of (a) [Bmim] (b) [MBmim] cations and amino acid (c) [Phe], (d) [Trp], (e) [Tyr] anions. The atomic labeling scheme is shown along with.

Figure 2.

Optimized structures of (a) [Bmim][Phe], (b) [Bmim][Trp] and (c) [Bmim][Tyr] ion pairs. Hydrogen bonding interactions are depicted as broken lines.

Figure 3.

Optimized structures of (a) [MBmim][Phe], (b) [MBmim][Trp] and (c) [MBmim][Tyr] ion pairs. Hydrogen bonding interactions are depicted as broken lines.

Figure 4.

ESP mapped isodensity surface (0.001 a.u) in isolated (a) [Bmim], (b) [MBmim] cations, as well as (c) [Phe], (d) [Trp] and (e) [Tyr] anions along with (f) [Bmim][Phe] and (g) [MBmim][Phe] ion pairs.

Figure 5.

Angular scatter plot of C=O---H angles as a function of O---H separations. See text for details.

Figure 6.

Color-filled RDG isosurfaces depicting Non-covalent interaction (NCI) regions in (a) [Bmim][Phe] and (c) [MBmim][Phe] ion pairs. Green regions denote O---H and lp---π interactions while the red isosurface refers to steric effects. The NCI index plot of function 1 (sign (λ2) ρ values) on the x-axis versus function 2, the reduced density gradient (RDG) on the Y-axis for the same have also been shown in (b) [Bmim][Phe] and (d)[MBmim][Phe] ion pairs.

Figure 7.

Dispersive, orbital and steric contributions along with total binding energies accompanying cation-anion binding in the regime of M05-2x level of theory.

Figure 8.

Fermi contact (FC), spin-dipole (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO) components contributing to total spin-spin coupling for ion pairs.

Figure 9.

A plot showing correlation of indirect J(O,H) spin-spin coupling constant versus hydrogen bond distances distinguishing (a) inter and (b) intra molecular hydrogen bonding. See text for details.

Figure 10.

Isotropic, in-plane and out-of-plane NICS components as a function of distance (in Å) for (i) imidazole ring and (ii) phenyl ring for [Bmim][AA] ion pairs. See text for details.

Figure 11.

Isotropic, in-plane and out-of-plane NICS components as a function of distance (in Å) for (i) imidazole ring and (ii) phenyl ring for [MBmim][AA] ion pairs. See text for details.

Figure 12.

A graph showing correlation between NICSzz scan and distances (Å) for (a) imidazole and (b) phenyl rings in [Bmim] and [MBmim] ion pairs.



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Page 44 of 58

44 Figure 13.

Infra red spectra for the (a) [Bmim][Phe] and (b) [MBmim[Phe] ion-pairs.


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45

(a) [Bmim]

(c)[Phe]

−

+

+

(b) [MBmim]

(d) [Trp]

−

(e) [Tyr]

−

Figure 1



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Page 46 of 58

46

(a) [Bmim][Phe]

(b) [Bmim][Trp]

(c) [Bmim][Tyr] Figure 2.


Page 47 of 58

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47

(a) [MBmim][Phe]

(b) [MBmim][Trp]

(c) [MBmim][Tyr] Figure 3.



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Page 48 of 58

48

+

+

(a) [Bmim]

(b) [MBmim]

−

(c)[Phe]

(f) [Bmim][Phe]

−

(d)[Trp]

−

(e)[Tyr]

(g)[MBmim][Phe] Figure 4.


Page 49 of 58


49

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 5.



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Page 50 of 58

50

(a) [Bmim][Phe]

(b) [Bmim][Phe]

(c)[MBmim][Phe]

(d)[MBmim][Phe] Figure 6.


Page 51 of 58


51

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Figure 7.



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52

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Figure 8.


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53

(a)

(b) Figure 9.



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54 (i)

Imidazole ring

(ii)

(a)

Phenyl ring

(b) [Bmim][Phe]

(c)

(d) [Bmim][Trp]

(e)

(f) [Bmim][Tyr] Figure 10.


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55 (i)

Imidazole ring

(ii)

(a)

Phenyl ring

(b) [Bmim][Phe]

(c)

(d) [Bmim][Trp]

(e)

(f) [Bmim][Tyr] Figure 11.



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(a) Imidazole ring scan

(b) Phenyl ring scan Figure 12.


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57

(a)[Bmim][Phe]

(b)[MBmim][Phe] Figure 13.



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Noncovalent interactions underlying aromatic amino acid based ionic liquids. 268x184mm (96 x 96 DPI)

ACS Paragon Plus Environment

Page 58 of 58

Electronic Structure, NMR, SpinâSpin Coupling, and Noncovalent

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