Fabrication of Supramolecular Chirality from Achiral Molecules at the

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Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation Lu Lin,†,‡ Zhen Zhang,‡ Yuan Guo,*,‡,§ and Minghua Liu*,‡ †

National Center for Nanoscience and Technology, Beijing 100190, P. R. China Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China § University of Chinese Academy of Sciences, Beijing 100049, P. R. China ‡

S Supporting Information *

ABSTRACT: We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

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INTRODUCTION Supramolecular assemblies can find applications in enantioselective catalysis,1,2 nonlinear optics,3−6 and molecular devices.7,8 In the past decades, significant interests have been drawn to the construction of chiral assemblies9−17 and the mechanism of chiral induction, transcription, and amplification.18−25 So far, strategies for the fabrication of self-assemblies with supramolecular chirality have been well established, many of which concern chiral assembly from achiral molecules, referred to as building blocks, through π−π stacking, hydrogen bonding, coordination, and van der Waals interactions.12,26−29 It has been shown that achiral molecules can form special spatial arrangements, typically helices, under certain circumstances and give rise to supramolecular chirality.30 The handedness of the helices is determined by the helical directions in the assemblies, and it can be readily controlled by various methods, including chiral templates,31,32 stirring vortices,33,34 and magnetic forces.16 In contrast, there is very limited report on controlling the enantiomeric excess in supramolecular assemblies. As compared with bulk media, supramolecular chirality can be achieved more readily at interfaces because of the noncentrosymmetric nature in two dimensions.17 Up to now, © XXXX American Chemical Society

although fabrication and control of supramolecular chirality at gas/liquid, gas/solid, and liquid/solid interfaces have been systematically investigated,30,35−38 little information is available on supramolecular chirality at liquid/liquid interfaces. Liquid/ liquid interfaces play important roles in many chemical and biological processes such as membrane transport, electron transfer, solvent extraction, phase-transfer catalysis, and nanoparticle assembly.39−46 Molecules adsorbed at liquid/ liquid interfaces are more likely to form aggregates because the capacity of an liquid/liquid interface is ∼10−10 mol/cm2, almost two orders smaller than that of the air/water interface.47 Watarai and coworkers have carried out pioneering studies in this field, demonstrating that achiral porphyrin derivatives could form chiral aggregates at liquid/liquid interfaces.48−53 Nevertheless, detailed information on the fabrication of supramolecular chirality at liquid/liquid interfaces is still lacking because conventional methods for chirality detection, such as circular dichroism (CD), optical rotatory dispersion (ORD), and scanning probe microscopy (SPM), are not Received: December 7, 2017 Revised: December 14, 2017 Published: December 15, 2017 A

DOI: 10.1021/acs.langmuir.7b04170 Langmuir XXXX, XXX, XXX−XXX

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75° with respect to the surface normal. SHG signals at 400 nm were collected in the reflected direction with a high-gain photomultiplier tube (R585, Hamamatsu) and a gated photon counter (SR400, Stanford Research Systems). The incident polarization was continuously adjusted with a half-wave plate driven by a computercontrolled stepper motor. The output polarization was fixed at either s or p with an analyzer.

suitable for characterization of chirality at liquid/liquid interfaces. In the past two decades, second-order nonlinear optical spectroscopy, including second harmonic generation (SHG) and sum frequency generation (SFG), has proven to be powerful tools in the studies of interfacial chirality due to its interface-selectivity and chiral-sensitivity.54−56 In particular, they are more suitable for in situ probe of supramolecular chirality at the liquid/liquid interfaces. Comparison of the nonlinear optical intensities under different polarization combinations can quantitatively determine the interfacial chirality in terms of the chiral sign and the enantiomeric excess.23,57−67 Besides, molecular orientation and conformation at the interfaces can also be determined through polarization-resolved measurements.68−74 In this report, we employ SHG to investigate the fabrication of supramolecular chirality at water/1,2-dichloroethane interface and its dependence on the bulk concentration of the building blocks in the organic phase. 5-Octadecyloxy-2-(2pyridylazo)phenol (PARC18, Figure 1) is chosen as building

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RESULTS AND DISCUSSION The interfacial chirality and molecular orientation can be derived from the incident polarization dependence of the SHG intensities. Relations between the SHG intensity and the incident polarization can be expressed as follows60 Is ∝ |a1χxxz sin 2α + a 7χyxz cos2 α|2 Ip ∝ |(a 2χxxz + a3χzxx + a4χzzz ) cos2 α + a5χzxx 2 sin 2 α + a6χyxz sin α cos α|

where χijk are the nonzero tensor elements of the second-order susceptibility for chiral interfaces with in-plane isotropy. The subscript s denotes output polarization parallel to the interface and p denotes polarization in the plane defined by the surface normal and the direction of light propagating; ai (i = 1−7) are the Fresnel coefficients and α is the polarization of the incident light. A detailed description of eq 1 can be found in the Supporting Information. To quantitatively describe the enantiomeric excess, the degree of chiral excess (DCE) has been introduced, which is defined as59,67 2(I45° − I135°) ΔI = I I45° + I135°

(2)

In the following, we will first use s-polarized detection to characterize the supramolecular chirality because previous studies have pointed out that s-polarized detection is more sensitive to interfacial chirality compared with p-polarized detection,59 then we use the combination of s- and p-polarized detection to assess the orientational angle of PARC18 molecules at the interface. Figure 2 shows the s-polarized SHG curves at various bulk concentrations of PARC18 in the organic phase. At medium concentrations (0.025−0.075 mM), there is a remarkable difference between the SHG intensities when the incident polarization is at 45 or 135°, indicating the emergence of supramolecular chirality at the interface resulted from PARC18 stacking. At both lower and higher concentrations, on the contrary, the differences are almost negligible, indicating the absence of supramolecular chirality. Although surface optical activity can also be due to in-plane anisotropy,78,79 it occurs mostly in the case of Langmuir−Blodgett films or crystals. In our experiments, the interface is bounded by centrosymmetric bulk phases that should be with in-plane isotropy.80 Hence the optical activity observed here is from chiral aggregation of PARC18 molecules. These results demonstrate that the supramolecular chirality of PARC18 assemblies at the liquid/ liquid interface is strongly dependent on its bulk concentration in the organic phase. This phenomenon can be explained by considering the molecular densities at the liquid/liquid interface. At lower concentrations, the absence of supramolecular chirality can be ascribed to the relatively low density of PARC18 molecules at the interface where achiral PARC18 molecules mainly exist as monomers instead of assemblies. At higher concentrations, however, the disappearance of supra-

Figure 1. Molecular structure of PARC18 and definitions of orientational angle θ and twist angle ψ.

blocks mainly because PARC18 assemblies display strong supramolecular chirality at the air/aqueous interface.59,75 Herein we show that PARC18 assemblies exhibit supramolecular chirality at water/1,2-dichloroethane interface, and its bulk concentration in the organic phase can modulate this supramolecular chirality. We also estimate the orientational angle and twist angle of PARC18 molecules at the interface and discuss their effects on the supramolecular chirality. The orientational angle changes slightly over the concentration range, and the twist angle determines the supramolecular chirality. On the basis of our observation and analysis, we propose molecular mechanism of PARC18 chiral assembly at the liquid/liquid interface.

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(1)

EXPERIMENTAL SECTION

PARC18 was synthesized and purified as described in the literature.76,77 1,2-Dichloroethane (purity >99.8%) was purchased from Acros Organics and used as received. Ultrapure water (18.2 MΩ· cm) was supplied from a Millipore system. PARC18 was dissolved in 1,2-dichloroethane, and the liquid sample was contained in a square cell made of fused silica. For SHG experiments, a mode-locked femtosecond Ti:sapphire laser (Tsunami 3960C, Spectra-Physics) was used. The pulse width was 80 fs and the repetition rate was 82 MHz. The fundamental wavelength was 800 nm and the incident angle of the laser beam was B

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Figure 2. s-Polarized SHG curves at various bulk concentrations of PARC18 in the organic phase. The circles represent experimental results and the solid lines are fits to eq 1. At medium concentrations, the SHG intensities are different when the incident polarization is at 45 or 135°, indicating the existence of supramolecular chirality, whereas at lower or higher concentrations, the difference is negligible, which means the interface is achiral.

Figure 3. p-Polarized SHG curves at various bulk concentrations of PARC18 in the organic phase. The circles represent experimental results and the solid lines are fits to eq 1.

Obviously, details of the molecular structures at the interface are required to resolve this contradiction. The p-polarized SHG curves together with fits to eq 1 are shown in Figure 3. Combined with fitting of the s-polarized curves, four nonzero independent tensor elements, namely, χzzz, χzxx, χxxz, and χyxz, are obtained, as listed in the Supporting

molecular chirality seems rather counterintuitive. It has been reported that supramolecular chirality is generally more favorable at higher molecular densities in Langmuir monolayers at the air/water interface.13,60 As such, the higher concentrations might also have promoted the formation of the supramolecular chirality at the liquid/liquid interface. C

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Langmuir Information. These tensor elements are linear combinations of molecular hyperpolarizabilities βijk. Hence, by appropriately assuming the β terms, the molecular orientational angle can be quantitatively retrieved. At neutral pH, PARC18 adopts a planar geometry,81 which is usually treated as uniaxial with only one dominant molecular hyperpolarizability denoted as βccc.82 However, βccc does not contribute to the macroscopic chiral tensor element χyxz.55,63 Therefore, the uniaxial symmetry is invalid to characterize the supramolecular chirality of PARC18 at the liquid/liquid interface, and additional molecular hyperpolarizability must be taken into account. Considering that PARC18 molecule has approximately C2v symmetry with a planar geometry and contains a transition near resonant with the second harmonic frequency, it is reasonable to suggest another nonzero molecular hyperpolarizability βcaa.83 Then, the macroscopic tensor elements can be related to the molecular hyperpolarizabilities as63

Figure 4. Degree of chiral excess (red, left vertical axis) and molecular orientational angle (blue, right vertical axis) at various bulk concentrations. The supramolecular chirality is first enhanced with increasing bulk concentration and starts decreasing after 0.035 mM. The orientational angle shows a similar trend to that of the supramolecular chirality.

χzzz = Ns(⟨cos3 θ⟩βccc + ⟨sin 2 θ cos θ cos2 ψ ⟩βcaa) 1 Ns(⟨sin 2 θ cos θ⟩βccc + ⟨cos θ sin 2 ψ + cos3 θ cos2 ψ ⟩βcaa) 2 1 = Ns(⟨sin 2 θ cos θ⟩βccc − ⟨sin 2 θ cos θ cos2 ψ ⟩βcaa) 2 1 = Ns(⟨sin 2 θ sin ψ cos ψ ⟩βcaa) 2

χzxx = χxxz χyxz

(3)

where θ is the orientational angle, ψ is the twist angle, and Ns is the number density of PARC18 molecules at the interface. The angular brackets denote the average over the inside variables. In principle, given narrow distributions of the orientational and twist angles, the values of θ and ψ can be determined using eq 3 combined with the fitting results of the macroscopic tensor elements. However, as Simpson and coworkers have pointed out,84 although χyxz can serve as a useful tool for assessing the supramolecular chirality at the interface, directly relating it to the molecular structure is nontrivial. We hence use χzzz, χzxx, and χxxz to evaluate the molecular orientation. Details of the calculations can be found in the Supporting Information. To elucidate the correlation between the molecular orientation and the supramolecular chirality, we also calculate the DCE, an indicator of supramolecular chirality, using χyxz and χxxz. Figure 4 shows the plot of molecular orientation and DCE against the bulk concentration of PARC18. At the lowest concentration of 0.005 mM, the orientational angle is ∼32°, and the interface is nearly achiral. With the increasing bulk concentration, the orientational angle gets larger and reaches a maximum around 36° as the bulk concentration is 0.035 mM. Meanwhile, the DCE also gradually increases to a maximum ∼26%. After that, increasing the bulk concentration gives rise to the decrease in both the orientational angle and the supramolecular chirality. When the bulk concentration approaches 0.3 mM, the orientational angle reaches ∼30° and the supramolecular chirality vanishes. According to the definition, DCE is a function of both the orientation angle θ and the twist angle ψ. The dependence of DCE on θ and ψ is illustrated in Figure 5. For a certain ψ, DCE increases slowly with θ when θ is 45°. The range of the orientational angle can thus be categorized into two regions: insensitive region where DCE depends weakly on θ and sensitive region where DCE depends strongly on θ. In the present case, the value of θ lies in the insensitive region, and changes in θ have little effects on DCE.

Figure 5. 3D plot of DCE against the molecular orientational angle θ and the twist angle ψ. The ratio of βcaa and βccc is assumed to be 0.15. When θ is larger than 45°, DCE grows rapidly with θ; when θ is smaller than 45°, DCE is predominantly determined by ψ.

In other words, the twist angle ψ and its angular distribution predominantly determine the DCE. At a low bulk concentration, PARC18 molecules exist as monomers at the interface and can rotate freely with respect to the molecular axis, resulting in a random distribution of ψ and zero χyxz. As a result, the interface is achiral at a low bulk concentration. At medium bulk concentrations, more PARC18 molecules are adsorbed at the interface, which cause strong interactions between adsorbed molecules. Such intermolecular interactions make PARC18 molecules form assemblies in which they can no longer rotate freely. In the meantime, PARC18 molecules have to tilt to the interface and rotate with respect to its molecular axis to minimize the dipole−dipole repulsions between the head groups,85 which lead to a larger θ and a nonzero ψ with a narrower distribution. As a result, supramolecular chirality gradually appears at medium bulk concentrations. With continually increasing bulk concentration, adsorbed PARC18 molecules at the interface become crowded so that they have to tilt to the surface normal and rotate with respect to the molecular axis to minimize the occupied area. Eventually, PARC18 molecules adopt a face-toface geometry with a smaller orientation angle and a twist angle that is close to zero, followed by the disappearance of D

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Figure 6. Schematic illustration of PARC18 supramolecular chirality at the interface. Green blocks represent conjugated chromophores of PARC18 molecules. At low and high concentrations, PARC18 molecules tilt less to the interface and form achiral structures. At medium concentrations, PARC18 molecules tilt more to the interface and form chiral assemblies.

assemblies during compression 59 because in that case PARC18 molecules tilt more to the surface.87 In fact, at the air/water interface, PARC18 molecules experience weak hydrophobic and hydrophilic forces, which can hardly confine them to a 2D environment so that PARC18 molecules cannot achieve a face-to-face arrangement before the monolayer collapses upon compression. Compression of PARC18 monolayer at the air/water interface can cause decrease in orientational angle that hinders supramolecular chirality and increase in twist angle that promotes supramolecular chirality. The combined effects make the supramolecular chirality remain nearly unchanged through the compression process.

supramolecular chirality. Figure 6 illustrates possible arrangements of PARC18 molecules at the liquid/liquid interface. The proposed mechanism that crowded adsorption makes supramolecular chirality vanish is supported by previous studies on phospholipid monolayers at the air/water interface.86 In the liquid-expanded phase with moderate surface pressure, enantiomerically pure phospholipid molecules can form chiral aggregates, whereas in the liquid-condensed phase with high surface pressure they merely form achiral domains.86 One may expect multilayer adsorption of PARC18 molecules at the liquid/liquid interface when the bulk concentration is sufficiently high. To confirm whether there is multilayer, we estimate the relative density of PARC18 molecules at the interface using χzzz/cos3 θ, which is approximately proportional to Ns according to eq 3. The plot of the density against the bulk concentration can be well-fitted by Langmuir adsorption model (Figure 7), from which the

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CONCLUSIONS We investigate the supramolecular chirality of PARC18 assemblies and the orientation of PARC18 molecules at the water/1,2-dichloroethane interface as well as their dependence on the bulk concentration of PARC18 in the organic phase. It turns out that at low surface densities, PARC18 molecules at the interface exist mainly as monomers and the interface is achiral. At moderately higher surface densities around half-full coverage, PARC18 molecules tilt to the interface and form chiral assemblies to reduce the dipole−dipole repulsions between the headgroups, while near a fully covered monolayer PARC18 molecules tilt to the surface normal and adopt a faceto-face geometry, giving rise to achiral assemblies. The results presented here provide in-depth understanding of the formation of supramolecular chirality at the molecular level and benefit the modulation of supramolecular chirality. Because supramolecular chirality originates from asymmetric arrangement of the building blocks, it should be controlled by tuning the molecular orientation and twist. Liquid/liquid interface can provide suitable environment for controlling the molecular arrangement by adjusting the bulk concentration, the composition of the organic phase, and the pH or the ionic strength in the aqueous phase. It is thus expected that supramolecular chirality can be manipulable at the liquid/ liquid interface. Future work will be focused on precise and dynamic control of supramolecular chirality at liquid/liquid interfaces, which will be of general interest.

Figure 7. Coverage of PARC18 at the interface plotted against the bulk concentration. The circles represent the calculated coverage and the solid line is fit to the Langmuir model. The coverage is obtained by dividing the density with the maximum adsorption density from the fitting.

coverage is obtained by dividing the density with the maximum adsorption density. Details of the fitting can be found in the Supporting Information. Figures 7 and 4 indicate that the supramolecular chirality is more likely to form in a half-full monolayer. It is worth emphasizing that although similar trends for the orientational angle and supramolecular chirality have been observed, change in the supramolecular chirality here is subject to the twist angle of the PARC18 molecules rather than their orientation. This insight can interpret the different dependence of supramolecular chirality of PARC18 assemblies on bulk concentration or molecular density between monolayers at the liquid/liquid interface and at the air/water interface. At the air/water interface, surface pressure or molecular density has little effects on the supramolecular chirality of PARC18

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.7b04170. Detailed description of eq 1, fitting results of SHG curves, calculations of orientational angle, and Langmuir fitting of the adsorption. (PDF) E

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AUTHOR INFORMATION

Corresponding Authors

*Y.G.: E-mail: [email protected]. *M.L.: E-mail: [email protected]. ORCID

Lu Lin: 0000-0003-1308-9158 Yuan Guo: 0000-0001-9644-0470 Minghua Liu: 0000-0002-6603-1251 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the Natural Science Foundation of China (NSFC 21227802, 21503235, 21673251) and the Ministry of Science and Technology of China (MOST 2013CB834504) for financial support.

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DOI: 10.1021/acs.langmuir.7b04170 Langmuir XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.langmuir.7b04170 Langmuir XXXX, XXX, XXX−XXX