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Langmuir Films of Anthracene Derivatives on Liquid Mercury II: Asymmetric Molecules

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Langmuir Films of Anthracene Derivatives on Liquid Mercury II: Asymmetric Molecules 2580 J. Phys. Chem. C 2007, 111, 2580-2587 Langmuir Films of Anthracene Derivatives on Liquid Mercury II: Asymmetric Molecules L. Tamam Department of Physics, Bar-Ilan UniVersity, Ramat-Gan 52900, Israel H. Kraack Department of Physics, Bar-Ilan UniVersity, Ramat-Gan 52900, Israel E. Sloutskin Department of Physics, Bar-Ilan UniVersity, Ramat-Gan 52900, Israel B. M. Ocko Department of Physics, BrookhaVen National Laboratory, Upton, New York 11973 P. S. Pershan Department of Physics and DEAS, HarVard UniVersity, Cambridge, Massachusetts 02138 E. Ofer Department of Physics, Bar-Ilan UniVersity, Ramat-Gan 52900, Israel M. Deutsch* Department of Physics, Bar-Ilan UniVersity, Ramat-Gan 52900, Israel ReceiVed: June 23, 2006; In Final Form: NoVember 28, 2006 The structure and phase sequence of liquid-mercury-supported Langmuir films (LFs) of anthrone and anthralin were studied by surface tensiometry and surface-specific synchrotron X-ray diffraction. In the low-coverage phase the molecules are both side-lying, rather than the flat-lying orientation found for anthracene and anthraquinone. In the high-coverage phase, the molecules are either standing up (anthrone) or remain side- lying (anthralin) on the mercury surface. In contrast with the symmetric anthracene and anthraquinone, both high-coverage phases exhibit long-range in-plane order. The order is different for the two compounds. The structural details, the role of molecular symmetry, the oxygen side groups, and the asymmetry-induced dipole moments are discussed. I. Introduction The previous paper1 detailed the reasons for undertaking the present study, discussed the measurement methods, and pre- sented the results obtained for mercury-supported Langmuir films (LFs) of anthracene and anthraquinone molecules, the structure of which is symmetric relative to both the long and short axes of the molecules. We present here surface tensiometry and X-ray diffraction results for two asymmetric derivatives of anthracene: anthrone and anthralin, shown in Figure 1. These molecules lack mirror Figure 1. Molecular structure of the molecules studied. (a) Anthrone, symmetry with respect to the long axis of the molecules, showing the numbering convention of the carbons; (b) anthralin. Arrows although the mirror symmetry with respect to the central short indicate keto-enol equilibria. The left side is the keto, which has two axis is preserved. The planar anthrone, C14H10O, is a keto form hydrogen atoms at the 10 position. The right side is the enol form, where only one hydrogen atom is bound at the 10 position, and the of 9-anthranol. Anthralin, C14H10O3 has two additional oxygens. - second hydrogen is bound to the oxygen atom at the 9 position of the Both isomers of the keto enol equilibria shown in Figure 1 molecule. can be isolated, but the keto form is the stable one because of the hydrogen OH‚‚‚O‚‚‚OH bonds between the CdO(H) moieties.2 In addition to presenting the results obtained for the asymmetric anthrone and anthralin molecules, we also discuss these results together with those obtained for the symmetric * Corresponding author. E-mail: [email protected]. antharcene and anthraquinone molecules in the previous paper.1 10.1021/jp063937g CCC: $37.00 © 2007 American Chemical Society Published on Web 01/20/2007 II: Asymmetric Molecules J. Phys. Chem. C, Vol. 111, No. 6, 2007 2581 Figure 3. (a) Measured Fresnel-normalized X-ray reflectivity curves (open circles) for anthrone at the nominal area (per molecule) and time Figure 2. π-A isotherm of a LF of anthrone on mercury (circles and (since deposition) indicated. The box model fits (lines) are also shown. solid line). The dashed line is a fit by the Vollmer equation, yielding (b) The surface-normal electron density profiles obtained from the fits, 2 an exclusion area of A0 ) 53 Å /molecule. The arrows mark the corresponding to the lines in part a. Curves in parts a and in b are coverages where X-ray measurements were carried out. shifted from each other by 0.4 and 2, respectively, for clarity. II. Results listed nominal molecular area A and at the listed time after A. Anthrone: Isotherm. The measured pressure-area, π-A, deposition of the LF. Fits to the box model discussed in the 1 isotherm of a LF of anthrone on mercury at room temperature, previous paper (lines) yield the electron density profiles plotted - T ) 24 °C, is shown in Figure 2. A decrease of A from ∼300 in the corresponding lines in Figure 3b, where the mercury ) Å2/molecule to ∼95 Å2/molecule results in only a few millin- anthrone interface is taken as the z-axis origin, z 0Å. ewtons per meter increase in π, as expected for a dilute 2D gas Curves identical to the long-time ones shown in Figure 3 were of molecules. For A < 95 Å2/molecule, however, a steep rise also observed at T ) 4.7 °C and T ) 7.5 °C for the same occurs in π, from ∼8.5 mN/m at A ≈ 95 Å2/molecule to ∼51 coverages, provided that ∼2.5 h or more have passed since the mN/m at A ≈ 48 Å2/molecule. In contrast with other LFs on LF was spread. The XR curves measured for four different mercury, the fast-increasing region at 95 g A g 48 Å2/molecule samples, each studied at 2-3 coverages and 2-3 temperatures, of the isotherm can be only poorly fitted by the Vollmer lead to the conclusion that at high coverages the XR curves equation1 (dashed line in Figure 2, fitted to points in the range vary only with the time elapsed since the spreading of the film, 59 e A e 600 Å2/molecule), and yields an exclusion area of but not with temperature. At low coverages, the dominant 2 A0 ) (53 ( 1.5) Å /molecule. The area of a flat-lying anthrone variation is with time, although a weak dependence on tem- molecule should be equal to, or larger than, that of the perature cannot be ruled out. lw ) × ≈ × ) 2 anthracene, Acalcd l w 12 7.5 90 Å /molecule, We now discuss in details the XR results for low A, marked obtained in the previous paper.1 Here, l is the length and w is with arrow no. 1 in the isotherm in Figure 2, and high A, marked the width of the molecule. The fact that the exclusion area with arrow no. 2. obtained here is much smaller indicates that at least near the 1. Low CoVerage. The modulation period in the XR curves steep rise the molecules are not lying flat on the surface. In at the nominal coverage of A ) 48 Å2/molecule, slightly below fact, A0 is closer to the cross section of the anthracene standing the onset of the plateau in the isotherm, is found to decrease ld ) × ≈ × ) 2 on its side: Acalcd l d 12 3.8 45 Å /molecule, with increasing time following the spreading of the film. This where d is the thickness of the anthracene molecule normal to corresponds to an increase in the thickness of the layer with its plane. However, the unit cell dimensions obtained from the time. The fit of the XR curve measured 1 h after film spreading grazing-incidence diffraction measurements of anthralin in the yields a uniform LF of a (fixed) 8 Å thickness and a (fitted) side-lying phase, discussed below, indicate that the presence electron density of F)(0.28 ( 0.02) e/Å3. Attempts to fit the of the oxygen moieties increases the effective thickness of the XR curve with a thickness of d ≈ 4 Å failed. This thickness is anthralin molecules by ∼0.7 Å over that of anthracene. close to the width of the molecule and therefore supports the Assuming that this conclusion also holds for anthrone, which suggestion above that the molecules at this coverage are side- ld ) also has an oxygen moiety, this results in a calculated Acalcd lying: the molecular plane is roughly normal to, and the l × d ≈ 12 × (3.8 + 0.7) ) 54 Å2/molecule for a side-lying molecular long axis is roughly parallel to, the mercury surface. anthrone molecule, in agreement with the exclusion area of A0 Three hours after deposition the period of the modulations is 2 -1 ) 53 Å /molecule obtained here from the Vollmer equation. shorter, ∆qz ≈ 0.48 Å , yielding an estimate of d ) 2π/∆qz ≈ As A is reduced below 48 Å2/molecule, a plateau is observed 13 Å for the layer thickness. The fact that this value is close to in the isotherm. Previous studies show that such plateaus the ∼12 Å length of a molecule implies that at that time a represent coexistence regions between different-structure considerable fraction, if not all, of the molecules stand up. To phases.3-7 Continuing the line of thought presented above, this allow for the coexistence between a side-lying (SL) phase and plateau may represent a coexistence between phases of side- a standing-up (SU) phase (which is observed to also be the lying and standing-up molecules. The latter phase is also found single, uniform, phase in the high-coverage regime, discussed in alkyl chain molecules.3,5-7 These suggestions, derived here below), we adopt a model used in previous studies for similar from the isotherm alone, are supported by the X-ray measure- coexistence regions.3,5-7 The LF is represented by two layers. ments discussed in the next two subsections. The lower layer is 8 Å thick and comprises the side-lying B. Anthrone: Surface-Normal Structure. Figure 3a shows molecules plus the lower part of the standing-up molecules. The a set of Fresnel-normalized X-ray reflectivity (XR) curves upper layer, of thickness ∼4 Å, comprises the upper part of the measured (open circles) at room temperature, T ) 24 °C, at the standing-up molecules.
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