Synthesis of Ultrathin Nanosheets of Perylene - Crystal Growth & Design

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Synthesis of Ultrathin Nanosheets of Perylene Yiding Lai, Huihui Li, Jiannan Pan, Jia Guo, Longtian Kang, and Zhanmin Cao Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg5015016 • Publication Date (Web): 17 Feb 2015 Downloaded from http://pubs.acs.org on February 18, 2015

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Crystal Growth & Design

Synthesis of Ultrathin Nanosheets of Perylene Yiding Lai, †,‡,§ Huihui Li,‡,§ Jiannan Pan,‡,§ Jia Guo,†,‡,§ Longtian Kang*,‡,§and Zhanmin Cao *,† †

College of Metallurgy and Ecological Engineering, University of Science and Technology

Beijing, Beijing, 100083 (P.R. China) ‡

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou, 350002 (P. R. China). §

Key Laboratory of design and assembly of functional nanostructures, Chinese Academy of

Sciences, Fuzhou, 350002 (P.R. China)

ACS Paragon Plus Environment

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ABSTRACT: Here, we report free-standing nanosheets with the thickness of 1.1 nm, however their width decreases to ~ 50 nm and RWT is ∆G(hkl does the surface ) )

grows. The lower

≠ ∆G(hkl )

is, the faster the growth of surface is until it disappears. The structure of

molecule crystal means that

≠ should ∆G(hkl )

closely relate to space steric hindrance when a molecule

in solution phase joins in a crystal surface.21 Based on structure of α-phase perylene, we can speculate

∆G±≠(001) < ∆G±≠( 010) ≈ ∆G±≠(100) for

perylene intrinsic crystal, while

∆G±≠(001) > ∆G±≠(010) ≈ ∆G±≠(100) after

CTAB adsorbs on the ±(001) planes. Therefore, perylene nanoflakes can be easily obtained in


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CTAB solution when the growth of ±(001) planes is limited by CTAB.13 An interesting phenomenon is that so-called “selective adsorption” of CTAB can be gradually destroyed in further growth stage as ∆µ increases. It may be attributed to stronger interaction of peryleneperylene than that of perylene-CTAB, which finally results in the growth of ±(001) plane faster and in the formation of thicker nanoflake, even rod-like crystal structure as the concentration of PeClO4 increases from 1.0 mM to 3.0 mM and 5.0 mM. In brief, the formation of perylene UTNs is not only dependent on CTAB micelle-induced 2D nucleation but also on selective adsorption of CTAB on ±(001) plane of perylene crystal as well as aging time. The effect of shape and size of perylene crystal on optical properties were also studied based on UV-Vis absorption spectra in Fig. 4 and photoluminescence (PL) spectra in Fig. S7. Blueshift of the strongest absorption peaks at the range from 300 nm to 450 nm can be found from rods, UTNs to nanoflake in water as compared with perylene solution. It is usually explained as “size-effect” due to lattice softening when all of these crystals were seen as “sphere”.14 Indeed, the sequence for the size of these “spheres” is rod >UTNs >nanoflake, which is consistent with the maximal size of perylene crystal, as seen in Fig. 1 and Fig. 2 . According to the explanation, the red-shift of absorption peak at ~470 nm, which is ascribed to the formation of aggregate, is easily understood as size-effect of aggregate. Unfortunately, we cannot explain the change of absorption peaks between 250 nm and 350 nm. The peak at 262 nm is attributed to the absorption of perylene monomer, while the peak at ~282 nm comes from the corresponding aggregate. However, as compared with the absorption of perylene monomer at 262 nm, more red-shift of the absorption peak of UTNs than that of rod can not be understood according to above mechanism of “size effect”. Why? Usually, the peaks from 250 nm to 350 nm are seen from electronic transition (ET) at intramolecular short axis direction (Y) of perylene ( see inset


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map in Fig. 4).14,22-23 The red-shift of absorption peaks means that as compared to the energy level of monomer, that of ET in aggregate reduces due to limited molecule oscillation. More red-shift of absorption peak also means that aggregates form more and the size increases along those directions in some plane perpendicular to perylene ring. In α-form perylene crystal, the special plane can be approximately seen as (001) plane because the angle of (001) plane with perylene molecules is close to 90º (see Fig. 2E). Therefore, more red-shift of absorption peak of perylene crystal between 250 nm and 350 nm, as compared to absorption of monomer at 262 nm, theoretically reflects the increase of the size of perylene crystals along those directions in (001) plane, which also meets our results. As shown in Fig. 1 and Fig. 2, the dimension of nanoflake, rod and UTNs in the (001) plane is 250 nm, 400 nm and 800 nm, respectively. Obviously, the red-shift of absorption peak of perylene crystal at violet region still meets size-effect when asprepared crystals were treated as 2D flake rather than “sphere”. Actually, the absorption peaks at the range from 300 to 600 nm in Fig. 4 is not only relevant to ET from in-plane (X-Y plane), but also to ET from out-plane. 22-23 Thus, all of crystal structures could be approximately seen as “sphere”. More blue-shift of absorption peaks occurs when the “sphere” becomes smaller. It reminds us that the size effect of crystal is closely associated with its orientation and/or morphology. Unfortunately, we cannot find any clues on the change of thickness of perylene crystal along ±[001] directions from the red-shift, blue-shift and the change of intensity of steady-state absorption peak. For the same reasons, we cannot also gain any information on UTNs from PL spectra in Fig. S7.


13


262 nm

282 nm

470 nm Y

e Absorbance

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d X

c

b a 250 300 350 400 450 500 550 600 650 700

Wavelength(nm)

Figure 4. Absorption spectra of a) perylene in CH2Cl2, b) nanoflake in water, c) rod in water, d) UTNs in water and e) bulk powder. In conclusion, we have developed a facile and efficient method to prepare UTNs, which formed through only weak π-π bond and/or Van der Waals forces in LPCR system. In the work, the shape-controlled synthesis of α-form perylene crystal were achieved by controlling the growth of ±(001) planes when different PeClO4 concentration was used in the CTAB-assisted chemical reaction. UTNs of perylene prone to forming at low monomer µ and short aging time, while thicker nanoflakes, even rods appeared at high monomer µ and long aging time due to destroyed CTAB selective-adsorption on the ±(001) planes in further growth stage of 2D nucleus. It was proved that the formation of perylene crystal in our experiment may be attributed to CTAB-induced 2D nucleation and layer-and-layer growth. The change of UV-Vis absorption spectra of different shape of perylene crystal reminded us that we must take the shape of crystal into account in order to investigate more realistic size-effect. Unfortunately, steady-state optical spectra are not an efficient way to detect the formation of the perylene UTNs due to complicated ET. Further study on UTNs is in progress. In a word, an efficient path to prepare UTNs of 3D


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crystal formed via only weak intermolecular interaction was achieved in CTAB-assisted chemical reaction on the base of the mechanism of soft-template-assisted 2D nucleation and limited layer-and-layer growth of 2D nucleus. The work is expected to promote the research and application of nanosheets of organic small molecule semiconductor.

ASSOCIATED CONTENT Supporting Information Detail experimental procedures, MS-EI Mass spectra, 400 M 1H NMR spectra, supplementary SEM images, AFM image, XRD patterns, UV-Vis absorption spectra and fluorescence spectra as well as the change of conductivity of CTAB in the mixture with its concentration. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * [email protected]; [email protected] . Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We gratefully acknowledge the financial from the National Natural Science Foundation of China (No.21252001, 21473204), the Special Project of National Major Scientific Equipment Development of China (No. 2012YQ120060).


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For Table of Contents Use Only

Synthesis of Ultrathin Nanosheets of Perylene Yiding Lai, Huihui Li, Jiannan Pan, Jia Guo, Longtian Kang* and Zhanmin Cao*

Ultrathin nanosheets (UTNs) of α-form perylene crystal with thickness less than 10 nm were synthesized by controlling its growth along the [001] direction in liquid-phase chemical reaction (LPCR), in which CTAB-induced two-dimension (2D) nucleation and layer-and-layer growth model were proved.


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Synthesis of Ultrathin Nanosheets of Perylene - Crystal Growth & Design

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