Liquid Phase Epitaxial Growth and Optical Properties of Photochromic

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Liquid phase epitaxial growth and optical properties of photochromic guest encapsulated MOF thin film Wen-Qiang Fu, Min Liu, Zhi-Gang Gu, Shu-Mei Chen, and Jian Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00935 • Publication Date (Web): 18 Jul 2016 Downloaded from http://pubs.acs.org on July 19, 2016

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Crystal Growth & Design

Liquid phase epitaxial growth and optical properties of photochromic guest encapsulated MOF thin film Wen-Qiang Fu,a Min Liu,a Zhi-Gang Gu,*b Shu-Mei Chen*a and Jian Zhangb a

b

College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, PR China

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fuzhou, P. R. China

ABSTRACT: The reversible photochromic molecule azobenzene was encapsulated into pores of MOF using a modified liquid-phase epitaxial layer-by-layer method successfully. The obtained thin film not only has an oriented, homogenous film with effective guest encapsulation, but also has an isomerisation between tran- and cis- azobenzene in MOF pores under UV and visible light irradiation. Furthermore, the photoluminescent property was studied for azobenzene loaded HKUST-1 thin film with different temperature. This facile preparation strategy and optical property of photochromic guest encapsulation into porous MOF thin film will provide the development of new optical thin film materials possessing photoswitching and photoluminescent properties. KEYWORDS: Liquid phase epitaxial growth; MOF thin film; photochromism; photoluminescent

Introduction The phenomenon of photochromism is well-known as the light induced reversible change of colour, which has developed rapidly to improve the established materials and to discover new devices and sensors for applications.1-5 As photochromic molecules, azobenzene derivatives with two phenyl rings separated by an -N=Ndouble bond, represent the most widely studied photochromism systems.6-8 Upon irradiation with appropriate wavelength light, it is possible to switch between transand cis- isomerisation. The large change in the geometry and polarity of the molecule

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associated with the reversible light induced isomerisation has attracted considerable attention for a wide range of applications on data storage, optical switching, polarization holography, and liquid crystal devices due to its high light sensitivity.7, 8 Incorporation

of

azobenzene

in

various

self-assembled

materials,

such

as

supramolecules, polymers and Ionic liquids, has facilitated the modulation of their reversible functional properties.9-11 Particularly, so far many researchers have introduced the azo-compounds on the porous solid materials to obtain photo-functional materials and study the photochemical behaviour.12-15 As a class of hybrid inorganic-organic porous materials, metal organic frameworks (MOFs) are crystalline materials formed by connecting metal ions via organic linkers, provide a candidate for many applications in gas storage and separation, catalysis, magnetism and sensing.16-18 The high ordered micropores in MOFs provide as micro-containers for encapsulating functional guest to design new materials and study the interaction between host framework and guest species.19,

20

Although there are

some azobenzene group containing MOFs for preparing new photoswitching MOFs,21-23 the synthesis of the molecules with azobenzene group for building MOFs is very difficult and time-consuming.24-26 Therefore, the facile strategy is encapsulating the commercial azobenzene molecules with photochromism into porous MOF to develop composite materials with new or enhanced property. Although in last decade some functional guests (e.g. quantum dot, dye molecules, lanthanide ions) have been encapsulated into the pores of MOFs by using on-pot hydrothermal method or immersing the guest solutions,27 the compositions of the obtained materials with these methods are not easy to control, and

limited to encapsulate guest with high efficiency.

In our recent work, we have developed a modified liquid phase epitaxial (LPE) method for encapsulation of guest (Ti-oxo clusters and lanthanide coordination compounds) in the pores of HKUTST-1 (Cu3BTC2, H3BTC = 1,3,5-Benzenetricarboxylic acid) with in situ layer by layer fashion.28, 29 Thus approach offers an efficient method to control the growth orientations, thickness and homogeneity of thin films. More importantly, the well-defined layer-by-layer LPE assembly fashion encapsulates the functional guest into MOFs without disrupting the growth of the MOF structures. As an extension of


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our previous works, herein, we use modified LPE method to encapsulate azobenzene molecule directly into MOF thin film (scheme 1 bottom and Scheme S1), since it can offer

a

high

effective

and

homogeneous

encapsulation.

The

commercial

trans-azobenzene was selected as the photochromic guest species, which are well known for preparing photoswitching materials and studying the photochemistry in dynamic behavior. The typical 3-D MOF HKUST-130 containing large numbers of ordered micropores was chosen as the host framework for guest encapsulation. Here the photochromic guests were encapsulated into MOF thin film using modified LPE method successfully and used for studying the photochromic behavior between transand cis- isomerisation under photo-induce or temperature, which may open a facile strategy to develop new composite materials for the applications in optical sensors and devices.

Scheme 1. Schematic presentation of the reversible isomerization between tran- and cis-azobenzene under photo-induce (top); the in situ layer-by-layer growth of



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trans-azobenzene encapsulated HKUST-1 thin film using modified LPE method, showed a cis- to trans-azobenzene@HKUST-1 film (bottom).

Experimental section Materials and Instruments. All the reagents and solvents employed were commercially available and were used as received without further purification. The quartz glass substrates were treated with a mixture of concentrated sulfuric acid and hydrogen peroxide (30 %) with a volume ratio 3:1 at 80 °C for 30 minutes and then cleaned with deionized water and dried under nitrogen flux for the next preparation. The samples grown on functionalized Au substrate were characterized with infrared reflection absorption spectroscopy (IRRAS). IRRAS data were recorded using a Bruker Vertex 70 FTIR spectrometer with 2 cm-1 resolution at an angle of incidence of 80° relative to the surface normal. Powder X-ray diffraction (PXRD) analysis was performed on a MiniFlex2 X-ray diffractometer using Cu-Kα radiation (λ = 0.1542 nm) in the 2θ range of 5–20° with a scanning rate of 0.5° min−1. Scanning electron microscope (SEM) images for the morphology of thin films were measured by JSM6700. XPS spectra for the azobenzene@HKUST-1 thin film was measured by ESCALAB 250Xi. UV-vis spectra for the solid samples were performed on Lambda35. Fluorescence spectra for the sample in present work were performed on an Edinburgh Analytical instrument FLS920. Preparation of functionalized substrates. The COOH-functionalized self-assembled monolayers (SAMs) on Au were prepared by immersing Au substrates into 1mM/L ethanolic solutions of 16-Mercaptohexadecanoic acid (MHDA) for 24 hours and then rinsed with the pure ethanol and dried under nitrogen flux for the next preparation. The OH-terminated quartz glass substrates were treated with a mixture of concentrated sulfuric acid and hydrogen peroxide (30%) with a volume ratio 3:1 at 80 °C for 30 minutes and then cleaned with deionized water and dried under nitrogen flux for the next preparation. Fabrication of HKUST-1 thin film HKUST-1 thin films used in the present work were grown on OH-terminated quartz glass substrate using the liquid-phase epitaxy (LPE) spray method, which yields thin film with [111]orientation.


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The HKUST-1 thin film were fabricated using the following diluted ethanolic solutions: copper acetate (1 mM) and BTC (1,3,5-benzenetricarboxylic acid) (0.4 mM). The modified pump method is adopted in this work which is descripted in the earlier work. The immersion times were 15 min for the copper acetate solution and 30 min for the BTC solution. Each step was followed by a spray step with pure ethanol to remove residual reactants. A total of 100 growth cycles were used for HKUST-1 grown on functionalized Au and quartz glass substrates in this work. Fabrication of trans-azobenzene@HKUST-1 thin film The trans-azobenzene@HKUST-1

thin film were fabricated using the following diluted

ethanolic solutions: copper acetate (1 mM), BTC (1,3,5-benzenetricarboxylic acid) (0.4 mM) and trans-azobenzene solution (0.5 mM). The modified pump method is adopted in this work which is descripted in the earlier work. The immersion times were 15 min for the copper acetate solution, 30 min for the BTC solution and 10 min for trans-azobenzene solution. Each step was followed by a spray step with pure ethanol to remove residual reactants. A total of 100 growth cycles were used for trans-azobenzene@HKUST-1 grown on functionalized Au and quartz glass substrates in this work.

Results and Discussion The azobenzene molecule is very important on the application of the light emission materials. Recently the azobenzene functionalized organic linkers used to assembly azo-MOF exhibits the expected isomerization when exposed to UV and visible light. However, the synthesis of azobenzene functionalized linkers is expensive and time-consuming. The facile way to synthesize the azo-containing MOF is encapsulating the azobenzene into MOF pores, which also can be shown the expected isomerization and applied for the photoswitching. The UV-Vis spectra of azobenzene ethanolic solution is dominated by two absorbencies, the intense wavelength π-π* absorbance band at ~317 nm and the weak n-π* absorbance band around 432 nm as shown in scheme 1 (top) and Figure S1. After irradiation with 365 nm for 0, 1, 6, 11, 21 and 31 min respectively, the n-π* absorbance around 432 nm increases and the π-π* absorbance around 317 nm is decreased, indicating the occurrence of trans- to cis-



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photoisomerization. When the sample is exposed to the visible light irradiation for 1, 2, 3, 5, 10 and 20 min, respectively, the the increased π-π* absorbance band at ~317 nm and the decreased n-π* absorbance band at ~432 nm showed that the spectrum changes continuously from the cis- to the trans-state, demonstrating a good reversible photochromic phenomenon under different wavelength light irradiation. While previous studies of functional guest were encapsulated into MOF pores with high orientation, homogeneous and high effective using LPE layer by layer method, the commercial azobenzene was encapsulated into MOFs using the same method. The setup of preparation procedure was shown in Figure S1, which was called modified LPE pump method. During the preparation, the Cu(OAc)2, H3BTC, trans-azobenzene ethanolic solutions and pure ethanol solutions were injected into the reaction cell with hydroxyl-functionalized quartz glasses and 16-Mercaptohexadecanoic acid (MHDA) SAMs-functionalized Au substrate sequentially. The reaction solution was pumped out from cell after each reaction step. Then a thin film was obtained after repeating 100 cycles, which is named trans-azobenzene@HKUST-1 thin film. The obtained trans-azobenzene@HKUST-1 composite film was characterized by XRD, IRRAS, SEM, EDS and XPS. The out of plane X-ray diffraction showed XRD peaks of all the samples at 6.8, 13.6, 11.6 and 17.5° are in accord with the simulated XRD peaks at (200), (400), (222) and (333) of HKUST-1, indicating that the framework of thin film maintained the crystallinity and grow along [100] and [111] orientations on the functionalized quartz glasses (Figure 1a). Compare to the simulated powder XRD of pristine HKUST-1 grown on quartz glass, there a weak peak at (200) and (400) with [100] orientation due to the flexible azobenzene molecules influence the perfect growth crystalline orientation. Using this method to grown trans-azobenzene@HKUST-1 film on MHDA-SAM functionalized Au substrate (MHDA = 16-Mercaptohexadecanoic acid), the relative intensities of (200)/(400) were decreased comparing to the pristine HKUST-1 thin film(Figure S2), which can demonstrate the tans-azobenzene was loaded in

the

pores

of

HKUST-1.31,

32

For

study

the

IRRAS

(Infrared

Reflection-Absorption Spectroscopy) spectra of trans-azobenzene@HKUST-1 films, the new IRRAS absorbance bands (Figure 1b) at 1535 cm-1 are ascribed to -N=N-


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vibrations of trans-azobenzene and the change in the reflection adsorption spectra at ~515 nm (Figure 1f), combining to the Raman shift (Figure 1d) at 1538, 1003, 826 and 742 cm-1 and color change in the optical images (Figure 2a,b) showing the molecule trans-azobenzene was encapsulated into HKUST-1 film successfully. Furthermore, the XPS spectra (Figure 1e) at 403 ev is identical to the N 1s in azobenzene. The optical image with rainbow colour (Figure 1c) and SEM images (Figure 2c) showed a homogeneous composite film and EDS data (Figure S3) displayed an effective encapsulation with 20% (calculated by the ratio of N/Cu).

Figure 1. the out plane XRD (a), IRRAS (b), Raman spectra (d) and reflection spectra (f) of HKUST-1 thin film and azobenzene encapsulated HKUST-1 thin film prepared by in situ LPE method; optical image with rainbow colour (c) and XPS spectra (e) of azobenzene encapsulated HKUST-1 thin film prepared by in situ modified LPE method.



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Figure 2. The optical morphology of HKUST-1 thin film (a) and azobenzene encapsulated HKUST-1 thin film and SEM image of azobenzene encapsulated HKUST-1 thin film.

In order to investigate photoisomerization of the obtained composite film, the OH-functionalized quartz glass was chosen as the substrate for preparation of trans-azobenene@HKUST-1 thin film. Compare to the UV-vis spectra of azobenzene solution, the UV-vis spectra of trans-azobenzene encapsulated HKUST-1 on quartz glass showed a different absorbance bands using pristine HKUST-1 thin film with 100 cycles as background (Figure 3). The absorbance bands of at ~270 and ~370 nm were accord to that of solid powder azobenzene (Figure 3a). The absorbance band of at ~270 nm was decreased (tans- to cis- photoisomerization) after UV light irradiation for 1, 6, 15, 30 min in the UV-vis spectra of azobenzene@HKUST-1 film and was increased (cis- to tans- photoisomerization) after visible light irradiation for 1, 6, 15 and 30 min, showing that a photoswitching thin film was obtained.


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Figure 3. The UV−Vis absorption spectra of trans-azobenzene@HKUST-1 thin film and powder solid azobenzene. Time-dependent UV−Vis absorption spectra of trans-azobenzene@HKUST-1 thin film grown on quartz glass with

365 nm

irradiation for 0, 1, 6, 15 and 30 min, respectively; followed by visible light irradiation for 1, 6, 15 and 30 min, respectively.



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Figure 4. photoluminescent property (a) of azobenzene@HKUST-1 thin film at the excitation wavelength 374 nm under 303, 323 and 353 K, respectively. Note: R- square is 0.892.

The photoluminescent property of azobenzene@HKUST-1 thin film has been investigated and shows the emission maxima at ~560 nm (λex=374 nm, Figure S4) as shown in Figure 4a, which is attributable to luminescent emission of powder azobenzene molecule due to Cu(II) in HKUST-1 can quench the luminescence of the host framework and identical to the luminescent property of solid azobenzene (Figure S5).

In

addition,

the

temperature

dependent

photoluminescent

property

of

azobenzene@HKUST-1 thin film was carried under 303, 323 and 353 K showed that a slightly decreased intensity after increasing the temperature. Figure 4b showed there was a linear relationship between relative intensity and temperature after fitting the relative intensity of the absorbance band at 560 nm. The photoluminescent property of azobenzene loaded into HKUST-1 thin film under different temperature demonstrated


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the photoisomeric guest can be loaded into MOF thin film to form the dynamics optical film material with photoluminescent emission.

Conclusion In summary, we have applied a modified liquid phase epitaxial pump method for preparation of photochromic molecule azobenzene loaded MOF HKUST-1 with high oriented and homogeneous thin film. The obtained thin film not only had a photoisomerization behaviour under ultraviolet (tans- to cis-) and visible light irradiation (cis- to tans-) when azobenzene was encapsulated into HKUST-1 pores, but also had a temperature dependent photoluminescent emission. This study of azobenzene encapsulation into porous MOF thin film can provide a facile strategy for preparing the photochromic thin film materials and open a new dynamics optical properties for the development of multifunctional optical devices and sensors.

ASSOCIATED CONTENT Supporting Information. Experimental and characterization details; additional figures and images; XRD patterns, EDS and photoluminescent spectrum. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * Corresponding Author e-mail: [email protected] and [email protected]

ACKNOWLEDGMENT This work is financially supported by the NSFC (21425102, and 21521061).

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For Table of Contents Use Only

Liquid phase epitaxial growth and optical properties of photochromic guest encapsulated MOF thin film Wen-Qiang Fu,a Min Liu,a Zhi-Gang Gu,*b Shu-Mei Chen*a and Jian Zhangb a

b

College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, PR China

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fuzhou, P. R. China

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Synopsis: An in situ liquid phase epitaxy (LPE) layer-by-layer approach is developed to successfully load photochromic molecule azobenzene into MOF HKUST-1 thin film, giving an oriented and homogenous composite azobenzene@HKUST-1 thin film. The obtained azobenzene@HKUST-1 film has photoswitching behavior and photoluminescent property, showing a good potential for functional optical sensors and devices.


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Liquid Phase Epitaxial Growth and Optical Properties of Photochromic

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