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Supplementary Information

Centimetre scale micropore alignment in oriented polycrystalline

Metal-Organic Framework films via heteroepitaxial growth.

Paolo Falcaro1, 2, 3, 4*, Kenji Okada5, 6, Takaaki Hara5, Ken Ikigaki5, Yasuaki Tokudome3, 5, Aaron

Thornton2, Anita J. Hill2, Timothy Williams7, Christian Doonan4, Masahide Takahashi3, 5*

1 Graz University of Technology, Institute of Physical and Theoretical Chemistry

Stremayrgasse 9/Z2, 8010 Graz. 2Division of Materials Science and Engineering, CSIRO, Private

Bag 33, Clayton South, MDC, Victoria 3169, Australia. 3 International Institute for Nano/Meso

Materials Science, Osaka Prefecture University, Sakai, Osaka, Japan. 4 Department of Chemistry,

The University of Adelaide, Adelaide, South Australia 5005, Australia. 5Department of Materials

Science, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka, Japan. 6

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita,

Osaka, Japan. 7 Monash Centre for Electron Microscopy, Monash University, Victoria 3800,

Australia.

Contents Figure S1. Schematic illustration showing crystal lattice of Cu(OH)2 and Cu2(BDC)2 .................... 3

Figure S2. Time evolution of Cu2(BDC)2 MOFs from Cu(OH)2 nanotubes ................................... 4

Figure S3. Energy dispersive X-ray analysis on Cu2(BDC)2 MOFs ............................................... 5

Figure S4. Experimental setups of XRD measurments ................................................................. 6

Figure S5. Conversion of Cu(OH)2 nanotube array to Cu2(BDC)2 forest ....................................... 7

Figure S6. Proposed unit cell of Cu2(BDC)2 MOFs at the interface............................................... 8

Figure S7. Summary of Cu-based MOFs prepared using different ligands ................................... 10

Figure S8. Cross-sectional FE-SEM images and corresponding schematics of oriented Cu2(BDC)2

MOFs grown at different reaction time ...................................................................................... 11

Figure S9. Self-standing film of oriented Cu2(BDC)2 MOFs ...................................................... 12

Figure S10. SEM and XRD investigation of oriented Cu(OH)2 nanobelt films ............................ 13

© 2016 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NMAT4815

NATURE MATERIALS | www.nature.com/naturematerials 1

http://dx.doi.org/10.1038/nmat4815

2

Figure S11. SEM and XRD investigation of oriented Cu2(BDC)2 MOF films .............................. 14

Figure S12. Comparison between oriented MOFs in the present study and MOFs previously reported

and classified as oriented MOFs ............................................................................................... 15

Figure S13. SEM and XRD investigation of oriented Cu2(BDC)2(DABCO) MOFs on Cu(OH)2

nanobelts. ............................................................................................................................... 17

Figure S14. N2 gas isotherms of Cu2(BDC)2(DABCO) film. ...................................................... 18

Figure S15. Ag nanoparticles impregnation into an oriented Cu2(BDC)2(DABCO) film ............... 19

Figure S16 XRD patterns of DMASP-doped and undoped Cu2(BPDC)2 ..................................... 20

Figure S17. Fluorescence measurements setup and details ......................................................... 21

Figure S18. Polarization photoluminescence measurements of Cu2(BDC)2(DABCO) after

impregnation of DMASP ......................................................................................................... 22

Figure S19. Comparison of anisotropic optical properties on reported surface mounted MOFs ..... 23

Figure S20. Schematic illustration of the fabrication procedure for oriented Cu(OH)2 nanobelt films

on a substrate .......................................................................................................................... 25





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Figure S1. Schematic illustration showing crystal lattice of Cu(OH)2 and Cu2(BDC)2 from ac and ab

projections, respectively. This illustration corresponds to crystal structure on the surface of Cu(OH)2

nanotubes and nanobelts. Cu positions are highlighted by different colors for both crystals (green for

Cu(OH)2 and blue for Cu2(BDC)2). These values indicate that Cu(OH)2 and Cu2(BDC)2 MOFs provide

lattice matching conditions for heteroepitaxial growth.





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Figure S2. Time evolution of Cu2(BDC)2 MOFs from Cu(OH)2 nanotubes. Schematic illustration of

(a) Cu(OH)2 and (b) Cu2(BDC)2 MOFs growth on vertically-oriented Cu(OH)2 nanotubes exposing

the hydroxides to the ligand solution. SEM images of Cu2(BDC)2 MOFs prepared at different

conversion time (0, 60, 150, and 300 s) (c)-(f).





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Figure S3. Energy dispersive X-ray analysis on Cu2(BDC)2 MOFs grown from vertically-oriented

Cu(OH)2 nanotubes on a Cu-coated silicon wafer. The elemental map shows that the MOF crystals

homogeneously grow on the Cu(OH)2 nanotube film.





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Figure S4. Schematic illustration of the experimental setups for (a) out-of-plane (θ-2θ), (b) in-plane

(2θχ/φ) and (c) azimuthal angle dependence (φ) measurements.

Out-of-plane measurements are performed in the typical (θ-2θ) configuration. Thus the sample

position is fixed while both source and detector move maintaining the geometrical configuration θ-

2θ1.

For in-plane measurements, the position of the X-ray source is fixed while the detector moves parallel

to the substrate; simultaneously the sample stage rotates with half speed of the detector (θχ = φ)2. Two

initial sample orientations were set in order to confirm the oriented polycrystalline MOF film nature.

First setting: the X-ray incident angle is set parallel to the longitudinal direction of nanobelts, then the

detector scans the sample typically in the 0-20° angular range (). Second setting: the X-ray incident

angle is set perpendicular to longitudinal direction of nanobelts and the detector moves again in the

0≤≤20° range.

In the azimuthal angle dependence measurement, both the X-ray incident beam and the detector angles

are fixed. Note that the detector is positioned to a diffraction angle (2θχ) of interest3. Then the sample

stage rotates from 0º to 360º.

The in-plane investigation with different sample rotation angles and azimuthal angle dependence

measurements are considered powerful methods to confirm orientation of crystal face perpendicular

to the substrate4,5,6. Supplementary Videos 1-3 are proposed to provide a better understanding of the

experimental set-ups used to carry out the out-of-plane, in-plane and azimuthal angle dependence

measurements.





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Figure S5. Conversion of Cu(OH)2 nanotube array to Cu2(BDC)2 forest. (a) Schematic illustration of

Cu2(BDC)2 MOFs grown on vertically-oriented Cu(OH)2 nanotubes. (b) XRD patterns collected for

powder (black) and film using out-of-plane (OOP: blue) and in-plane (IP: red) geometries. SEM image

of (c) Cu(OH)2 nanotube array grown on a Cu film and (d) Cu2(BDC)2 MOF crystals grown on the

Cu(OH)2 nanotubes.





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Figure S6. Proposed unit cell of Cu2(BDC)2 MOFs at the interface from selected area electron

diffraction (SAED). (a) SAED obtained at the interface between Cu(OH)2 nanotube and MOF crystal.

(b) Slightly tilted Cu2(BDC)2 sheets with P2 symmetry at the vicinity of interface proposed from

SAED of (a). (c) Unit cell of reported Cu2(BDC)2 MOFs with P4 symmetry. (d) Unit cell of slightly

tilted Cu2(BDC)2 MOFs at the interface with P2 symmetry. Although the SAED suggests P2 symmetry

for Cu2(BDC)2 MOFs at the interface, XRD results (Fig. 3d, e and Supplementary Fig. S5) indicate

Cu2(BDC)2 MOFs with P4 symmetry. (e) A proposed structural model of Cu2(BDC)2 crystallites on

Cu(OH)2 surfaces. Red triangle and green bar indicate the MOF crystallite and Cu(OH)2, respectively,

nanorod shown in an inset of (a), and yellow circle corresponds to the measured spot of SAED.





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These results, can be explained by the fact that the Cu2(BDC)2 MOFs are distorted and slightly tilted

locally at the interface (P2 symmetry), however; in the majority of the film the distortion between the

MOF sheets relaxes and the MOF exhibits P4 symmetry. This distortion results from an interlayer

space of 5.80Å for the Cu2(BDC)2 sheets with P4 symmetry which is slightly larger than twice the

length of the [100] (5.90Å) lattice parameter of Cu(OH)2. Accordingly, the slight mismatch at the

interface is compensated by the distortion of MOF sheets which is accommodated by their flexible

structure.

It should be noted that the basic angle of a MOF crystal is in good agreement with a tilted angle of

MOF sheets from SAED. (f) Schematic illustration of a MOF crystal consisting of slightly tilted MOF

sheets. (g) TEM image of a MOF crystal. (h) Proposed unit cell of Cu2(BDC)2 with P2 symmetry at

the interface between Cu(OH)2 and the MOF.





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Figure S7. Summary of Cu-based MOFs prepared using different ligands. The out-of-plane and in-

plane XRD measurements were conducted on the Cu-based MOFs grown on oriented Cu(OH)2

nanobelt films. The values of lattice mismatch were calculated between the a axis of MOFs and the c

axis of Cu(OH)2. Please note that the schematic showing irradiation of the MOF film by the X-ray

beam in each of the different set ups (OOP, IPpara, IPperpen), depicts the MOF crystals, (blue) on the

Cu(OH)2 oriented nanobelts, as separated for visual clarity. For an actual representation of the MOF

film, please refer to the SEM image and the schematics proposed in Figure S8.





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Figure S8. Cross-sectional Field Emission-SEM (FE-SEM) images of oriented Cu2(BDC)2 MOFs

grown on Cu(OH)2 at different reaction time (0, 2 and 10 minutes). The cross-section images were

taken from (a)-(c) perpendicular and (d)-(f) parallel direction with respect to the longitudinal side of

Cu(OH)2 nanobelts. These FE-SEM images indicate that all the Cu2(BDC)2 MOF crystals are

connected from the bottom. (g) Total thickness of Cu2(BDC)2 MOF film on Cu(OH)2 as a function of

the conversion time. After c.a. 10 min conversion time, no further increase is detected. The thickness

is measured by stylus profilometer. (h) Azimuthal angle dependence of in-plane XRD signal of (010)

diffraction. Such an orientation is maintained for longer conversion times (1 and 12 hours). Conversion

time exceeding 12 hours were not investigated. (i) A conversion experiment on free Cu(OH)2

nanoblets in solution was performed and investigated with infrared spectroscopy. FTIR spectra of

Cu(OH)2 nanobelts (black line), H2BDC (red line) and Cu2(BDC)2 prepared from Cu(OH)2 nanobelts

in 15 min conversion time (blue). This spectroscopic investigation demonstrates that Cu(OH)2

nanobelts can be completely converted to Cu2(BDC)2 MOF within 15 min conversion time.





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Figure S9. Self-standing film of oriented Cu2(BDC)2 MOFs (conversion time 10 min). Cu2(BDC)2

MOFs grown on oriented Cu(OH)2 nanobelts were detached from the Si wafer by dissolving (acetone)

a sacrificial layer situated between the Cu2(BDC)2 MOFs and Si wafer (a)-(c). The detached

Cu2(BDC)2 MOF film possess sufficient mechanical strength to be moved onto a different substrate

(i.e SiO2 support) (d)-(i). This result, showing the fabrication of a self-standing MOF film, confirms

that the constituent MOF crystals are physically connected to each other. It should be noted that this

method allows a MOF film to be deposited, with controlled orientation, on any substrate including

conducive, semiconductive and insulating materials with desired shapes. This versatility is highly

desirable for practical applications.





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Figure S10. SEM and XRD investigation of oriented Cu(OH)2 nanobelt films. (a) SEM image of an

oriented Cu(OH)2 nanobelt film. (b) In-plane XRD patterns of the oriented Cu(OH)2 nanobelt. X-ray

incident angle was varied (black line: perpendicular to longitudinal direction of nanobelts, red line:

parallel to those). (c) Azimuthal angle dependence of intensity profiles (φ scan) of the (200) (black

line) and (002) (red line) reflection.





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Figure S11. SEM and XRD investigation of oriented Cu2(BDC)2 MOF films. (a) SEM image of

Cu2(BDC)2 MOFs grown on oriented Cu(OH)2 nanobelts (inset with a schematic showing the MOF

film growing on the Cu(OH)2 nanobelt film). (b) In-plane XRD patterns of the Cu2(BDC)2 crystalized

on the oriented Cu(OH)2 nanobelt film. X-ray incident angle was varied (black line: perpendicular to

the longitudinal direction of nanobelts, red line: parallel to the longitudinal direction of nanobelts). (c)

Azimuthal angle dependence of intensity profiles (φ scan) of the (002) reflection of Cu(OH)2 (black

line) and (100) reflection of Cu2(lattice constants. The result supports the heteroepitaxial growth of

Cu2(BDC)2 on Cu(OH)2. BDC)2 (red line). (d) Azimuthal angle dependence of intensity profiles (φ

scan) of the (200) reflection of Cu(OH)2 (black line) and (010) reflection of Cu2(BDC)2 (red line).

These XRD measurements confirm that the a axis of Cu2(BDC)2 crystals is codirectional with the c

axis of Cu(OH)2 crystals. Correspondingly the b axis of Cu2(BDC)2 crystals is codirectional with to

the a axis of Cu(OH)2 crystals as expected from the





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Figure S12. Comparison between oriented MOFs in the present study and MOFs previously reported

and classified as oriented MOFs. Three general approaches are reported in literature for the fabrication

of oriented MOFs: (1) combined layer-by-layer growth and the Langmuir-Blodgett methods (e.g. by

R. Makiura and H. Kitagawa group 7 , 8 ), (2) layer-by-layer growth on SAM (Self-Assembled

Monolayer) (e.g. by C. Wöll, R. Fischer and J. T. Hupp groups9,10,11), (3) MOF growth on SAM (e.g.





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by T. Bein group12). To compare these reported methods with the here proposed heteroepitaxial growth,

the reported protocols were followed for the fabrication of oriented MOFs on cm scale substrates (c.a.

1 cm x 1 cm squared substrate). NAFS-13 (PdTCPP-Cu, (TCPP=Tetrakis(4-

carboxyphenyl)porphyrin)) was prepared combining the layer-by-layer growth with the Langmuir-

Blodgett methods (Sci. Rep. 3, 2506 (2013), Nature Mater. 9, 565 (2010)). Cu2(BDC)2 and

Cu2(BPDC)2 were prepared using the layer-by-layer growth on SAM approach (J. Am. Chem. Soc.

133, 8158 (2011), Sci. Rep. 2, 921 (2012)). Cu3(BTC)2 was prepared by MOF growth on SAM

approach (J. Am. Chem. Soc. 129, 8054 (2007)). Sample preparation time (substrate preparation time

and MOF growth time) is shwon in the table (left column). The time required for the synthesis was

the minimum to obtain an adequate intensity of XRD patterns. As shown in the XRD results, all the

synthesis procedures allow for the growth of MOF crystals with out-of-plane orientation. On the other

hand, in-plane measurements with sample rotation and azimuthal angle dependence of intensity

profiles clearly indicate preferential orientation only for the heteroepitaxial method proposd in this

work. This means that the heteroepitaxial growth mechanism is unique and orients MOF crystals both

parallel and perpendicular to the substrate. Additionally, from substrate preparation to the final MOF

film, the heteroepitaxial oriented MOF films only takes a few hours; substantially shorter compared

to the previously reported protocols.





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Figure S13. Oriented Cu2(BDC)2(DABCO)13 MOFs on Cu(OH)2 nanobelts. (a,b) Top-view and cross

section FE-SEM images of the oriented Cu2(BDC)2(DABCO) MOFs prepared using the

heteroepitaxial growth from aligned Cu(OH)2 nanobelt film. (c) XRD patterns from the same

Cu2(BDC)2(DABCO) MOF film; out-of-plane (blue line), in-plane (red and black line, X-ray incident

angle is parallel and perpendicular to longitudinal direction of nanobelts at = 0°). (d) Azimuthal angle

dependence of intensity profiles of the (200) reflection of Cu(OH)2 at a diffraction angle of 34.03

(black line) and (001) reflection of Cu2(BDC)2(DABCO) at a diffraction angle of 9.17° (red line). The

Cu2(BDC)2(DABCO) MOFs epitaxially-grown on aligned Cu(OH)2 nanobelt film were prepared by

the following process. The aligned Cu(OH)2 nanobelt films were immersed into a solution containing

10 mL of methanol, 7 mg of H2BDC, and 4.8 mg of DABCO at 60 ºC for 90 min. The lattice mismatch

between the a axis of Cu2(BDC)2(DABCO) and the c axis of Cu(OH)2 is ~ 0.76%, leading to

heteroepitaxial growth of Cu2(BDC)2(DABCO) on Cu(OH)2.

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Figure S13. Oriented Cu2(BDC)2(DABCO)13 MOFs on Cu(OH)2 nanobelts. (a,b) Top-view and cross

section FE-SEM images of the oriented Cu2(BDC)2(DABCO) MOFs prepared using the

heteroepitaxial growth from aligned Cu(OH)2 nanobelt film. (c) XRD patterns from the same

Cu2(BDC)2(DABCO) MOF film; out-of-plane (blue line), in-plane (red and black line, X-ray incident

angle is parallel and perpendicular to longitudinal direction of nanobelts at �= 0°). (d) Azimuthal angle

dependence of intensity profiles of the (200) reflection of Cu(OH)2 at a diffraction angle of 34.03�

(black line) and (001) reflection of Cu2(BDC)2(DABCO) at a diffraction angle of 9.17° (red line). The

Cu2(BDC)2(DABCO) MOFs epitaxially-grown on aligned Cu(OH)2 nanobelt film were prepared by

the following process. The aligned Cu(OH)2 nanobelt films were immersed into a solution containing

10 mL of methanol, 7 mg of H2BDC, and 4.8 mg of DABCO at 60 ºC for 90 min. The lattice mismatch

between the a axis of Cu2(BDC)2(DABCO) and the c axis of Cu(OH)2 is ~ 0.76%, leading to

heteroepitaxial growth of Cu2(BDC)2(DABCO) on Cu(OH)2.





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Figure S14. N2 gas isotherms of Cu2(BDC)2(DABCO) film. The MOF film was removed from the Si

substrate and subjected for N2 sorption experiment at 77K. Activation was carried out at 110 C in

vacuum for 12 hours. Type-I isotherm clearly indicates the microporous nature of the film14. The BET

surface area is estimated 723 m2/g and pore volume is 0.60 cm3/g. The sample weight was corrected

with the TG-DTA result, which indicates the weight fraction of Cu2(BDC)2(DABCO) in the

MOF/Cu(OH)2 composite film as 43 %.





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Figure S15. Ag nanoparticles impregnation experiment shows the open porosity of

Cu2(BDC)2(DABCO) for metal ion solution. The Cu2(BDC)2(DABCO) MOF film was immersed in a

methanolic solution of AgNO3 for 60 min and exposed to UV irradiation (500W D2 lamp, 365 nm) for

15 min to induce the formation of nanoparticles from the Ag cations15. The, the resultant film was

washed with ethanol twice. A subsequent cross sectional SEM investigation was performed. (b) Cross

sectional SEM observation and energy dispersive X-ray spectroscopy (EDS) for Cu, Ag, O and Si.

Secondary electron image (SEI) is also shown. The images clearly prove that Ag ion is homogeneously

distributed across the thickness of the Cu2(BDC)2(DABCO) MOF film, indicating that the Ag cations

can diffuse through the open porosity of the oriented MOF film.





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Figure S16 XRD patterns of (a) DMASP-doped Cu2(BPDC)2 and (b) undoped films. The crystalline

orientation is retained irrespective of the dye doping procedure.





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Figure S17. Fluorescence measurements setup and details. (a) Experimental setup of fluorescence

measurements, (b) molecular structure of 4-[4-(dimethylamino)-styryl]pyridine (DMASP).





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Figure S18. Polarization photoluminescence measurements of Cu2(BDC)2(DABCO) after

impregnation of DMASP. (a) the oriented Cu2(BDC)2(DABCO) was impregnated with DMASP by

immersing the film in a methanolic solution of DMASP for 30 min. (b) The dye (DMASP)

accommodated in pores which are oriented to the predetermined direction (c) 2D photoluminescence

spectra of the oriented Cu2(BDC)2(DABCO) film on Si substrate impregnated with DMASP, where 0

indicates a parallel light polarization to long axis of Cu(OH)2. The polarization angle dependence of

photoluminescence spectra was measured under 340 nm light excitation with JASCO FP-8300

Spectrofluorometer equipped with polarizer. (d) Azimuthal plot of fluorescence intensity response of

the DMASP guest molecules at 470 nm to linearly polarized light. The most intense luminescent

response is observed at 90 and 270, indicating that the transition dipole moment of the dye is parallel

to the a axis of the MOF and also c axis of Cu(OH)2. This demonstrates a preferential alignment of the

dye within the pores aligned along the a axis.





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Figure S19. Comparison of anisotropic optical properties on reported surface mounted MOFs. (a)

Azimuthal plot of absorption intensity response of NAFS-13 to linearly polarized light. NAFS-13

MOF samples were prepared by Prof. Rie Makiura following the recipe proposed in Makiura et al.

Sci. Rep. 3, 2506 (2013) in presence of the dye (as for the preparation of the heteropeitaxial grown

MOF film). However, no fluorescence intensity was detected, therefore we collected an azimuthal

absorption intensity scan (0-180°). (b) Azimuthal plot of fluorescence intensity response of the

DMASP doped SURMOF (Cu2(BPDC)2 grown on SAM) to linearly polarized light. No

photoluminescence dependence on the polarization angle of the excitation light was observed. The

SURMOF was prepared following the Layer-by-Layer (LbL) approach proposed by Arslan et al. J.

Am. Chem. Soc. 133, 8158 (2011) and Liu et al. Sci. Rep. 2, 921 (2012).* (c), (d) Azimuthal plots of

fluorescence intensity of DMASP in the oriented Cu2(BPDC)2 and Cu2(BDC)2(DABCO) films grown

on oriented Cu(OH)2 nanobelts. For sample preparation, see Figure S18. Both oriented MOF films

show polarization-dependent fluorescence.

Note: Dye impregnation experiment was also performed for the oriented HKUST-1 on SAM prepared

according to Biemmi et al. J. Am. Chem. Soc. 129, 8054 (2007).[12] However, the impregnation of

* The SURMOF samples were grown on Au-coated substrates using Step-by-step methodology (Shekhan, Fischer, Wöll et al. J. Am. Chem. Soc. 129, 15118 (2007)). The gold substrates were functionalized by self-assembled monolayers, SAMs, of 16-mercaptohexadecanoic acid (MHDA). These substrates were subjected to following procedure: (1) immersion in a 1 mM solution of Cu2(CH3COO)4·H2O in ethanol. (2) Then the substrate was rinsed with ethanol and dried in stream of Nitrogen. (3) The substrate was immersed in an ethanolic solution of organic linker (H2BPDC, 0.1 mM and DMASP dye, 0.5 mM) at room temperature. (4) Again, the substrate was rinsed with ethanol and dried in stream of Nitrogen. The steps (1-4) were repeated 50 times.





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HKUST-1 with the dye did not afford any detectable luminscent intensity. Additionally, Azimuthal

plot of absorption intensity of these MOFs to linearly polarized light could not be collected due to the

Au-coating that prevents transmission measurements.





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Figure S20. Schematic illustration of the fabrication procedure for oriented Cu(OH)2 nanobelt films

on a substrate (e.g., Si wafer, SiC, plastic); (a) A water bath and a syringe containing Cu(OH)2

nanobelts dispersed in ethanol, (b) the dispersed nanobelts are spread from the syringe on the water

surface to form a nanobelt single layer which flows from one side of the container to the other, (c) the

nanobelt layer arrives to the another side of the container where nanobelts align on a parallel fashion.

(d) An oriented nanobelt layer is formed at the water/air interface, (e) then a substrate is carefully

placed in contact with the nanobelt layer, (f) the oriented film is transferred to the substrate.





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