Supporting Information

Carboxylic Acid-Protruding Zincophosphate Sheets Exhibiting Surface Mechanochemical Reactivity and Intriguing Nano-Morphological Reversibility

Ling-I Hung,[a] Hsiang-Yi Yi,[a] Yu-Chieh Shih,[a] Chia-Her Lin[b] and Sue-Lein Wang*[a,b]

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2018

Instrumentation Information

Experimental section

Table S1. Crystal Data and refinement results

Table S2. Elemental analysis data

Figure S1. ORTEP for 1

Figure S2. Two unique trigonal bipyramidal zinc centers in 1

Figure S3. Structure plots for mineral tarbuttite and 1

Figure S4. TGA curves for 1 and 2-amino-1,4-benzenedicarboxylic acid

Figure S5. Variable temperature PXRD patterns for 1

Figure S6. PXRD patterns for 1 and 1-14C

Figure S7. TGA curves for 1 and 1-14C, and 1-14C_removed.

Figure S8. IR spetra for 1 and 1-14C

Figure S9. NMR spetra for 1 and 1-14C

Figure S10. SEM images for nanorods immersed in various solvents

Figure S11. PXRD patterns for 1, nanorods, nanorods after immersed in various solvents

Figure S12. PXRD patterns for 1, nanorods and restored lamella crystals

Figure S13. TGA curves for 1 and restored lamella crystals

Figure S14. The N2 adsorption–desorption isotherms for 1 and restored lamella crystals

Instrumentation Information

1. Single crystal X-ray diffractometer system:

Single-crystal X-ray diffraction intensity data were collected on a Bruker APEX DUO diffractometer equipped with a CCD area detector and Mo and Cu Kα radiation (λ = 0.71073 Å and 1.54178 Å, respectively); all data calculations were performed by using the PC version of the SHELXTL program package.

2. Powder X-ray diffractometer:

Room-temperature powder diffraction patterns were measured on a Bruker D2 PHASER desktop diffractometer at 300-W (30 kV, 10 mA) power.

Variable temperature PXRD patterns were measured with continuously heating rate 10 oC·min-1 by using synchrotron radiation (λ = 1.03321 Å) at the National Synchrotron Radiation Research Center (NSRRC) at beam line 01C, Taiwan.

3. TG analyzer:

TGA curves were measured on a Perkin-Elmer Pyris 1 thermal analyzer with samples held in platinum pans in a continuous N2 flow atmosphere and heated at a constant rate of 10 oC min-1.

4. Elemental analysis:Elemental analysis was carried out on a Foss Heraeus CHN-O-Rapid analyzer with 3-5 mg of each sample.

5. Scanning Electron Microscopy JEOL-7000F field emission scanning electron microscope

6. NMR

13C Solid-state nuclear magnetic resonance (NMR) spectra were recorded on Bruker DSX-400WB NMR SPECTROMETER.

7. Ultrasonic bath sonicator

The sonication was performed using a DELTA® Ultrasonic Cleaner, with 150W output power.

Experimental section

Surface wettability modification(1) Solution reaction:

Powder sample of 1 was stirred with decylamine in a molar ratio of 1:1 in 5ml dimethylformamide (DMF) for one day. The product was washed repeatedly three times by ethanol to remove unreacted decylamine and collected by centrifugation before characterization.

(2) Grinding in solid state:Powder sample of 1 was ground with myristylamine in a molar ratio of 1:2 using an agate mortar and a pestle. The grinding was being continued for 15 mins. Thereafter the product (denoted as 1-14C) was washed by ethanol to remove unreacted myristylamine and collected by centrifugation. The washing was repeated three times.

Lamella-to-nanorod transformation (1) Sonication of 1 in HCl(aq) to form nanorods:

1 ml HCl(aq) (pH = 1) was added into a plastic vial containing 15 mg of 1 powder. The color of powder changed instantly from white to yellow when in contact with HCl(aq). Then the vial was sonicated for 15 mins using a bath-type sonicator. Settle the powder down from HCl(aq) by centrifugation and use a pipette tip to remove the supernatant. The SEM sample was prepared by directly transferring a small portion of the powder onto a holder (Si wafer).

(2) Solvent-assisted morphological reversibility:1 ml acetone was added to the above-mentioned vial containing yellow powder and residual HCl(aq). The color of powder changed back into white instantly as shown in Fig. 2. Acetone was replaced with various solvents, water, chloroform, ethanol and DMF. All the samples were collected by centrifugation for SEM and PXRD.

Table S1. Crystal Data and refinement results. 1-400 and 1-440 represent for the individual crystals of 1 heated at 400ºC and 440ºC for 1 hour.

*There was 65% loss of –COOH in per formula of compound 1, estimated from single-crystal X-ray diffraction data. The benzoic acid (-COOH) lost CO2 and became

Compound name 1 1-400 1-440*Chemical formula Zn2PO4(NH2HBDC) Zn2PO4(C7.35H6NO2.70)

Formula weight 405.85 376.07

Temperature (K) 296(2)

Wavelength (Å) 0.71073

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 17.071(1) Å a = 16.8677(7) Å a = 16.729(1) Å

b = 6.5675(4) Å b = 6.5703(3) Å b = 6.5166(5) Å

c = 9.5925(6) Å c = 9.6035(4) Å c = 9.6364(6) Å

= 90.974(2)° = 90.205(2)° = 90.977(3)°

Volume (Å3) 1075.3(1) 1064.31(1) 1050.3(1)

Z 4

Density (calculated)(Mg/m3) 2.507 2.533 2.378

Absorption coefficient (mm-1) 4.652 4.700 4.743

F(000) 800 738

Crystal size (mm3) 0.11 x 0.09 x 0.02 0.16 x 0.12 x 0.02 0.10 x 0.08 x 0.01

Theta range of data collection 3.581 to 28.326° 2.415 to 26.362 2.435 to 28.368°

Index ranges-22 ≤ h ≤ 22, -8 ≤

k ≤ 6, -12 ≤ l ≤ 12

-19 ≤ h ≤ 21, -8 ≤ k

≤ 8, -12 ≤ l ≤ 11

-22 ≤ h ≤ 22, -8 ≤ k ≤ 4, -

12 ≤ l ≤ 12

Reflections collected 9510 8940 8326

Independent reflections2654

[R(int) = 0.0345]

2654

[R(int) = 0.0345]

2619

[R(int) = 0.0359]

Completeness (%) 98.7 99.9 99.8

Max. and min. transmission 0.9485 and 0.7962 0.9485 and 0.8924 0.9485 and 0.7766

Data / restraints / parameters 2654 / 0 / 181 2172 / 0 / 181 2619 / 0 / 182

Goodness-of-fit on F2 1.055 1.052 1.059

Final R indices [I>2sigma(I)]R1 = 0.0282,

wR2 = 0.0610

R1 = 0.0205,

wR2 = 0.0457

R1 = 0.0434,

wR2 = 0.1081

R indices (all data)R1 = 0.0354,

wR2 = 0.0632

R1 = 0.0272,

wR2 = 0.0475

R1 = 0.0552,

wR2 = 0.1150

Largest diff. peak and hole (e·Å-3) 0.610 and -0.603 0.388 and -0.292 2.501 and -0.732

phenyl -H

Table S2. Elemental analysis (EA) data

N(%) C(%) H(%)1 (cal.) 3.45 23.66 1.491 (exp.) 3.47 23.54 1.571-14C 3.63 25.83 2.06

Footnote: 1-14C is denoted for the sample of NTHU-17 ground with myristylamine (14C-amine). Compared to the experimental results of 1, 14C-amine was successfully grafted onto the surface of 1 as indicated by the increase of C, N, H values.

Figure S1. ORTEP for 1. The thermal ellipsoids are drawn in 50% probability.

Figure S2. Two unique trigonal bipyramidal zinc centers in 1: (left) the Zn(1)2O8 dimer contains six μ3-O shared by two zinc and one phosphorus centers; (right) Zn(2)NO4 shares corners with two Zn(1)2O8 dimers and three PO4 tetrahedra. (Enlarged balls, red for O and blue for N are from carboxylate and amino groups of NH2HBDC.)

Figure S3. Structure plots for mineral tarbuttite and 1: (left) A three dimensional framework of tarbuttite composed of Zn2O6(OH)2 edge-sharing infinite chains interconnected with edge-sharing Zn2O8 dimers and PO4 tetrahedra. Enlarged red balls represent for the μ3-OH groups of tarbuttite; (right) A single sheet of two-dimensional hybrid structure of 1. It may be viewed when the μ3-OH groups are replaced by the tri-chelate ligand, NH2HBDC, the original edge-sharing Zn2O6(OH)2 infinite chains of tarbuttite are truncated into singular ZnNO4 trigonal bipyramids to form a delaminated zincophosphate sheet in compound 1 with both sides covered by -COOH arrays.

200 400 600 800 1000

0

20

40

60

80

100W

eigh

t (%

)

Temperature (oC)

1 NH2H2BDC

Figure S4. TGA curves (under flowing N2 gas) for 1 and 2-Amino-1,4-benzenedicarboxylic acid (NH2H2BDC).

10 20 30 40Two theta

Figure S5. Variable temperature PXRD patterns (λ = 1.0332 Å) for 1

5 10 15 20 25 30 35 40Two theta

1-14C 1 (obsd.) 1 (cald.)

Figure S6. PXRD patterns (λ = 1.5418 Å) for 1 calculated (black), 1 observed (red), and 1-14C (blue)

0 200 400 600 800 100040

50

60

70

80

90

100

Wei

ght (

%)

Temperature (oC)

1 1-14C 1-14C_removed

Figure S7. TGA curves (under flowing N2 gas) for 1, 1-14C and 1-14C_removed. 1-14C_removed represents for the sample of 1-14C treated by HCl(aq) to remove the grafted myristylamine.

Figure S8. IR spectra for 1 (black) and 1-14C (red): the IR spectrum of 1-14C revealed that the alkane (C-H) vibrations at 2850 cm-1 and 2921 cm-1 (in green box) appeared due to the alkyl chain of grafted myristylamine .

Figure S9. 13C solid state NMR spectra for 1 (black) and 1-14C (red): chemical shift for the alkane (C-H) was observed in the range of 0-50 ppm (in green box) whereas no obvious change of chemical shift for C=O at 170 ppm. No chemical shifts corresponding to C-N bond to confirm the occurrence of amidation between surface –COOH and myristylamine.

(a) (b)

(c)

Figure S10. SEM images for nanorods immersed in various solvents: (a) ethanol; (b) chloroform; (c) water. No image for DMF because the nanorods dissolved in DMF thoroughly.

Figure S11. PXRD patterns (λ = 1.5418 Å) for 1 (black), nanorods (red), nanorods after immersed in various solvents: nanorods in water (blue), nanorods in chloroform (pink), and nanorods in ethanol (green). The inset shows the relative intensity of each pattern.

5 10 15 20 25 30 35 40Two theta

nanorods in ethanol nanorods in chloroform nanorods in water nanorods 1

5 10 15 20 25 30 35 40Two theta

5 10 15 20 25 30 35 40Two theta

R-NTHU-17 nanorods NTHU-17

Figure S12. PXRD patterns (λ = 1.5418 Å) for 1 (black), nanorods (red), and restored lamella crystals (blue).

0 200 400 600 800 100050

60

70

80

90

100

Temperature (oC)

Wei

ght (

%)

Figure S13. TGA curves for 1 (red) and restored lamella crystals (black).

0.0 0.2 0.4 0.6 0.8 1.0-6

-4

-2

0

2

4

6

8

10

12

V ads(cm

3 /g)

P/P0

Figure S14. The N2 adsorption–desorption isotherms for 1 (in green) and restored lamella crystals (in blue). The reassembled bulk lamella showed no porosity and low surface area, an insignificant change from 1 with a non-meaningful measurement result of negative value.