Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal-Organic Nanoclusters into Pores of Molecular Frameworks

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1 Electronic Supplementary Information Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal-Organic Nanoclusters into Pores of Molecular Frameworks Zhi-Gang Gu, a Hao Fu, a Tobias Neumann, c Zong-Xiong Xu, a Wen-Qiang Fu, a Wolfgang Wenzel, c Lei Zhang, a Jian Zhang a and Christof Wöll b a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China b Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany c Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany Table of content Materials and instrumentation Synthesis of [Ti 4 O 4 (R/S-C 20 O 2 H 12 ) 6 ] (C 3 H 7 NO 2 ) 2 (R-Ti-MOC and S-Ti-MOC) Table 1. Crystal Data and Structure Refinement of Ti 4 O 4 (R/S-BINOL) 4 (R- and S-Ti-MOC). Preparation of functionalized substrates Fabrication of HKUST-1 thin film Direct immersing encapsulation of Ti-MOC into HKUST-1 thin film Figure S1. The CD spectra of Ti 4 O 4 (R-BINOL) 4 (R-Ti-MOC) encapsulated HKUST-1 thin film via direct immersing approach. In situ LPE layer-by-layer Fabrication of (HKUST-1)(Ti-MOC) thin film Figure S2. The fabrication setup and the in situ LPE layer-by-layer growth procedure of (HKUST-1)(Ti-MOC) thin film with the hand spray method: (1), (2), (3) and (4) for Cu(OAc) 2, BTC, ethanol and Ti-MOC solution, respectively. Figure S3. XRD of (HKUST-1)(Ti-MOC) grown on quartz substrate glass with in situ layer-by-layer Ti-MOC encapsulation of MOF thin film and HKUST-1 sample. Figure S4. The molecules model of empty HKUST-1 and (HKUST-1)(Ti-MOC).

2 Figure S5. The CD spectra of probe molecules methyl-d-lactate and methyl-l-lacate Figure S6. IRRAS spectrum of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded HKUST-1 thin film via direct loading approach. Figure S7. (a) XRD data of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded Cu 2 (Dcam) 2 dabco thin film via in situ layer-by-layer encapsulation approach; (b) IRRAS spectrum of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded Cu 2 (Dcam) 2 dabco thin film via in situ layer-by-layer encapsulation approach. Figure S8. CD of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC), Cu 2 (Dcam) 2 dabco and (Cu 2 (Dcam) 2 dabco)(r-ti-moc) thin film. Figure S9. (a) XRD of MOF-2 and (MOF-2)(R-Ti-MOC) thin film; (b) CD of (MOF-2)(R-Ti-MOC)thin film. Figure S10. Powder XRD data (a) and IR spectrum (b) of powder HKUST-1 before and after immersing into Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) solution for 12 h. Figure S11. Powder XRD data of obtained floccule prepared by using a mixture of reactants of Cu(OAc) 2, H 3 BTC and the MOC at 65 for 2 days. Figure S12. CD spectrum of obtained floccule prepared by using a mixture of reactants of Cu(OAc) 2, H 3 BTC and the MOC at 65 for 2 days. Figure S13. CD spectrum of pristine (HKUST-1)(R-Ti-MOC) thin films with different cycles (20, 40 and 60 cycles). Materials and instrumentation All the reagents and solvents employed were commercially available and were used as received without further purification. 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

3 performed on a MiniFlex2 X-ray diffractometer using Cu-Kα radiation (λ = nm) in the 2θ range of 4 20 with a scanning rate of 0.5 min 1. Circular dichroism (CD) experiments were recorded with a Bio-logic MOS-450 CD Spectrometer at room temperature. CD Spectra recorded for the pure quartz glass plate (which was also used as the substrate for SURMOF thin film preparation) were used as a reference. CD Spectra were recorded from 600 to 200 nm in 1 nm steps using a 20 nm min -1 scan speed. Transmission electron microscope (TEM) images and EDS recorded for Ti-MOC loaded HKUST-1 thin films were used JEM-2010F. The mass of the titanium oxo-cluster was determinated by mass spectroscopy (MS) DECAX Scanning electron microscope (SEM) images for the morphology of thin films were measured by JSM6700. Synthesis of Ti 4 (OH) 4 (R/S-BINOL) 6 ((R)-Ti-MOC and (S)-Ti-MOC) A mixture of R- or S-BINOL (286mg, 1 mmol, BINOL =1,1'-Bi-2-naphthol), tetraisopropyl titanate (0.6mL, 2 mmol), isopropanol (1 ml) and Dimethylformamide (DMF, 1 ml) was sealed in a 10 ml sealed glass bottle and heated at 60 C for 24h, and then cooled to room temperature, finally the red bulk crystals R-Ti-MOC and S-Ti-MOC were collected for characterization.

4 Table 1. Crystal Data and Structure Refinement of Ti-MOCs Ti 4 O 4 (R/S-BINOL) 4. Ti 4 O 4 (R-BINOL) 4 (DMF) Ti 4 O 4 (S-BINOL) 4 (DMF) 2 Chemical formula Ti 4 C 126 H 90 N 2 O 18 Ti 4 C 126 H 90 N 2 O 18 M Crystal system orthorhombic orthorhombic Space group P P a /Å (2) (2) b /Å (4) (4) c /Å (3) (3) α / β / γ / V/Å (3) (3) Z 4 4 T /K 293(2) 293(2) F(000) D calcd / g cm µ /mm λ /Å R 1 [I = 2σ(I)] a wr 2 [I = 2σ(I)] b R 1 (all data) wr 2 (all data) GOF

5 Preparation of functionalized substrates The OH-functionalized self-assembled monolayers (SAMs) on Au were prepared by immersing Au substrates into 1mM/L ethanolic solutions of 11-mercapto-1-undecanol (MUD) 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 MHDA modified Au substrate and OH-terminated quartz glass substrate using the liquid-phase epitaxy (LPE) spray method, which yields thin film with [100] and [111]orientation, respectively. 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 spray method is adopted in this work which is descripted in the earlier work. The spray times were 15 s for the copper acetate solution and 25 s for the BTC solution. Each step was followed by a spray step with pure ethanol to remove residual reactants. A total of 60 growth cycles were used for HKUST-1 grown on functionalized Au and quartz glass substrates in this work.

6 Characterization of HKUST-1 was carried out by XRD (Fig. 1a and Fig. S6) and IRRAS (Fig. 1b). The diffraction peak at 6.8 and 13.6, 11.6 and 17.5 are in accord with the simulated XRD peaks at at (200) and (400),(222) and (333) of HKUST-1, respectively, which show the framework of thin film is grown along [100] orientation on SAMs of MHDA Au substrates (Fig.2a) and [111] orientation on OH-functionalized quartz glass (Fig. S6). The presence of a broad and strong band at cm -1 is assigned to vibrations of COO - of HKUST-1 (Fig.1b). Direct immersing encapsulation of Ti-MOC into HKUST-1 thin film To compare in situ LPE layer-by-layer encapsulation approach, another encapsulation approach, direct immersing experiment was carried out. HKUST-1 thin film on the gold or quartz glass substrates were put into a flask and then evacuated to 0.2 kpa at room temperature for 30 min. Subsequently, the sample was immersed in a freshly prepared solution of Ti 4 O 4 (R -BINOL) 4 in ethanol (0.1 mm, drops of DMF for dissolve) kept at 65 degree. After an immersion time of 12 h the sample was removed from the solution, rinsed with pure ethanol, and finally dried in a flux of nitrogen gas for further investigation. The CD data (Fig. S4) of the treated sample show there is no chiral character, demonstrating there is no Ti 4 O 4 (R -BINOL) 4 in HKUST-1 thin film using direct immersing approach.

7 CD / mdeg directed Ti 4 O 4 (R-BINOL) 6 loaded HKUST Wavelength / nm Figure S1. The CD spectra of Ti 4 O 4 (R-BINOL) 4 (R-Ti-MOC) encapsulated HKUST-1 thin film via direct immersing approach.

8 In situ LPE layer-by-layer encapsulation of Ti-MOC into HKUST-1 thin film Mass spectra (Fig. S2) of Ti-MOC solution shows it is very stable in solution status, demonstrating this cluster is suited for in situ encapsulation of Ti-MOC into HKUST-1 using LPE layer-by-layer fashion. Using the same LPE spray method, (HKUST-1)(Ti-MOC) thin films prepared by grown on MUD modified Au substrate and OH-terminated quartz glass substrate along [111] orientation. The (HKUST-1)(Ti-MOC) thin film were fabricated using the following diluted ethanolic solutions: copper acetate (1 mm) and BTC (0.4 mm) and Ti 4 O 4 (R/S-BINOL) 4 (0.1 mm). The spray times were 15s, 25s and 10s for Cu(OAc) 2, H 3 BTC and Ti-MOC solution, respectively. There was waiting time for 30s between steps and each step was followed by a 3s spray step with pure ethanol to remove residual reactants. A total of 60 growth cycles were used for in situ LPE layer-by-layer Ti-MOC encapsulation in HKUST-1 thin film in this work. Calculations The optimization of the geometry of the MOC in the MOF cavity was performed in several steps. First, the BINOL ligands were manually distorted to fit the NP into the large pore of HKUST-1. The optimization of the precise structure of the fairly large MOC was performed by first increasing the MOF lattice constant by 10 % (Scaling factor 1.1) and then optimizing the MOC-structure by using the Hartree-Fock approach as implemented in MOPAC 1. In the next step, a scaling factor of 1.08 was

9 used for the MOF, and the MOC-structure again optimized using the Hartree-Fock approach. A total of four steps (MOF scaling factors 1.1, 1.08, 1.05, 1.0) were used. During the last two steps, the Ti-, O- and H-atoms of the inner part of the cluster were kept fixed. 1. James JP Stewart, Stewart Computational Chemistry, Colorado Springs, CO (2012).

10 Figure S2. The fabrication setup and the in situ LPE layer-by-layer growth procedure of (HKUST-1)(Ti-MOC) thin film with the hand spray method: (1), (2), (3) and (4) for Cu(OAc) 2, H 3 BTC, ethanol and Ti-MOC solution, respectively.

11 Figure S3. XRD of (HKUST-1)(Ti-MOC) grown on quartz substrate glass with in situ layer-by-layer Ti-MOC encapsulation of MOF thin film and HKUST-1 sample.

12 Figure S4. The molecules model of empty HKUST-1 and (HKUST-1)(Ti-MOC).

13 CD / mdeg (+)-MeLt (-)-MeLt Wavelength / nm 400 Figure S5. The CD spectra of probe molecules (+)-Methyl-D-Lactate ((+)-MeLt) and (-)-methyl-l-lacate ((-)-MeLt)

14 direct loading of Ti O (R-BINOL) into HKUST Absorbance Ti 4 O 4 (R-BINOL) 6 HKUST Wavenumbers / cm -1 Figure S6. IRRAS spectrum of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded HKUST-1 thin film via direct loading approach.

15 Figure S7. (a) XRD data of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded Cu 2 (Dcam) 2 dabco thin film via in situ layer-by-layer encapsulation approach; (b) IRRAS spectrum of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) loaded Cu 2 (Dcam) 2 dabco thin film via in situ layer-by-layer encapsulation approach.

16 CD / mdeg Cu 2 (Dcam) 2 dabco CD / mdeg Ti 4 O 4 (R-BINOL) 6 Ti 4 O 4 (R-BINOL) 2 (Dcam) 2 dabco Wavelength / nm Figure S8. CD of Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC), Cu 2 (D-cam) 2 dabco and (Cu 2 (D-cam) 2 dabco)(r-ti-moc) thin film.

17 Figure S9. (a) XRD of MOF-2 and (MOF-2)(R-Ti-MOC) thin film; (b) CD of (MOF-2)(R-Ti-MOC) thin film.

18 Figure S10. Powder XRD data (a) and IR spectrum (b) of powder HKUST-1 before and after immersing into Ti 4 O 4 (R-BINOL) 6 (R-Ti-MOC) solution for 12 h.

19 powder XRD of the floccule react from the mixed reagent powder XRD of R-Ti-MOC I simulated XRD of HKUST-1 simulated XRD of R-Ti-MOC θ / O Figure S11. Powder XRD data of obtained floccule prepared by using a mixture of reactants of Cu(OAc) 2, H 3 BTC and the MOC at 65 for 2 days. 40 R-Ti-MOC mixture synthesis R-BINOL CD / mdeg Wavelength / nm Figure S12. CD spectrum of obtained floccule prepared by using a mixture of reactants of Cu(OAc) 2, H 3 BTC and the MOC at 65 for 2 days.

20 20 CD / mdeg cycles 40 cycles 60 cycles wavelength / nm Figure S13. CD spectrum of pristine (HKUST-1)(R-Ti-MOC) thin films with different cycles (20, 40 and 60 cycles).