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1 Eectronic Suppementary Materia (ESI) for Journa of Materias Chemistry A. This journa is The Roya Society of Chemistry 7 Suppementary Information Enhanced Properties of Meta-Organic Framework Thin-Fims Fabricated via a Coordination Moduation-controed Layer-by-Layer processes Suttipong Wannapaiboon, a,b Kenji Sumida, c,d, * Katharina Dichert, b Min Tu, b,e Susumu Kitagawa, c Shuhei Furukawa, c and Roand A. Fischer a, * a Chair of Inorganic and Meta-Organic Chemistry, Technica University of Munich, Lichtenbergstr., D-8578 Garching, Germany. Fax: +9() ; Te: +9() ; E-mai: roand.fischer@tum.de b Chair of Inorganic Chemistry II, Ruhr-University Bochum, Universiteatstr. 5, D-78 Bochum, Germany. c Institute for Integrated Ce-Materia Sciences (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 66-85, Japan. d Centre for Advanced Nanomaterias, Schoo of Physica Sciences, The University of Adeaide, Adeaide, SA 55, Austraia. Emai: kenji.sumida@adeaide.edu.au e Center for Surface Chemistry and Cataysis, Kathoieke Universiteit Leuven, Ceestijnenaan f box 6, Leuven, Begium. Experimenta Materias The starting materias (Tabe S) were prepared using procedures described in our previous pubications. Basic zinc acetate (ZnO(OAc)6), a product of the subimation of zinc acetate dihydrate at 8 C under vacuum, was used as the pre-formed secondary buiding unit (SBU) meta precursor. The purity of basic zinc acetate was characterized by powder X-ray diffraction (PXRD) prior to using foof syntheses. Three different,5-aky-substituted--carboxypyrazoe moecues i.e.,5-dimethy--carboxypyrazoe (HDM), -methy-5-ethy--carboxypyrazoe (HME) and,5-diethy-- carboxypyrazoe (HDE) were used as the organic inkers. The purity of organic inkers was proved by H nucear magnetic resonance (NMR) spectroscopy. Acetic acid was used as a coordination moduator in these experiments. Syntheses of MOF powders by igand repacement approach and integration of coordination moduation with the igand repacement approach The preiminary studies invoved the syntheses of three different anaogues of ZnO(carboxypyrazoate) MOFs (i.e. Zn-DM, Zn-ME and Zn-DE, Tabe S) as buk powders by direct mixing of the pre-formed meta secondary buiding unit (SBU) soution with the organic inker soution within a screw-capped jar, so-caed igand repacement approach. The.6 mm of ZnO(OAc)6 soution in ethano and the.8 mm of organic inker soution (HDM and HME in : v/v ethano/water mixture and HDE in 5: v/v ethano/water mixture) were used as precursor soutions. In order to study the infuences of coordination moduation, acetic acid was seected as a coordination moduator and added to the reaction. Specificay, acetic

2 acid was firsty mixed with the ZnO(OAc)6 soution. Subsequenty, the organic inker soution was sowy added to the reaction mixture. The moduator-to-inker moar ratio (rl) was varied from to 5 for the syntheses of the three anaogue MOFs and furthermore increased up to in the case of Zn-DM. After mixing the precursor soutions at room temperature, the reaction mixtures were eft in the oven at 5 C for h in order to achieve compete crystaization under this equiibrium condition. The products were coected by centrifugation and repeatedy washed with ethano for times. The activation of as-synthesized MOF powders was conducted at C under vacuum for days prior to the adsorption measurements. Fabrication of MOF fims by integration of coordination moduation with LPE process Herein, Au-coated quartz crysta microbaance sensors (QCM, commerciay avaiabe by Q- Sense, AT cut type of quartz crysta, Au eectrode, diameter mm, thickness. mm and fundamenta frequency ca..95 MHz) were used as the substrates. Prior to the fabrication of MOF thin-fims, the substrates were immersed in M soution of 6-mercaptohexadecanoic acid (MHDA) in ethano and 5% v/v acetic acid for h in order to functionaize the substrate surface. Sef-assembed monoayer (SAM) formed by thio bonding of MHDA moecues on the Au surface provides the -COOH terminated functionaity at the substrate surface; consequenty, were used for fabrication of MOF fims. For each experiment, the precursor soutions were freshy prepared as foow: ZnO(OAc)6 soution (.5 mm) in ethano, HDM and HME soution (.5 mm) in : v/v ethano/water mixture and HDE in 5: v/v ethano/water mixture. Acetic acid (used as the coordination moduator) was mixed in the ZnO(OAc)6 soution. Three different MOF fims (Zn-DM, Zn-ME and Zn-DE) were fabricated by integrating coordination moduation with the LPE process for 5 cyces at controed temperature of C using the automated QCM instrument (Q-Sense E Auto) operated in the continuous fow mode with a fow rate of L min -. In each deposition cyce, the functionaized QCM substrate was aternatingy exposed to the precursor soutions as foow: ZnO(OAc)6 mixed with acetic acid min, ethano (as a sovent) 5 min, organic inker min and finay ethano 5 min. In order to investigate the infuences of the moduator, the moduator-to-meta moar ratio (rm) were varied ranging from to 5. Three main sets of experiments were performed: (A) MOF fims grown for tota 5 cyces without sef-seeding ayer (in other words, the ZnO(OAc)6 soution mixed with acetic acid was used from the first deposition cyce), (B) MOF fims grown for cyces on top of the pre-deposited MOF fims of the same type grown by typica LPE method without using moduator for 5 cyces as a sef-seeding ayer (here, the ZnO(OAc)6 soution mixed with acetic acid was used from the sixth deposition cyce), and (C) MOF fims grown for tota 5 cyces without sef-seeding ayer, however mixing acetic acid with the inker soution instead of the ZnO(OAc)6 soution. Moreover, the MOF fims grown by typica stepwise LPE method were grown as a contro experiment. The change of QCM frequency was recorded in situ during the MOF fim fabrication to study the MOF fim growth.

3 Characterization of MOF powders Crystaine phase and purity of the obtained MOF powders were characterized by powder X- ray diffraction (XRD) patterns coected on an X Pert PanAnaytica instrument (Bragg- Bentano geometry with automatic divergent sits, Cu K radiation, range from 5 to 5, scan step size., position sensitive detector, operated at ambient atmosphere). Morphoogy of the synthesized MOFs was determined by scanning eectron microscopic (SEM) images coected on a JEOL JSM-75F eectron microscope using an emission votage of 5 kv. The sampes were activated to remove the residue sovent moecues, then attached to the sampe hoder using doube-side carbon tape, and were coated with osmium nanopartices to increase the conductivity before oading into the SEM instrument. To investigate the adsorption properties of the MOF powders, nitrogen sorption measurements at 77 K were performed on a BELSORPmax adsorption anayzer (BEL Japan, Inc.). The specific surface area was cacuated using the Brunauer-Emmett-Teer (BET) mode. Characterization of MOF fims The fabricated MOF fims were identified the crystaine phase by powder XRD using an X Pert PanAnaytica instrument (Bragg-Bentano geometry, Cu K radiation, range from 5 to with scan step size of. ). Two-dimensiona grazing incidence X-ray diffraction (D-GIXRD) were performed at Beamine 9, DELTA Synchrotron faciity, Germany (using X-ray waveength of. Å, incidence ange of.6 and refined sampe-to-detector distance of. mm) to characterize the crysta orientation of the fabricated MOF fims. Top view and cross section SEM images were taken by an environmenta scanning eectron microscope (ESEM, FEI ESEM Dua Beam TM Quanta D FEG) in order to investigate surface morphoogy and surface coverage of the MOF fims. Here, the sampes were sputtered with carbon before oading to the SEM instrument. Infrared refection adsorption spectra of the activated MOF fims were measured inside a govebox by a Bruker Apha-P FTIR instrument operated with the externa refection modue. Sorption properties of the MOF fims were carried out on an environmenta-controed quartz crysta microbaance (BEL-QCM- instrument, BEL Japan), of which the schematic setup is iustrated in Scheme S. A the adsorption experiments were measured at controed temperature of 5 C and methano was used as probe moecues. To activate the MOF fims, the sampes were firsty immersed in dichoromethane for h to exchange the residue sovent moecues within the MOF pore with highy voatie dichoromethane moecues. Finay, the fims were activated in-situ within the BEL-QCM instrument by heating at 8 C together with a dry He purging with a fow rate of sccm for tota h. After activation, the sampes were cooed down to 5 C. When the change of QCM frequency was stabe within the range of ±5Hz in min, the masses of the MOF fims (as a conversion according to Sauerbrey s equation of the difference between the QCM frequency at the fina activation and the fundamenta frequency of the QCM substrates) were recorded. After that, methano adsorption isotherms were coected by varying the reative vapor pressure (P/P) of saturated methano vapor in He gas fow at 5 C from. to 95.%. The adsorption amounts were cacuated according to the Sauerbrey s equation.

4 Tabe S Starting materias for ZnO(,5-diaky--carboxypyrazoate) (Zn-L) MOF powder syntheses by coordination-moduation assisted igand repacement approach and for fabrication of MOF thin fims by empoying coordination moduation method in conjunction with stepwise iquid phase epitaxia process, reported in this study MOF fims Meta precursor Organic inkers Moduator O OH. ZnO(,5-dimethy-- carboxypyrazoate) (Zn-DM) ZnO(CHCOO)6 N N H CHCOOH (HDM) O OH. ZnO(-methy-5-ethy-- carboxypyrazoate) (Zn-ME) ZnO(CHCOO)6 N N H CHCOOH (HME) O OH. ZnO(,5-diethy-- carboxypyrazoate) (Zn-DE) ZnO(CHCOO)6 N N H CHCOOH (HDE) MFC- - sccm carrier gas QCM ce He MFC- - sccm condenser MFC- - sccm MFC- - sccm PC vaporiser (organic sovent) Scheme S Schematic experimenta setup of an environmenta controed quartz crysta microbaance (BEL-QCM) used for organic vapor adsorption experiments of MOF thin fims

5 Normaized Intensity / a.u. Normaized Intensity / a.u.. Preparation of ZnO(,5-diaky--carboxypyrazoate) powders by integrating coordination moduation with igand repacement approach r L / degree Zn-DM powders r L / degree Figure S Powder X-ray diffraction patterns for Zn-DM powders synthesized by combining coordination moduation with igand repacement approach at 5 C using acetic acid as the moduator with various moduator-to-inker moar ratio (rl) ranging from to comparing with the Zn-DM powder synthesized by igand repacement approach without using the moduator. The numbers in the figure indicate the Mier indices of the diffractions. 5

6 Normaized Intensity / a.u. Normaized Intensity / a.u. Normaized Intensity / a.u. Normaized Intensity / a.u. * * r L 5 Zn-ME powders r L / degree / degree Figure S Powder X-ray diffraction patterns for Zn-ME powders synthesized by combining coordination moduation with igand repacement approach at 5 C using acetic acid as the moduator with rl = - 5. The numbers in the figure indicate the Mier indices of the diffractions. * * * * * * * * * * * * r L 5 Zn-DE powders 5 r L / degree / degree Figure S Powder X-ray diffraction patterns for Zn-DE powders synthesized by combining coordination moduation with igand repacement approach at 5 C using acetic acid as the moduator with rl = -. The numbers in the figure indicate the Mier indices of the diffractions. 6

7 Figure S Scanning eectron microscopy (SEM) images of Zn-DM powders synthesized at 5 C by (a) igand repacement approach without using the moduator (rl = ) comparing with Zn-DM powders synthesized by integrating coordination moduation into the procedure using acetic acid as the moduator with rl of (b), (c) and (d) 5. Figure S5 Scanning eectron microscopy (SEM) images of Zn-ME powders synthesized at 5 C by (a) igand repacement approach without using the moduator (rl = ) comparing with Zn-ME powders synthesized by integrating coordination moduation into the procedure using acetic acid as the moduator with rl of (b), (c) and (d). 7

8 Figure S6 Scanning eectron microscopy (SEM) images of Zn-DE powders synthesized at 5 C by (a) igand repacement approach without using the moduator (rl = ) comparing with Zn-DE powders synthesized by integrating coordination moduation into the procedure using acetic acid as the moduator with rl of (b), (c) and (d). N Adsorbed amount / mmo g N sorption 77K of Zn-DM powders using r L of (a) (b) (c) (d) 5 adsorption desorption Reative pressure / P/P Figure S7 N sorption isotherm at 77 K of the Zn-DM powders synthesized at 5 C by integrating coordination moduation with the igand repacement approach using rl ratio of (a), (b), (c) and (d) 5. 8

9 N Adsorbed amount / mmo g - N Adsorbed amount / mmo g N sorption 77K of Zn-ME powders using r L of (a) (b) adsorption desorption Reative pressure / P/P Figure S8 N sorption isotherm at 77 K of the Zn-ME powders synthesized at 5 C by integrating coordination moduation with the igand repacement approach using rl ratio of (a) and (b). N sorption 77K of Zn-DE powders using r L of (a) (b) (c) 8 6 adsorption desorption Reative pressure / P/P Figure S9 N sorption isotherm at 77 K of the Zn-DE powders synthesized at 5 C by integrating coordination moduation with the igand repacement approach using rl ratio of (a), (b) and (c). 9

10 . Integration of coordination moduation in the LPE-based fabrication of Zn-L thin-fims on quartz crysta microbaance (QCM) substrates A. Zn-DM fims Figure S Two-dimensiona grazing incidence X-ray diffraction patterns (D-GIXRD) of Zn- DM fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with various moduatorto-meta ratio (rm) from to 5). The synchrotron parameters are X-ray waveength. Å, incidence ange.6 and refined sampe-to-detector distance. mm. Figure S Cross-sectiona view SEM images of Zn-DM fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm = - 5.

11 Transmittance Normaized F / Hz Methano Adsorbed / mmo g K adsorption desorption 5. Methano adsortion kinetics at P/P =., 98 K Reative vapor pressure / P/P Adsorption time / s Zn-DM 5 Figure S Methano sorption isotherms at 5 C and adsorption kinetics at P/P =. measured using the environmentay controed quartz crysta microbaance (QCM) of Zn-DM fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm = Wavenumber / cm - Figure S Infrared refection absorption spectra (IRRAS) of Zn-DM fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as moduator by mixing it with the ZnO(OAc)6 soutions with rm = - 5.

12 Normaized Intensity / a.u. B. Zn-ME fims degree Figure S Powder X-ray diffraction patterns (XRD) of Zn-ME fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6 of (a).5 mm and (b). mm, HME.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. Figure S5 SEM images of the surfaces of Zn-ME fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HME.5 mm and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =.

13 Figure S6 Cross-sectiona view SEM images of Zn-ME fims fabricated at C via integration of coordination moduation with LPE fabrication process using rm =. Figure S7 D-GIXRD patterns of Zn-ME fims fabricated at C via integration of coordination moduation with LPE fabrication process without sef-seeding ayer; using ZnO(OAc)6.5 mm, HME.5 mm and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. The synchrotron parameters are X-ray waveength. Å, incidence ange.6 and refined sampe-to-detector distance. mm.

14 methano adsorbed / mmo g - Normaized Intensity / a.u. Normaized F / Hz K adsorption desorption Reative vapor pressure / P/P Adsorption time / s Methano adsortion kinetics at P/P =., 98 K Zn-ME Figure S8 Methano sorption isotherms at 5 C and adsorption kinetics at P/P =. measured using the environmentay controed quartz crysta microbaance (QCM) of Zn-ME fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. C. Zn-DE fims degree Figure S9 Powder X-ray diffraction patterns (XRD) of Zn-DE fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6 of (a).5 mm and (b). mm, HDE.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =.

15 Figure S SEM images of the surfaces of Zn-DE fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDE.5 mm and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. Figure S Cross-sectiona view SEM images of Zn-DE fims fabricated at C via integration of coordination moduation with LPE fabrication process using rm =. 5

16 Methano adsorbed / mmo g - Normaized F / Hz Figure S D-GIXRD patterns of Zn-DE fims fabricated at C via integration of coordination moduation with LPE fabrication process without sef-seeding ayer; using ZnO(OAc)6.5 mm, HDE.5 mm and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. The synchrotron parameters are X-ray waveength. Å, incidence ange.6 and refined sampe-to-detector distance. mm K. Methano adsortion kinetics at P/P =., 98 K 6 adsorption desorption Reative vapor pressure / P/P Adsorption time / s Zn-DE Figure S Methano sorption isotherms at 5 C and adsorption kinetics at P/P =. measured using the environmentay controed quartz crysta microbaance (QCM) of Zn-DE fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm =. 6

17 Normaized Intensity / a.u. F / Hz. Probing the roe of coordination moduation in optimizing LPE fabrication A. Zn-DM fims fabricated on sef-seeding Zn-DM ayer prepared by conventiona LPE process cyces-pre-deposited Zn-DM as seeding without using the moduator 6 8 Deposition time / min Figure S In-situ monitoring of QCM frequency during the fabrication of Zn-DM fims at C via integration of coordination moduation with LPE fabrication process on the 5-cycespre-deposited Zn-DM fims fabricated without using moduator as a sef-seeding ayer; using ZnO(OAc)6.5 mm, HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the ZnO(OAc)6 soutions with rm = degree Figure S5 XRD patterns of Zn-DM fims fabricated at C with various rm ratio via integration of coordination moduation with LPE fabrication process on the pre-deposited, sefseeding Zn-DM ayer fabricated without using the moduator for 5 cyces (corresponding with the growth data in Figure S) 7

18 Figure S6 GIXRD patterns of Zn-DM fims fabricated at C with various rm ratio by empoying coordination moduation method in conjunction with LPE process on the predeposited, sef-seeding Zn-DM ayer fabricated without using the moduator for 5 cyces. Synchrotron parameters are X-ray waveength. Å, incidence ange.6 and refined sampe-to-detector distance 87. mm. Figure S7 SEM images of the surfaces of Zn-DM fims fabricated at C with various rm ratio via integration of coordination moduation with LPE fabrication process on the predeposited, sef-seeding Zn-DM ayer fabricated without using the moduator for 5 cyces. 8

19 methano adsorbed / mmo g - F / Hz 98 K Reative vapor pressure / P/P Figure S8 Methano adsorption isotherms at 5 C using the environmentay controed quartz crysta microbaance (QCM) of Zn-DM fims fabricated at C with various rm ratio via integration of coordination moduation with LPE fabrication process on the sef-seeding Zn-DM ayer fabricated without using the moduator for 5 cyces B. Zn-DM fims fabricated by the coordination moduation-controed LPE process by mixing acetic acid [Zn O(OAc) 6 ] =.5 mm, [H DM] =.5 mm moduator mixed with inker soution 6 8 Deposition time / min Figure S9 In-situ monitoring of QCM frequency during the fabrication of Zn-DM fims at C via integration of coordination moduation with LPE fabrication process without seeding ayer; using ZnO(OAc)6.5 mm and HDM.5 mm as precursor soutions, and acetic acid as coordination moduator by mixing it with the HDM soutions with various rm ratio 9

20 Normaized Intensity / a.u degree Figure S XRD patterns of Zn-DM fims fabricated at C via integration of coordination moduation with LPE fabrication process; using ZnO(OAc)6.5 mm and HDM.5 mm as precursor soutions, and acetic acid as coordination moduator by mixing it with the HDM soutions with various rm ratio (corresponding with the growth data in Figure S9) methano adsorbed / mmo g - 98 K 8 6 [Zn O(OAc) 6 ] =.5 mm, [H DM] =.5 mm moduator mixed with inker soution Reative vapor pressure / P/P Figure S Methano adsorption isotherms at 5 C using the environmentay controed quartz crysta microbaance (QCM) of Zn-DM fims fabricated at C via integration of coordination moduation with LPE fabrication process without sef-seeding ayer; using ZnO(OAc)6.5 mm and HDM.5 mm as precursor soutions and acetic acid as coordination moduator by mixing it with the HDM soution with various rm ratio