Isotropic and Anisotropic Growth of MetalâOrganic Framework (MOF

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Isotropic and Anisotropic Growth of Metal-Organic Framework (MOF) on MOF: Logical Inference on MOF Structure Based on Growth Behavior and Morphological Feature Sora Choi, Taeho Kim, Hoyeon Ji, Hee Jung Lee, and Moonhyun Oh J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b08821 • Publication Date (Web): 11 Oct 2016 Downloaded from http://pubs.acs.org on October 13, 2016

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Journal of the American Chemical Society

Isotropic and Anisotropic Growth of Metal-Organic Framework (MOF) on MOF: Logical Inference on MOF Structure Based on Growth Behavior and Morphological Feature Sora Choi,‡ Taeho Kim,‡ Hoyeon Ji, Hee Jung Lee, and Moonhyun Oh* Department of Chemistry, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul, 120-749, Korea Supporting Information Placeholder

ABSTRACT: The growth of one metal-organic framework (MOF) on another MOF for constructing a hetero-compositional hybrid MOF is an interesting research topic because of the curiosity regarding the occurrence of this phenomenon and the value of hybrid MOFs as multifunctional materials or routes for fine-tuning MOF properties. In particular, the anisotropic growth of MOF on MOF is very fascinating for the development of MOFs possessing atypical shapes and heterostructures or abnormal properties. Herein, we clarify the understanding of growth behavior of a secondary MOF on an initial MOF template, such as isotropic or anisotropic ways associated with their cell parameters. The isotropic growth of MIL-68-Br on the MIL-68 template results in the formation of core-shell type MIL-68@MIL-68-Br. However, the unique anisotropic growth of a secondary MOF (MOF-NDC) on the MIL-68 template results in the semi–tubular particles, and structural features of this unknown secondary MOF are successfully speculated for the first time on the basis of its unique growth behavior and morphological characteristics. Finally, validation of this structural speculation is verified by the powder X-ray diffraction and the selected area electron diffraction studies. The results suggests that the growth behavior and morphological features of MOFs should be considered as important factors for understanding the MOFs’ structures.

INTRODUCTION Metal-organic frameworks (MOFs) and porous coordination polymers (CPs) have received great attention not only because of their various structural topologies and chemical tunabilities but also their several useful properties and applications, such as gas storage, gas separation, catalysis, sensing, and recognition.1–12 The researchers are attempting to produce micro- or nano-scaled CP particles (CPPs)13–22 including micro- or nano-MOFs because these materials can extend application areas or enhance the properties of the original CPs and MOFs. Indeed, micro- or nano-scaled CPPs and MOFs display enhanced properties and have been utilized in unique application areas such as magnetic resonance imaging (MRI) contrast agents, drug delivery vessels, and bio-sensing.18–22 The conjugation of MOF materials with other materials, such as silica, polystyrene, magnetic particle, and noble metal particle,23–28 is a noble strategy for producing MOF-based functional materials. Not only the conjugation of MOFs with other materials but also the controlled conjugation of MOFs with different types of MOFs29–34 to form hybrid MOFs containing more than two types of MOFs in one particle is a central goal in the MOF development; this is because the management of the composition and structure of MOFs is essential for fine tuning their properties. These hybrid MOF materials with precise heterocompositions or heterostructures will provide great opportunities to overcome their inherent weak points or to obtain user’s desirable properties. However, no many studies have examined the construction of hybrid MOFs

through the continuous growth of a secondary MOF on an initial MOF.30–34 In particular, there are only few examples for understanding the hybrid MOF formation through the anisotropic growth of MOF on MOF,33,34 and the creation of a well-defined heterointerface between two completely different MOFs has rarely been demonstrated. Herein, we report the investigation of the isotropic and anisotropic growth of two MOFs, named MIL-68-Br (MIL standing for Materials of Institut Lavoisier) and MOF-NDC (NDC standing for naphthalene-1,4-dicarboxylic acid), on a microsized MOF template made from MIL-68. The isotropic growth of MIL-68-Br on the MIL-68 template resulted in the core-shell type MIL-68@MIL-68-Br. In addition, the fascinating anisotropic growth of MOF-NDC on the MIL-68 template resulted in the formation of unusual semi–tubular particles. In particular, the crystal structure of a new MOF (MOF-NDC) was speculated on the basis of its unique growth behavior and morphological features and the speculated structure was validated from powder X-ray diffraction (PXRD) and selected area electron diffraction (SAED) studies.

RESULTS AND DISCUSSION Three CPPs were first constructed from the solvothermal reactions of In(NO3)3 with one of the following three different but similar organic building blocks: terephthalic acid (benzene dicarboxylic acid, H2BDC), 2-bromoterephthalic acid (H2BDC-Br), and naphthalene-1,4-dicarboxylic acid (H2NDC) (Scheme 1). Technically, the three organic building blocks have identical lengths from one side of the carboxylic acid group to the other (Scheme 1); therefore,

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Scheme 1. Solvvothermal reacctions for the ssynthesis of CP PP-I–CPP-III. T The box showss ball-and-stickk representatio ons of the MIL--68 structure, whicch has a three-dimensional hexagonal struccture of [In(OH H)(BDC)]n, consisting of a on ne-dimensionaal metal ion chaain in the c directio on

structural and/oor morphologiccal similarities am mong the three CPPs made from theese organic buiilding blocks caan be expectedd. The three CPPs werre first characterrized by scanninng electron micrroscopy (SEM) and PXRD P (Figure 11). First of all, itt should be noteed that the hexagonal rods of MIL-68 (CPP-I, Figuure 1a), which has a three-dimensional hexagonal structure s of [Inn(OH)(BDC)]n consisting of a one--dimensional m metal ion chain inn the c directionn (box in Scheme 1), rresulted from thhe solvothermal reaction of In(N NO3)3 and H2BDC.35,36 A similar reacttion of H2BDC--Br instead of H2BDC with In(NO3)3 resulted in the formation of thhin micro-rods (CPP( q thin; it haas also II, Figure 1b). Even the resultting CPP-II is quite hexagonal facetts (bottom of Fiigure 1b), charaacteristic for the MIL68 structure. Inn addition, CPP P-II displayed a PXRD patternn (Figure 1f) almost iidentical to that of CPP-I (Figuure 1e) and a sim mulated PXRD patteern of MIL-68 ((Figure 1d). Thhese data clearlyy support that CPP-II has a three-ddimensional hexxagonal structure (denoted as MIL-668-Br), similar to the MIL-688 structure of C CPP-I. Overall, this indicates that thee bromo moietiies within H2BD DC-Br building blockss did not affecct the structurral or morphollogical change in CPPss synthesized froom H2BDC-Br. On the otheer hand, a solvoothermal reactiion of In(NO3)3 and H2NDC resulteed in the formaation of thin roods (CPP-III, F Figure 1c). Importantlly, these rods haave square facetts instead of thee characteristic hexaggonal facets of tthe MIL-68 struucture. The moorphological features of CPP-III will aid in undersstanding its struuctural features as well as its growth bbehavior on the MI-68 templatee. UnMIL-68 like CPP-I and CPP-II of the tthree-dimensionnal hexagonal M P-III has a quuite distinguishhable PXRD pattern structures, CPP (Figure 1g); thherefore, we cann imagine that itts structure (deenoted as MOF-NDC)) is different froom the MIL-688 structure. Thee additional bulky aroomatic rings of the NDC buildding blocks com mpared with the BDC bbuilding blockss may interrupt the formation of the

OFMIIL-68-like structture. The exact crystal structurre of a new MO ND DC was not avaailable at this pooint because thhe preparation oof a goood single crystall was not successsful. However, the speculationn of struuctural features of MOF-NDC on the basis off its unique grow wth behhavior and morpphological featuures, and the annalysis of its PXR RD andd SAED patternns will be discusssed later (Figurees 4, 5, and 7). T gas sorptionn properties of tthe resulting thrree CPPs were oobThe tainned from theirr N2 sorption issotherms. CPP-I of the MIL--68 struucture is knownn to be a quite pporous materiall,36 as shown inn its sorrption isotherms [red line in Fiigure S1; the Brrunauer–Emmeett– Telller (BET) surfface area and tootal pore volumee were 1564 m2g−1 andd 0.69 cm3g−1, reespectively]. Thhe BET surface area a and total poore vollume of CPP-II of the MIL-68--Br structure (10062 m2g−1 and 0.47 cm m3g−1, respectivelly) were slightlyy lower than thhose of CPP-I bbecauuse of the brom mo moieties withhin the MIL-68--Br structure (blue linee in Figure S1 and Table S1). Compared C with CPP-I made froom H2B BDC, the extra bromo moietiess within CPP-III decrease the vooid vollume within thee structure andd increase the rrelative weight pper uniit volume, thereeby reducing thee total pore voluume per a gram m of CP PP-II. N2 sorpttion isotherms of CPP-III of the MOF-ND DC struucture also dispplayed type I behavior, b typicaal of microporoous maaterials (purple line in Figure SS1), and its BET T surface area aand total pore volumee (597 m2g−1 and 0.27 cm3g−1, rrespectively) w were wer than those of o CPP-I and CPP-II C (Table S1). Pore size ddislow tribbutions of CPP P-I–CPP-III weere calculated from fr the non-loocal dennsity functionall theory (NLDF FT) method (F Figure S2). CPP P-I andd CPP-II have ttwo different poores (ca. 0.6 andd 1.2 nm), howevver, CP PP-III has only one dominant pore at ca. 0.7 nnm. Thermograavimeetric analysis (T TGA) curves andd infrared (IR) spectra of all saamplees are shown in F Figures S3 and SS4. Three CPPss (CPP-I–CPP--III) havve a similar therrmal stability, ass shown in their TGA curves (F Figuree S3).


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Figure 1. SEM images i of (a) hexxagonal rods of C CPP-I, (b) thin hhexagonal rods of CPP-II, and (cc) rectangular rodds of CPP-III. T The insets in (a) and a (b) show the heexagonal facets, aand the inset in ((c) shows a squaare facet. (d) Sim mulated PXRD pattern of MIL-688, PXRD patternns of (e) CPP-I, (f) CPP-II, and (g) CPP-III.

Scheme 2. Sch hematic repreesentation for constructing core– shell-type and d semi–tubularr-type hybrid--CPPs through h isotropic and aniisotropic grow wth of the secon ndary MOFs o on the MIL-68 templaate, respectivelly

As an essentiial subject, we hhave investigatedd growth behaviiors of MOFs on the ssurface of a miccro-MOF templlate (Scheme 2). Micro-MOF tempplate of MIL-68 (Figure 2a and F Figure S5a) as a short version of CPP P-I was first preepared using a ssynthetic methood reported before.366 The isotropic ggrowth of MIL--68-Br on the M MIL-68 template to prroduce the coree–shell-type MIIL-68@MIL-688-Br is foreseeable beccause the initial MIL-68 templaate and the secoondary MIL-68-Br havve virtually identtical structures, as verified from m their PXRD patternss (Figure S5a aand Figure 1f); therefore, the MOF system cannot recognize the ffact that the orrganic building block BDC-Br. Indeedd, the PXRD pattern was changed frrom BDC to B (Figure S5b) of the core–sshell-type hybrrid-CPP-II of MILPXRD pattern aas the 68@MIL-68-Brr displayed exacctly the same P initial MIL-68 ttemplate (Figurre S5a). SEM im mages (Figure 2) revealed the form mation of long hexagonal rods (hybrid-CPP-II ( I) as a result of the isootropic growth of the secondary MIL-68-Br oon the

MIIL-68 template. With increasinng time, the lenggth of the produuct draamatically increaased, with a smaall increase in thhickness comparred witth that of the iniitial hexagonal llump template ((Figure 2d). Thhere was no pure MIL-668 template rem mained after the reaction and thhere was no significantt pure MIL-68--Br generated aafter the reaction. Thhe contrast lighht and shade trransmission eleectron microscoopy (TE EM) and scannning TEM (STE EM) images (Fiigures 2e and f)) of hyb brid-CPP-II weell depicted an M MIL-68 templatte core portion aand a nnewly grown MIL-68-Br shell poortion, indicatinng the formationn of corre–shell-type M MIL-68@MIL-68-Br. Noticeabbly, the elemenntal maapping images ((Figure 2f) show wed a core–sheell structure whhere broomine atoms exiist in the entire particle, with weak w distributionn at thee center of the pparticle. In addiition, EDX specctrum profile scanninng data of hybriid-CPP-II (Figuures 2g and h) confirmed the fformaation of well-sttructured core––shell-type MIL L-68@MIL-68--Br. Broomine atoms, ass a component of the MIL-68--Br shell, were ddistribbuted over the entire particle; however, they were dominantt at thee edge of the rodd, which is a typpical distributionn tendency for tthe sheell portion withiin a core–shell sttructure (Figurees 2g and h). T relative am The mounts of the M MIL-68 core andd MIL-68-Br shhell witthin MIL-68@M MIL-68-Br weree determined frrom the 1H NM MR speectrum. First, hybrid-CPP-II h was digested in i a co-solventt of aceetic acid-d4 andd DMSO-d6; thhe relative ratioo of H2BDC aand H2B BDC-Br, and thhus, the relative amounts of thee MIL-68 core aand MIIL-68-Br shell w within hybrid--CPP-II were ddetermined to be 1:33.65 by integratiing the peaks coorrelated to H2B BDC and H2BD DCBr (Figure 2i). N2 sorption isotherrms of hybrid-C CPP-II (green lline in F Figure 2j) reveaaled that its BE ET surface area (1346 m2g−1) aand 3 −11 total pore volume (0.58 cm g , Table S1) vaalues are situatted MILrouughly between tthose of MIL-688 (red line of Fiigure 2j) and M 68--Br (blue line off Figure 2j).



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NDC and In(N NO3)3, the resultting particle sizze of hybrid-CP PPH2N III increased with keeping the sem mi-tubular shapee (Figure S6). A As a conntrol experimennt, the growth off MIL-68 on thee MOF-NDC teemplaate resulted in thhe similar semi-ttubular particless (Figure S7). T The PX XRD pattern off hybrid-CPP-IIII (Figure 4b)) showed the coexistence of both MIL-68 and MOF-NDC M struuctures within tthe parrticles. All peakks from both MIL-68 core andd MOF-NDC shhell were found in the PXRD pattern of hybrid-CPP P-III. The ratioo of DC and NDC w within the particlles, and thus, the relative amouunts BD of the MIL-68 corre and MOF-N NDC shell were determined to be B and H2ND DC 1:11.11 by integratiing the peaks coorrelated to H2BDC in the 1H NMR sspectrum of hyybrid-CPP-III (Figure 3e). T The 1:11.11 molar ratioo of MIL-68 coore and MOF-N NDC shell withhin hyb brid-CPP-III corresponds c to tthe 1:1.30 weighht ratio of MIL--68 corre and MOF-ND DC shell (for tthis calculation, we have assum med thaat MOF-NDC hhas a chemical foormula of [In(O OH)(NDC)]n sim milar with [In(OH)(BDC)]n for M MIL-68.). The grrowing amountt of OF-NDC on the MIL-68 template was relativeely lower than thhat MO of M MIL-68-Br, as vverified from thheir final sizes (F Figures 2c and 3c) 3 andd the relative rattios of the initiaal and the secondary MOFs withhin hyb brid-CPP-II (11:3.65) and hyb brid-CPP-III (1:1.11). ( N2 soorptionn isotherms oof hybrid-CPP-III (MIL-68@ @MOF-NDC) reveaaled that its BET surface area (1021 m2g−1) aand total pore vvolum me (0.46 cm3g−1) values are locaated between thoose of MIL-68 aand MO OF-NDC (Figuure 3f). These vvalues were quitte similar to thoose (10017 m2g−1 and 0.45 cm3g−1, reespectively) callculated from tthe sim mple sum of the 1:1.30 weight ccontributions off pure MIL-68 aand MO OF-NDC withinn hybrid-CPP-IIII.

Figure 2. SEM iimages of (a) thee initial micro-teemplates of MIL--68, (b) the intermediatees, and (c) the coore–shell-type hyybrid-CPP-II off MIL68@MIL-68-Br.. (d) SEM imagges showing thee particle growtth. (e) TEM image andd (f) STEM imagge, with the elem mental mapping iimages of In (green) annd Br (orange) of hybrid-CPP-II. (g) and (h)) EDX spectrum profilee scanning data ffor bromine atom m of hybrid-CPP P-II of MIL-68@MIL-668-Br. (i) 1H NM MR spectrum of h hybrid-CPP-II digestd ed in acetic aciid-d4 and DMSO O-d6. (j) Comparison of N2 soorption isotherms of thee template (MIL L-68, red), CPP--II (MIL-68-Br, blue), and hybrid-CPP P-II (MIL-68@M MIL-68-Br, greenn).

The next atteempt for the invvestigation of thhe growth of MO OF on MOF was condducted using H2NDC as an orrganic building bblock. First, it shouldd be reminded that a totally different frameework (MOF-NDC) was w constructedd from the reacttion of In(NO3)3 and H2NDC, compared it with the formation of MIL-68-like M structures a H2BDC-Br. SEM images (Figure 3) of hyybridfrom H2BDC and CPP-III revealeed an obvious inncrease in particcle size and the exclusive formation oof the fascinatinng semi–tubular particles after 220 min. The pure MIL-68 template wass not remained after the reactioon and DC was not generated after thee reacthe significant ppure MOF-ND tion. The formaation of the sem mi–tubular particles was clearlyy confirmed again from TEM imagges (Figure 3d).. These semi–tuubular o the particles can be constructed ffrom the anisottropic growth of F-NDC on the six rectangular facets but not oon the secondary MOF two hexagonal facets f of hexagoonal lump templlates of MIL-68.. After the initial formaation of MOF-N NDC on the ac pplane of the tem mplate, MOF-NDC caan further grow w along to the c-axis to form semitubular particlees. As increasingg the reaction tim me or the amouunts of

Figgure 3. SEM imaages of (a) the iniitial micro-templlates of MIL-68 aand (b)) the intermediattes. (c) SEM andd (d) TEM imagges of hybrid-CP PPIII of semi–tubularr-type MIL-68@MOF-NDC. Thhe bottom imagess in (a))-(c) clearly shoow the particle ggrowth. (e) 1H NMR spectrum m of hyb brid-CPP-III digested in acetic aacid-d4 and DMSSO-d6. (f) Compparisonn of N2 sorptionn isotherms of the template (MIL L-68, red), CPP--III (M MOF-NDC, bluee), and hybrid d-CPP-III (MIL L-68@MOF-ND DC, greeen).

T This unusual anisotropic a groowth for the production p of tthe uniique semi–tubular particles cann be understood on the basis of tthe celll parameter diffferences betweeen MIL-68 and M MOF-NDC. First, we must pay attenntion to the facct that the grow wth of MOF-ND DC was very efficient oon the six rectanngular facets, w which expose thee ac


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plane of MIL-68. To grow efficciently on the acc plane of the M MIL-68 F-NDC should have an identtical one-dimennsional structure, MOF metal ion chainn in the directionn of the c axis annd thus have ann identical c cell param meter with the M MIL-68 templatte. In addition, M MOFNDC should haave an identical repeating unit iin the direction of the a axis with thee MIL-68 struccture (Figure 55). Initially, a threedimensional rhhombic structurre (Figure 5c) was consideredd as a possible candiddate for the MO OF-NDC structture. When thee onedimensional meetal ion chain iss propagated in a zigzag, as desccribed in Figure 5b, a three-dimensioonal hexagonal structure of M MIL-68 (crystal system: orthorhombicc) should occurr. On the other hand, when this one-dimensional metal ion chain iis propagated inn onedirection, as deescribed in Figuure 5c, a three-ddimensional rhoombic structure (crysttal system: hexaagonal) should bbe produced. However, no correlatiion between thhis imaginary rhhombic structurre and the obtained P PXRD pattern oof MOF-NDC was found. Wee then focused on its m morphological features. fe In manny cases, the morrphology of MOFs and CPPs inndicates their innner-structure information.36–40 Thee square or rectaangular facets off CPP-III madee from MOF-NDC, instead of hexagoonal facets, indiccate that MOF--NDC possibly has a sqquare or rectanggular structure instead of a hexaagonal or rhombic struucture. A three-ddimensional squuare structure (F Figure 5d, crystal system: tetragonal)) was next considered as a poossible OF-NDC. Thiss three-dimensioonal square struucture structure of MO could possibly bbe formed from m the simple adjjustment of the angle between the organic building bblock wings (grreen lines in thee schematic representtation) interactting with the onne-dimensional metal ion chain (Figuure 5d).

Figure 4. PXR RD patterns of ((a) CPP-III of MOF-NDC, (bb) hyL-68. brid-CPP-III oof MIL-68@MO OF-NDC, and (cc) CPP-I of MIL This speculated three-dimennsional square structure s (Figurre 5d) mplate in the direection has well-matcheed lattices with tthe MIL-68 tem of the a and c aaxes but has a m mismatched lattiice in the directtion of the b axis; therrefore, it can grow on the six rrectangular faceets (ac plane) but cannnot grow on thee two hexagonaal facets (ab planne) of the MIL-68 tem mplate (Figure 55e). Finally, anallysis of PXRD

Figgure 5. (a) Scheematic and ball-and-stick repreesentations of onnedim mensional metaal ion chain wiithin MOF (M MIL-68 and MO OFND DC). (b) Zigzaag propagationn of one-dimennsional metal iion chaains (see metal ion chains 1 annd 2) for the forrmation of a thrreedim mensional hexaggonal structure oof MIL-68 (crysstal system: orthhorhoombic). (c) O One-direction ppropagation off one-dimensioonal chaains for the form mation of a threee-dimensional rhombic structuure (crrystal system: heexagonal). (d) One-direction O prropagation of onnedim mensional chainns for the formattion of a three-ddimensional squuare struucture of MOF--NDC (crystal ssystem: tetragonal). (e) The ppossiblle growth of MOF-NDC on thhe rectangular faacets (ac plane)) of thee MIL-68 templlate (left). The iimpossible grow wth of MOF-ND DC on the hexagonal facets f (ab planee) of the MIL-688 template (righht). ween two metal ion chains (twoo blue dots in FigF Thhe distance betw uree 5b) of MIL-688 is 10.887 Å, annd that (two bluue dots Figure 55d) of MOF-NDC M is ccalculated at 10.9922 Å from its PXRD P pattern.



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C at 2θ = 8.10, 9..74, 11.44, 16.222, 17.06, and 18.12° 4a)) of MOF-NDC were assigned to thhe (300), (320)), (330), (600),, (620), and (6330) plaanes of the threee-dimensional sqquare structure, respectively.

Figgure 7. (a) TE EM image of CP PP-III and (b) SAED patternn of MO OF-NDC obtainned from the reegion marked w with a circle in ((a). (c)) TEM image oof hybrid-CPP-III (MIL-68@ @MOF-NDC) aand (d)) SAED patternn of MOF-NDC C shell part obtaained from the regioon marked with a circle in (c).

Figure 6. (a) C Crystal structuree of MIL-68 projjected along thee [001] zone axis. (b) SSimulated SAED D pattern of MIL-68 along the [001] zone axis. (c) TEM image off MIL-68 tempplate and (d) experie m mental SAED ppattern of MIL-668 obtained froom the region marked with a circle in (c). (e) Crystal structure of MIIL-68 projected along the [3-10] zonee axis. (f) Simullated SAED patttern of MIL-68 along the [3-10] zonee axis. (g) TEM M image of MIL-68 template annd (h) SAED pattern of o MIL-68 obtaained from the region r marked w with a circle in (g). OF-NDC and MIL-68@MOF F-NDC verifiedd that patterns of MO MOF-NDC haas a three-dimennsional square structure. The measured PXRD patttern of MOF-N NDC was well m matched with thhe calculated patternn of the speculaated three-dimeensional square structure, as verifiedd by the whole pattern fitting using MDI Jadde 9.0 software (Figurre S8). The unit cell parameterrs of MOF-NDC calculated using MDI M Jade 9.0 sooftware were a = b = 32.765 Å, Å c= 7.182 Å, and α = β = γ = 90° (F Figure S8); thesee values, specificcally a and c cell parameters, were w well matched wiith those of MIIL-68. The repeating distance betweeen two metal iion chains (twoo blue dots in Figure 5b) of three-ddimensional heexagonal structuure of MIL-68 is 10.8887 Å, and that (two blue dots inn Figure 5d) of threedimensional squuare structure of o MOF-NDC iss calculated at 10.922 1 Å from its PXR RD pattern. In laast, six intensive PXRD peaks (F Figure

T additional evidence for the rationale oof the anisotroopic The groowth of MOF-N NDC on the acc plane (six recttangular facets)) of MIIL-68 template was w obtained froom the SAED ddata (Figures 6 aand 7). The simulatedd SAED patternns of MIL-68 sttructure along tthe u the softw ware [0001] and [3-10] zone axes weree obtained by using SinngleCrystal Verr. 2.3.3 (Figurees 6b and f). The experimenntal SA AED patterns oof MIL-68 tem mplate (Figures 6d and h) w were maatched well withh the simulated SAED patterns. In special, stroong spoots for Bragg reeflections of (0440), (060), (0880), (130), (1331), andd (260) were oobserved in thee experimental SAED patternss of MIIL-68 template. The d-spacingg values of d(040)), d(130), and d(131) ( were 9.208, 10.5388, and 5.631 Å , respectively. The T cell parametters of MIL-68 templaate derived from m these SAED patterns were a = 21..076, b = 36.8088, and c = 6.823 Å. Note that thhere is slight devviationn in these derivved cell parameeters compared to those obtainned from the single crrystal structure (a = 21.774, b = 37.677, and c = ED 7.2233 Å) possiblyy due to the sligght destruction during the SAE meeasurement. The SAED patternns of CPP-III and hybrid-CP PPIII are displayed in Figure 7. Thhe SAED patterrn of shell partt of hyb brid-CPP-III ((Figure 7d) waas exactly identtical to the SAE ED patttern of MOF-N NDC measured from CPP-III ((Figure 7b), whhich inddicated the shelll part of hybrid--CPP-III is idenntical to the MO OFND DC. In special, thhe d-spacing vallues of d(300) andd d(002) were 10.7713 andd 3.458 Å for CP PP-III, and 10.7764 and 3.443 Å for hybrid-CP PPIII, respectively. T The cell parameeters of MOF-N NDC derived froom SA AED pattern of h hybrid-CPP-IIII were a = b = 32.139 Å and c = 6.9916 Å. The a and c cell paraameters of MO OF-NDC are well w maatched with thosse of MIL-68 teemplate (3/2a = 31.614 Å and c = 6.8823 Å), but the b cell parameteer of MOF-NDC C is not correlatted witth that of MIL-668 template (b = 36.808 Å). Thhese SAED studdies


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support again the motive for the unusual anisotropic growth of MOF-NDC on the ac plane of MIL-68 template.

CONCLUSION In conclusion, we have demonstrated the fascinating isotropic and anisotropic growth of two MOFs, MIL-68 analogs (MIL-68-Br) and non-analog (MOF-NDC), on the MIL-68 template. Isotropic growth of MIL-68-Br on the entire surfaces of the MIL-68 template progressed to form core–shell-type MIL-68@MIL-68-Br. However, the unique anisotropic growth of MOF-NDC on the six rectangular facets (ac plane of MIL-68 structure) but not on the two hexagonal facets (ab plane) of the MIL-68 template produced abnormal semi–tubular particles. In addition, the structural features of MOFNDC were successfully speculated for the first time by considering its unique growth behavior and morphological characteristics; the validation of this structural speculation was confirmed from the PXRD and SAED studies of MOF-NDC. The growth behavior and morphological features of MOFs should be considered as important factors in the future for understanding the MOFs’ structures. The construction of a well-defined MOF-on-MOF structure is highly essential for producing multi-functional MOFs and fine tuning the properties of MOFs. The growth of MOF on MOF demonstrated here should provide a noteworthy guidance for the rational construction of hetero-compositional and functional MOF materials.

ASSOCIATED CONTENT Supporting Information Experimental details, Figure S1-S8, Table S1, and S2. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author [email protected]

Author Contributions ‡These authors contributed equally.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (no. NRF-2012R1A2A1A03670409 and NRF-2015R1A2A1A15053777).

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Isotropic and Anisotropic Growth of MetalâOrganic Framework (MOF

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