Vacuum-Mediated Single-Crystal-to-Single-Crystal (SCSC

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Vacuum Mediated Single-Crystal-to-Single-Crystal (SCSC) Trans-formation in Na-MOFs: Rare to Novel Topology and Activation of Nitrogen in Triazole Moieties Shagufi Naz Ansari, Sanjay K. Verma, Aleksandr A Garin, and Shaikh M. Mobin Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01753 • Publication Date (Web): 20 Feb 2018 Downloaded from http://pubs.acs.org on February 21, 2018

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Crystal Growth & Design

Vacuum Mediated Single-Crystal-to-Single-Crystal (SCSC) Transformation in Na-MOFs: Rare to Novel Topology and Activation of Nitrogen in Triazole Moieties Shagufi Naz Ansari,† Sanjay K. Verma,† Aleksandr A. Garin° and Shaikh M. Mobin*†‡§ †

Discipline of Chemistry, ‡Center for Biosciences and Bio-Medical Engineering and §Discipline of Metallurgy Engineering and Materials Science, Indian Institute of Technology Indore, Simrol, Khandwa Road, Indore 453552, India.° Samara Center for Theoretical Materials Science (SCTMS) Samara University, Samara 443011, Russia. ABSTRACT: We report rare example of facile in-situ synthesis of Na-MOF1 that undergoes

vacuum mediated SCSC transformations from rare parallel polycatenated kgd nets to new and novel 3-periodic 3,3,12-c net topology (named smm1). Further, SCSC transformation of NaMOF1 to Na-MOF2 reveals activation of N-N-atoms in 1,2,3-triazole unit. Na-MOF1 and NaMOF2 were authenticated by single crystal X-ray studies and the bulk was confirmed by PXRD studies. Owing to the structural flexibility, high porosity and its stability against any external forces such as heat, light and vapor, metal-organic frameworks (MOFs) has gained tremendous attention in the field of gas adsorption, drug delivery, energy storage, catalysis and fluorescent sensors.1-8 Apart from these applications the studies to simplify the complicated frameworks with simple topology has also been evolved as a fascinating tools. MOFs with several network topologies can be designed and synthesized using a simple node-and-linker approach.9 Highconnected nets with mixed connectivity such as (3,6)-, (4,6)-, (4,8)-, (3,7)-, (3,8)-, (3,10)-, and (3,12) connected frameworks are sporadically documented because of coordination number and geometric limitation.10-11 Moreover frameworks consisting of parallel polycatenated kgd-layers with (3,6)-connectivity are very rare.12-15 The construction of MOFs varies depending on the reaction conditions such as hydro/solvothermal methods, solvent, concentration, temperature, and ratio of reactants and pH.16 Although, the transition and lanthanides metals based MOFs has been explored extensively with an excellent properties but alkali or alkaline metal based MOFs remain unexplored. In specific, sodium based MOFs are very rare and involves challenging task due to the fact that sodium

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prefer to coordinate large ratios of solvents instead of organic linkers which results in unstable frameworks. Only recently, Yaghi et al reported two stable sodium MOFs; the MOF-705, [Na4(BDA)(CH3OH)(H2O)] and the extended version MOF-706, [Na4(BPDA)(H2O)2], BDA= (2S,2'S)-2,2'-(terephthaloylbis(azanediyl))disuccinate.17 The nitrogen rich 1,2,3-triazole containing derivatives synthesized via CLICK chemistry by a triple Huisgen 1,3-dipolar cycloaddition have gained considerable interest in the various field viz biological activities, material science, organic and coordination chemistry.18 Due to high aromaticity, they possess high stability under basic and acidic as well as reductive and oxidative conditions.19 The formation of newer materials with fascinating properties by employing SingleCrystal-to-Single–Crystal (SCSC) transformation techniques have gained wider popularity in last decade due to their potential applications in sensor technology, magnetic materials, catalysis and gas storage materials.20-21 The SCSC transformation by external stimuli such as heat, light and vapor are commonly employed and able to maintain the desired crystallinity after transformation at discrete and polymeric level.22-24 However, less explored is the high-vacuum mediated SCSC transformation where the transformed product results in the collapse of structure due to bond breaking and bond formation in the lattice which in turn results in loss of crystallinity. Thus, vacuum mediated SCSC transformation in which crystallinity is retained has been recognized as a challenging process.25 The in-situ alteration of ligand followed by formation of MOFs are mostly via hydro or solvo thermal techniques and leads to unusual structures.26-27 In order to explore the effect of the introduction of nitrogen rich moiety along with flexible functionality on the sorption as well as topology of MOFs, we report facile in-situ synthesis of Na-MOF1, as the first example of Na based parallel polycatenated framework (Scheme 1). A reaction of 1,3,5-triethynylbenzene and azidoglycine ethylester, using the standard “Click” conditions yielded {4-[3,5-Bis-(1-carbonylmethyl-1H-[1,2,3]triazol-4-yl)-phenyl]-[1,2,3]triazol1-yl}triacetate L(Et)3 with three flexible arms (Scheme S1). L(Et)3 has been characterized by 1H and

13

C NMR and authenticated by single crystal x-ray studies ( Figure S1-S3 and Table S1 ).

The crystal structure of L(Et)3 reveals that it lies about a three-fold axis. Further, colorless cube shaped tiny-crystals of the Na-MOF1 were obtained by in-situ basic hydrolysis reaction of L(Et)3 with aqueous solution of NaOH in methanol at RT for overnight stirring followed by


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simple slow evaporation of reaction mixture at RT (Scheme 1). To the best of our knowledge so far only one report is available which discussed the binding modes of tritopic linker (L3-)( L3-: deprotonated LH3) with La metal ion, which was prepared in two steps (i) isolation of {4-[3,5Bis-(1-carbonylmethyl-1H-[1,2,3]triazol-4-yl)-phenyl]-[1,2,3]triazol-1-yl}acetic acid (LH3) from ester L(Et)3 by using THF as solvent and then (ii) solvothermally reacting with La(NO3).6H2O salt at 100 oC (Scheme S2).28 However, in contrast we report a facile in-situ alteration of L(Et)3 and synthesis of Na-MOF1 at room temperature. Na-MOF1 is soluble in water, methanol and ethanol and can be recrystallized easily in its original form from these solvents.

Scheme 1. Schematic representation for synthesis of Na-MOF1. Na-MOF1 crystallizes in a trigonal crystal system with centrosymmetric space group R-3c (Figure 1 and Table S2). Asymmetric unit of Na-MOF1 contains one Na ion site connected by two µ2 bridging water molecules, one oxygen atom O(3) of free water molecule and one carboxylate (‒COO¯) oxygen atom from a L3‒ (Figure S4). Four oxygen atoms from µ2 bridging water molecules and one oxygen atom from terminal water molecule are at the equatorial position of Na(I) site, and rest two oxygen atoms from two ‒COO¯ of L3‒ ligands are in the axial position giving 7 coordination number to each Na atom (Figure S5). The bridging water molecules between the Na ions form a Na6(H2O)12 closed ring cluster.



Figure 1. Ball-stick model of Na-MOF1 showing the (a) Coordination environment around the Na ion centre, Na-Na distance (b) 3D packing along c-axis (c) Cis arrangement of three arms of L3‒ ligand (d) molecular-drone shape. Hydrogen atoms are removed for clarity, D represents centre core of metal cluster ring. The Na6(H2O)12 cluster shows Na-Na(adjacent) separation of 3.976(0) Å and Na-Na(opposite) distance of 7.724(0) Å (Figure1a), which are further linked to the neighboring clusters via 6L3‒ ligands in a polyhedral assembly (Figure S6) finally leading to the formation of a MOF (Figure 1b). The whole framework is further stabilized by intra/inter-molecular hydrogen bondings (Table S3) and π···π interactions (Figure S7). The Na–O bond distances including bridging and coordinated H2O molecules to Na-atoms are found to be in the range of 2.3249–2.7102 Å (Table S4). Furthermore, the asymmetric unit contains one highly disordered methanol molecule with partial occupancy in a special position, which cannot be resolved. Thus, SQUEEZE was applied to remove this disordered methanol molecule. L3‒ in Na-MOF1 shows unique features compared to the reported La-MOF with L3‒. L3‒ shows linear arrangement of La with only two-coordinated


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H2O molecules whereas Na-MOF1 shows highly hydrated Na6(H2O)12 cyclized core with 12 bridging water molecules and additional six coordinated water molecules. In La-MOF the two arms of L3‒ are in syn-position and the 3rd arm is in anti-position and in Na-MOF1 all the three arms of L3‒ are in syn-position bonded alternatively to each neighboring Na ions forming a molecular-drone shape (Figure 1c, 1d).

This highly hydrated cyclized Na-MOF1 that can easily yield good quality crystals which prompted us to explore the solid-state structural reactivity of dehydrated product by introducing single-crystal-to-single-crystal (SCSC) transformation technique by applying external stimuli such as vacuum. On exposure of Na-MOF1 crystal to vacuum (10-3 Torr) for 1.5 h results in transformed Na-MOF2 to our surprise by retaining the crystallinity as observed by reasonably good X-ray diffraction pattern (Scheme 2).

Scheme 2. SCSC transformation of Na-MOF1 to Na-MOF2 The X-ray analysis of post vacuum treated Na-MOF1 crystal shows similar trigonal, R-3c space group with about 25% shrinkage of overall cell volume, which established the formation of dehydrated Na-MOF2 (Table S2 and Figure 2). In Na-MOF2, each Na(I) site exists with coordination number 5, involving four coordinated O-atoms from three COO¯ unit and one N-



atom from 1,2,3-triazole ring of L3‒ (Figure 2a). The measured bond distances between two adjacent and oppositely located Na ions in metal cluster core were found to be contracted to 3.704(4) Å and 6.882(1) Å, respectively compared to Na6(H2O)12 cluster in Na-MOF1(Figure 2b). This dehydrated Na6 cluster further grows to form 3D-network (Figure 2c). The Na–O bond distances are in the ranges of 2.420(5)–2.867(9) Å and Na(1)‒N(3) bond distance is 2.486(6) Å. (Table S4). However, there also exists one slightly elongated Na(1)-N(2) bond distance of 2.930(7). The SCSC transformation from Na-MOF1 to Na-MOF2, results in the following: (i) contraction of metal cluster cavity size from 7.724(0) Å to 6.882(1) Å, due to the

Figure 2. Ball-stick model of Na-MOF2 showing: (a) 3D-network along c-axis (b) Coordination environment around Na ion (c) Na-Na bond distances. D represents centre core of metal cluster ring.


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removal of both bridging and coordinated water molecules and (ii) activation of the N-N atoms of 1,2,3-triazole ring. In Na-MOF1 the angle between the plane of central benzene ring and 1,2,3-triazole ring of L3‒ is found to be 6.57° with nearest Na---N non-bonding distances as Na(1)-N(2) 4.988 Å and Na(1)-N(3) 5.612 Å, whereas after vacuum with the dehydrated NaMOF2 the corresponding angle shows a deviation to 14.54° with formation of Na---N coordinate bond. Furthermore, the Centroid-Centroid distance increases from 3.421 Å to 3.575 Å in case of Na-MOF2. Although it is very tricky task to generate and predict a new MOF structure with a specific net topology on the basis of the metal cation and organic linker used as the reactants. However, we have compared the topologies of the Na-MOF1 and Na-MOF2 and found to be unique and interesting. In Na-MOF1, if organic ligands are considered as linkers, Na-based clusters can be identified as six-connected nodes. Thus, the topology of the structure can be simplified29 as a binodal 2periodic (6,3-c)kgd network (Figure 3a) with the point symbol (43)2(46.66.83). This kgd-layers are oriented perpendicular to (0,0,1) and catenated to two adjacent layers, resulting in Doc=2 and Is=114. So, these catenated layers forms a 3D parallel polycatenated array (Figure 3b). In Na-MOF2, as discussed earlier the angle between the planes of centroid benzene ring and 1,2,3-triazole ring has been increased in the process of vacuum due to which the two nitrogen of triazoles came closer to Na ions along with the loss of coordinated water molecules which were engaged in forming hydrogen bonds with the nitrogen atoms. This enhances the new bondings in the form of coordinate bonds between Na ion and nitrogen (The elongated Na-N bond was ignored while assigning topology of Na-MOF2) and it leads to unprecedented 3,3,12-c topology with point symbol: (4.62)6(46.624.824.1012)(63)2 (Figure 3c). We can see this new single 3D net as derived from the catenation of kgd-layers connected by an additional edge that correspond to a new bonding interaction between the Na and the nitrogen of the 1,2,3-triazole. This new topology shows also the feature of self-catenation14,30 of 8-membered rings (Figure S8, S9). These relations could be illustrated by procedure of network decomposition,31 which is realized in ToposPro program package. Procedure consisting of sequentially breaking of equivalent edges until the subnet of the net is no longer self-catenated32 (Figure S10-S12). We collected this net in ToposPro database as a new entry smm1 (Shaikh M. Mobin1).



Figure 3. The schematic view of (a) Underlying 6,3-c kgd net. (b) 2D+2D→3D parallel polycatenation of kgd nets. (c) Underlying 3,3,12-c net. Although proposing actual mechanism in case of MOFs is a challenging task. However, the SCSC transformation of Na-MOF1 to Na-MOF2 may be explained by the probable mechanistic pathways as shown in Scheme 3.


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Scheme 3. Proposed mechanistic pathways of Na-MOF1 to Na-MOF2 via (i) Removal of water molecules (ii) Rearrangement of carboxylate group and (iii) Activation of nitrogen atoms (coming closer from 3.623 Å to 3.334 Å). To better understand the probable mechanism we have taken a slice of the highly hydrated Na6(H2O)12 cluster of Na-MOF1. In the first step the highly hydrated Na6(H2O)12 undergoes removal of both bridging and coordinated H2O molecules followed by rearrangement of –COO¯ from bidentate in Na-MOF1 to µ2-bridged in Na-MOF2 retaining the Na6 clusters with shrinkage in cavity size as discussed earlier. This rearrangement leads to move the overall 1,2,3triazole unit closer to each other (from 3.623 Å to 3.334 Å) leading to the formation of NaMOF2 with new Na-N bonds as discussed earlier (Scheme 3). The Powder X-Ray Diffraction patterns of Na-MOF1 and Na-MOF2 are in agreement with the simulation (Figure 4), demonstrating the material’s bulk purity. The thermal studies (TGA) show that both Na-MOF1 and Na-MOF2 are highly stable upto 300oC (Figure S13). Na-MOF1 and Na-MOF2 are stable in air at room temperature (25°C) and in solvents such as ethyl acetate, acetone and tetrahydrofuran.



Figure 4. Powder XRD spectra of Na-MOF1 and Na-MOF2. N2 adsorption isotherms were performed at 77K for Na-MOF1 and Na-MOF2. The observed adsorption isotherm is typical of type-I behavior. The BET (Brunauer−Emmett−Teller) surface area of Na-MOF1 was determined to be 34.624 m2/g (Figure S14) which increases up to 103.182 m2/g in Na-MOF2 (Figure S15). The average pore diameter for Na-MOF1 and NaMOF2 are 3.288 nm and 2.003 nm, respectively. Further, to check the robustness of framework, the PXRD was recorded after degassing at 100 oC which suggest loss in crystallinity in NaMOF1 this may be due the loss of some water molecules from Na-MOF1. However, Na-MOF2 shows no change in PXRD after degassing at 100 oC, which suggest highly robust framework in Na-MOF2 compare to Na-MOF1 (Figure S16a and S16b). In summary, we report for the first time facile in-situ access to polyhedral based Na-MOF1, as the first example of Na based parallel polycatenated framework. SCSC transformation of NaMOF1 to Na-MOF2 was explored successfully despite being a challenging task to retain


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crystallinity after exposing to vacuum. This SCSC transformation of Na-MOF1 to Na-MOF2 reveals activation of N-N atoms of the 1,2,3-triazole unit. Moreover, the topology features of these MOFs were found to be from rare parallel polycatenated kgd nets to new and novel 3periodic 3,3,12-c net topology which we have named smm1. Furthermore, this complex SCSC transformation of Na-MOF1 to Na-MOF2 was elucidated by the mechanistic pathways. Owing to facile synthesis, stability and solubility, Na-MOF1 and Na-MOF2 may be employed for further applications such as energy storage, chemical sensing and catalysis. Supporting Information. Additional figures, spectra, TGA, PXRD, BET, selected bond length/angle table and Crystallographic Information for L(Et)3 (CCDC 1576279), Na-MOF1 (CCDC 1557239), Na-MOF2 (CCDC 1575898). AUTHOR INFORMATION Corresponding Author Shaikh M. Mobin: [email protected]. ACKNOWLEDGMENTS We thank Prof. David M. Proserpio for assistance with topology analysis. Authors are grateful to the Sophisticated Instrumentation Centre (SIC), IIT Indore for providing characterization facilities. SNA is thankful to MHRD, New Delhi, India for providing research fellowship. SKV is grateful to SERB, New Delhi, India for providing National Post-doctoral Fellowship. «AAG acknowledges the Russian Science Foundation (Grant No. 16-13-10158). S. M. M. thanks SERB-DST (Project No. EMR/2016/001113), New Delhi, India for financial support.

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For Table of Contents Use Only

Vacuum Mediated Single-Crystal-to-Single-Crystal (SCSC) Transformation in Na-MOFs: Rare to Novel Topology and Activation of Nitrogen in Triazole Moieties Shagufi Naz Ansari,† Sanjay K. Verma,† Aleksandr A. Garin° and Shaikh M. Mobin*†‡§

SCSC transformation of Na-MOF1 (6,3-c) to Na-MOF2 (3,3,12-c)

In-situ synthesis of Na-MOF1 undergoes vacuum mediated SCSC transformations from rare parallel polycatenated kgd nets Na-MOF1 to new and novel 3-periodic 3,3,12-c net topology Na-MOF2, rveals activation of N-N-atoms in 1,2,3-triazole unit.



In-situ synthesis of Na-MOF1 undergoes vacuum mediated SCSC transformations from rare parallel polycatenated kgd nets Na-MOF1 to new and novel 3-periodic 3,3,12-c net topology Na-MOF2, rveals activation of N-N-atoms in 1,2,3-triazole unit. 254x190mm (96 x 96 DPI)


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Vacuum-Mediated Single-Crystal-to-Single-Crystal (SCSC

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