Coordination Covalent Frameworks: A New Route for Synthesis and

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Covalent Coordination Frameworks: A New Route for Synthesis and Expansion of Functional Porous Materials Sameh K. Elsaidi, Mona H Mohamed, John S. Loring, Bernard Peter McGrail, and Praveen K. Thallapally ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b11116 • Publication Date (Web): 13 Oct 2016 Downloaded from http://pubs.acs.org on October 14, 2016

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ACS Applied Materials & Interfaces

Covalent Coordination Frameworks: A New Route for Synthesis and Expansion of Functional Porous Materials Sameh K Elsaidi, ¶ lapally ,* ¶

¶,⊥

⊥

¶

Mona H. Mohamed, John S Loring, Bernard. Pete McGrail,‡ Praveen K. Thal-

Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland, WA 99352, USA

⊥ ‡

Chemistry Department, Faculty of Science, Alexandria University, P.O.Box 426 Ibrahimia, Alexandria 21321, Egypt Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, WA-99352, United States

Keywords: two-step recticular chemistry, functional materials, adsorption, covalent coordination frameworks, separation

ABSTRACT: The synthetic approaches for fine-tuning the structural properties of coordination polymers or metal organic frameworks have exponentially grown during the last decade. This is due to the control over the properties of the resulting structures such as stability, pore size, pore chemistry and surface area for myriad possible applications. Herein, we present a new class of porous materials called Covalent Coordination Frameworks (CCFs) that were designed and effectively synthesized using a two-step reticular chemistry approach. During the first step, trigonal prismatic molecular building block was isolated using 4-aminobenazoic acid and Cr (III) salt, subsequently in the second step the polymerization of the isolated molecular building blocks (MBBs) takes place by the formation of strong covalent bonds where small organic molecules can connect the MBBs forming extended porous CCF materials. All the isolated CCFs were found to be permanently porous while the discrete MBB were nonporous. This approach would inevitably open a feasible path for the applications of reticular chemistry and the synthesis of novel porous materials with various topologies under ambient conditions using simple organic molecules and versatile MBBs with different functionalities which would not be possible using the traditional one step approach. The chemistry for connecting the molecular building blocks (MBBs) by strong bonds to isolate porous materials has received a great attention and pursues to flourish to remarka1-2 bly fast pace. This leads to the proliferation of new strategies for synthesis and design of porous materials. One-pot reaction is widely used for the synthesis of functional porous materials such as porous coordination polymers (PCPs) and 3-7 metal organic frameworks (MOFs). However, the one-pot synthesis has been impeded by long-term practical and conceptual challenges that preclude the synthesis by design “tailor-made structures” such as (1) the low solubility of ligands (2) harsh synthetic conditions (3) low reaction yield, (4) inability of expansion of certain frameworks, (5) failure to sustain the same topology even by using the same building 8-9 10-11 units. Two-step reaction is also used for the synthesis of

porous materials by connecting the previously prepared zero 12-13 dimensional MBBs (in the first step). These MBBs are 0D high-symmetry coordination complexes decorated by functional groups that are amenable for a subsequent synthesis in the second step to create an extended network structure. Further, two-step reaction is also used for the synthesis of porous materials by connecting the previously prepared zero dimensional MBBs (in the first step) and connecting the 10-13 MBBs with another metal ion in the second step. Zaworotko’s group recently employed the 2-step crystal engineering strategy to generate multinodal frameworks (binodal and trinodal nets) through connecting the trigonal prismatic MBBs either by metal ion or both metal ion and organic link12-14 er. Nevertheless, the chemistry of linking MBBs together by means of covalent bonds using organic synthesis to isolate extended porous structures is still unexplored. Most recently, Yaghi’s group aimed to develop the step-wise reticular synthesis to combine the chemistry of the MOFs with COFs. However, their efforts were unsuccessful due to the low sol15,13, 16 ubility of the titanium cluster that was used as MBB. Herein, we develop a new route for the synthesis and expansion of the functional porous materials that cannot be formed by the one-pot synthesis through connecting the MBBs by thermodynamically strong covalent bonds using simple organic units to form porous covalent coordination frameworks (CCFs). We coin the term Covalent Coordination Frameworks (CCFs) to elucidate the analogies to the synthet17-19 ic approach of Covalent Organic Frameworks (COFs) by using covalent bonds in connecting MBBs through simple organic reactions that merging the chemistry of COFs with MOFs. To the best of our knowledge, the utilization of covalent bonds for assembling MBBs in step-wise reaction to afford porous structures has not yet been reported. In this context, we report the first five examples of such structures; CCF-1-SE, CCF-2-SE, CCF-3-SE, CCF-4-SE and CCF-5-SE. MBBs are essential for controlling the directionali-

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ty of functional porous materials and endowing the stability, robustness and the desired physical properties for the corre20 sponding structures. The exploitation of MBBs in the design and construction of extended structures is an attractive synthetic approach and its connection by covalent bonds to form CCFs permits its reaction to take place in or near room temperature while maintains the integrity of MBBs throughout the reaction which is hard to be controlled using the one-pot synthesis. Diverse MBBs could be employed for the design and construction of CCFs. However, the utilized MBBs should possess certain criteria: (1) facile to synthesize, (2) robust, (3) good solubility, (4) highly symmetrical, (5) can be isolated and (6) decorated by functional groups that are amenable for subsequent synthesis. The consideration of geometry and chemistry of MBBs can lead to prediction of framework connectivity and in turn to direct the design and synthesis of targeted porous structures as well as to impart desired physical properties to the formed materials. Our strategy to making CCFs is to assemble decorated MBBs by covalent bonds based on the same synthetic approach of 17-18, 21 We have focused on this study on trigonal prisCOFs. matic MBBs since the aforementioned criteria are intimately attained. However the utilization of other MBBs is still underexplored in our lab. The trigonal prismatic clusters [M3(µ3-O)(RCO2)6] (Fe, Cr, In, V, Al) are known to be robust, stable and inexpensive where it can serve as MBBs for the synthesis of many exquisite MOFs that gained special attention due to their unique properties such as MIL-101, MIL-100 22-23 and MIL-88. The first five members of CCFs family, CCF1-SE, CCF-2-SE, CCF-3-SE, CCF-4-SE and CCF-5-SE are synthesized with a high yield at ambient condition based on the same triagonal prismatic MBB. Our past work has shown that a novel trigonal prismatic MBB of the formula [Cr3(µ3O)(RCO2)6]NO3 (R=4-aminophenyl) can be synthesized by the reaction of chromium (III) nitrate nonahydrate with 4aminobezoic acid in methanol to isolate a highly soluble 13 crystalline MBB. This MBB is decorated by 6-amino groups which are amenable for the subsequent organic synthesis by the reaction with small organic molecules such as di/trialdehyde, di-/tri-acid chloride or acid anhydride (linear or triangular organic connections) that lead to the polymerization of discrete MBBs by the formation of strong covalent bonds affording porous CCFs (see Figure 1). This approach would certainly lead to a new avenue for the synthesis of porous materials using versatile MBBs with different decorations that can be feasibly polymerized by simple organic reactions (Figure 2).

Figure1. Illustration of the two-step iso-reticular synthesis approach

Figure 2. Illustration of the different polymerization reactions of MBB-1 with aldehydes and acid chlorides in the second step.


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Figure 3. Infrared spectroscopy for CCF-1-SE and MBB-1.

In our two-step isoreticular approach, we isolate the aminodecorated trigonal prismatic MBB-1 in the first step by the reaction of Cr(NO)3.9H2O with 4-aminobenzoic acid in methanolic solution with formula unit [Cr3(µ3O)(RCO2)6]NO3. The isolated MBB-1 is 0D discrete salt and is soluble in water and polar organic solvents as DMF, DMA, EtOH, MeOH. The gas adsorption studies revealed that MBB-1 is non-porous. The reaction of amines with aldehydes, acid chlorides and acid unhydride are very well-known since several organic polymers prepared from amines, aldehydes and acid chlorides as monomers through simple condensation or Schiff base reaction. Therefore we chose the aminodecorated MBB-1 that is highly symmetrical, robust and soluble cluster decorated with 6 NH2 groups that are amenable to be used as monomer in the polymerization reaction in the second step by reaction with aldehydes or acid chloride to form extended porous Coordination Covalent Frameworks that are permanently porous and insoluble in all organic solvents and water even by heating. CCF-1-SE, CCF-2-SE, CCF-3-SE, CCF-4-SE and CCF-5-SE are synthesized by the reaction of MBB-1 with benzene-1,3,5-tricarboxaldehyde, 1,3,5-benzenetricarbonyl trichloride, terephthalaldehyde, terephthaloyl chloride and pyromellitic dianhydride, respectively. The polymerization reactions of MBB-1 were instantaneous which lead to low-crystalline porous CCFs (See SI for more synthesis details). Several attempts were made to improve the crystallinity of the final CCF by changing the reaction conditions but failed to produce crystalline material. Since the Cr-prismatic clusters are decorated with 6 amino

groups above and below the plane, it is hard to control over the polymerization step. To further support the formation of CCF, all the materials were examined by Fourier transform infrared analysis (FT-IR) to prove the formation of amide or imine bond. FT-IR revealed the formation of imine or amide bonds in the five CCFs structures by clearly observing their stretching vibrational frequencies as shown in Figure 3 (Fig. S1-S5 in Supporting Information). For example, the asymmetric stretching vibrations of –NH2 in MBB-1 was clearly ob-1 served at 1387 cm , upon formation of CCF-1-SE the asymmetric stretching vibrations were disappear and formation of imine (–C=N) symmetric and asymmetric stretching were -1 clearly visible at 1667 and 1166 cm . Similarly, respective functional groups were clearly seen in infrared spectroscopy to demonstrate the successful synthesis of CCF materials. Thermogravimetric analysis (TGA) were performed on the discrete MBB-1 and all CCFs which revealed that high thermal stability of all CCF structures compared to the discrete MBB-1 which is rapidly decomposed at 150 °C. The gas adsorption measurements revealed that all polymerized CCFs were found to be permanently porous while the discrete MBB-1 is non-porous (see figure 4). Few examples reported recently for synthesis of porous amorphous organic cages 24-27 and polymers, however the two step isoreticular approach we presented herein open a new avenue of unexplored class of materials (CCFs) that merge the Coordination and Organic synthesis approaches. There are several other MBBs that are facile to synthesize and isolated to be used as precursor for organic polymerization. Therefore, utilization of the organic synthesis to connect the MBBs that are just need the right organic units to get polymerized without losing their integrity could be the milestone for triggering a paradigm shift in the synthesis and expansion of infinite number of functional porous materials that cannot be easily synthesized using the previous routes of synthesis. The permanent porosity and architectural stability of CCFs were confirmed by collecting CO2 adsorption isotherms at 195 K of the activated samples which revealed BET surface area of 301, 2 156, 225 and 256 and 269 m /g for CCF-1-SE, CCF-2-SE, CCF3-SE, CCF-4-SE and CCF-5-SE, respectively (see Figure 3). Not all CCFs structures have showed porosity with N2 at 77K, which might be attributed to pore collapse or shrinking of the pore at such lower temperature, 77K. Therefore we decided to use CO2 at 195K to calculate the BET for all the structures. Only CCF-1-SE and CCF-5-SE have showed porosity with N2 at 77K (see Supporting Information), whereas it is clear from the shape of the N2 sorption isotherms that there are different pore sizes varying from micropores to mesopores. Single component gas adsorption isotherms for CO2 were collected at 298 K from 0-1 atm and the isosteric heats of adsorption were calculated using Virial equation for all CCF structures (see Supporting Information). CO2 uptakes of CCFs at 1atm and 298K was observed to be 44, 28, 31, 37 and 3 29 cm /g, for CCF-1-SE, CCF-2-SE, CCF-3-SE, CCF-4-SE and 28-29 CCF-5-SE, respectively, (see Supporting Information).



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In summary, we present a facile and potentially universal synthetic approach that leads to the formation of novel porous materials designated as Covalent Coordination Frameworks (CCFs) whereas the coordination polymers are synthesized using the same synthetic approach of Covalent Organic Frameworks (COFs) since the decorated molecular building blocks can be polymerized by simple organic reactions through the formation of strong covalent bonds. We expect that this finding will lead to synthesis of many novel porous materials that are previously unattainable.

Figure 4: Illustration of the permanent porosity of CCFs in comparison with the non-porous discrete MBB-1: CO2 adsorption collected at 195K for (a) MBB-1, (b) CCF-1-SE, (C) CCF-2-SE, (d) CCF-3-SE, (e) CCF-4-SE, and (f) CCF-5-SE.

ASSOCIATED CONTENT Supporting Information Synthetic procedures, PXRD data, FT-IR spectroscopy and additional gas adsorption isotherms.

AUTHOR INFORMATION Corresponding Author [email protected];

ACKNOWLEDGMENT

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This work was supported by the DOE EERE Office of Geothermal. PNNL is a multiprogram national laboratory operated for the DOE by Battelle Memorial Institute under Contract DE-AC05- 76RL01830.

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Table of Contents graphic

A two-step reticular chemistry approach to synthesize a new class of functional materials called coordination covalent frameworks


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Coordination Covalent Frameworks: A New Route for Synthesis and

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