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Synthesis and characterization of boric acid mediated metal-organic frameworks based on trimesic acid and terephthalic acid
Accepted Manuscript Synthesis and characterization of boric acid mediated metal-organic frameworks based on trimesic acid and terephthalic acid Demet Ozer, Dursun A. Köse, Onur Şahin, Nursen Altuntas Oztas PII:
S0022-2860(17)30426-X
DOI:
10.1016/j.molstruc.2017.03.120
Reference:
MOLSTR 23616
To appear in:
Journal of Molecular Structure
Received Date: 28 January 2017 Revised Date:
30 March 2017
Accepted Date: 31 March 2017
Please cite this article as: D. Ozer, D.A. Köse, O. Şahin, N.A. Oztas, Synthesis and characterization of boric acid mediated metal-organic frameworks based on trimesic acid and terephthalic acid, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.03.120. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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ACCEPTED MANUSCRIPT Synthesis and Characterization of Boric Acid Mediated Metal-Organic Frameworks Based On Trimesic Acid and Terephthalic Acid Demet Ozera*, Dursun A. Köseb, Onur Şahinc, Nursen Altuntas Oztasa a
Hacettepe University, Department of Chemistry, Ankara, Turkey Hitit University, Department of Chemistry, Corum, Turkey
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b
Sinop University, Scientific and Technological Research Application and Research Center, Sinop, Turkey
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ABSTRACT
The new metal-organic framework materials based on boric acid reported herein. Sodium
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and boron containing metal-organic frameworks were synthesized by one-pot self-assembly reaction in the presence of trimesic acid and terephthalic acid in water/ethanol solution. Boric acid is a relatively cheap boron source and boric acid mediated metal-organic framework prepared mild conditions compared to the other boron source based metal-organic framework. The synthesized compounds were characterized by FT-IR, p-XRD, TGA/DTA, elemental analysis,
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C-MAS NMR,
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B-NMR and single crystal measurements. The
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molecular formulas of compounds were estimated as C18H33B2Na5O28 and C8H24B2Na2O17 according to the structural analysis. The obtained complexes were thermally stable. Surface properties of inorganic polymer complexes were investigated by BET analyses and hydrogen storage properties of compound were also calculated.
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Keywords: Boric acid, Sodium, Trimesic acid, Terephthalic acid, B-MOF INTRODUCTION
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In recent years, metal-organic frameworks have attracted great attention because of their structural diversity, changeable surface area and pore size, optical, electrical and magnetic properties [1]. The metal-organic frameworks with high surface area used in different type of catalytic reactions [2]. Nanocrystalline metal-organic frameworks used to produce a thin film [3] and membrane [4]. Metal-organic frameworks are widely studied in gas storage, magnetic resonance imaging [5], the lithium ion battery [6] and drug delivery systems [7]. Metal-organic frameworks were modified according to reaction conditions (synthesis method, reaction time, reaction temperature, pressure) and reaction compositions (solvent, type of ligand, amount of starting materials, pH etc.) [8a-j]. One of their key advantages is possible to tune up their composition easily by changing the metal and organic linker sources [9]. Possible linkers are ranging from carboxylates, phosphonates, sulfonates, imidazolates, 1
ACCEPTED MANUSCRIPT amines, pyridyl and phenolates [10]. The preparation of metal-organic frameworks includes several methods: hydrothermal method, solvothermal method [11], microwave synthesis [12], electrochemical [13] and mechanochemical synthesis [14]. Compared with traditional porous materials,
metal-organic
frameworks
synthesize
under
mild
conditions
and
allow
modifications to synthesize new molecules. The first synthesis of boron containing metal-organic framework was prepared using boronic
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acid by El-Kader et.al. in 2007 [15]. They used tetra(4-dihydroxyborylphenyl)methane (TBPM) as boron source. Liu and coworkers reported examples of boron containing metalorganic frameworks are based on tris(4-pyridyl)durylborane as linker [16a-b]. Triarylboron functionalized metal complexes have contributed significantly to the development of organic
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light emitting diodes, sensors and florescence materials [17]. Blight et al synthesized the first example of a triarylboron-functionalized carboxylate metal organoboron framework in 2013 [18]. Metal-organic frameworks made from carboranes have advantages compared to aryl-
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based boranes with regard to structural rigidity, thermal and chemical stability [19]. Kennedy and coworkers reported metallocarborane-based metal organic framework [20a-b] because of their different chemical properties and exceptional thermal stability. In this work, metal-organic framework based on sodium, boron, trimesic acid and terephthalic acid were prepared by one-pot self-assembly reaction at 90 °C. We have successfully synthesized the first boric acid functionalized metal-organic frameworks. We used two
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different ligand that contain dicarboxylate and tricarboxylate. The complexes were characterized with FT-IR, p-XRD, TGA/DTA, elemental analysis,
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C-MAS NMR,
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B-NMR
and single crystal XRD (sc-XRD) measurements. The BET surface area was measured and
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hydrogen storage capacity was experimentally determined at 77 K and 1 bar pressure.
EXPERIMENTAL SECTION
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Reagents: All the reagents were analytical grade and were used as commercially obtained without further purification. Sodium bicarbonate (NaHCO3) (Merck, % 99.5), trimesic acid (C9H6O6) (Aldrich, % 95), terephthalic acid (C8H6O4) (Aldrich, % 98), boric acid (H3BO3) (Sigma, % 99.5) and ethanol (C2H5OH) (Sigma, % 99.8) were used to prepared metalorganic framework.
Synthesis of C18H33B2Na5O28: NaHCO3 (3 mmol) and trimesic acid (1 mmol) were dissolved in 20 mL deionized water at 90°C. Boric acid (3 mmo l) was added to solution and completely dissolved. The resulting solution was stirred and 20 mL ethanol was added. 17 days later white crystals were obtained.
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ACCEPTED MANUSCRIPT Synthesis of C8H24B2Na2O17: NaHCO3 (2 mmol) and terephthalic acid (1 mmol) were dissolved in 20 mL deionized water at 90°C. Boric a cid (2 mmol) was added to solution and completely dissolved. The resulting solution was stirred and 20 mL ethanol was added. 23 days later colourless crystals were obtained. Characterization of Complexes: C, H contents were determined by CHNS-932 LECO
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model elemental analysis instrument. Na, B contents were determined by Perkin Elmer DRC II model ICP-MS instrument. Thermal behaviour and stability were performed by Shimadzu DTG-60H system in a dynamic nitrogen atmosphere over the interval 25-1000 °C at a heating rate of 10 °C/min. FT-IR spectra were recor ded in 4000-400 cm-1 range with PerkinElmer Spectrum One instrument by KBr pellet technique. Powder X-ray diffraction
(λ=1.5418) radiation. Solid-state
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measurements were obtained on a Rigaku DMAX-2200 X-ray diffractometer with Cu Kα 13
C-NMR spectra were recorded in 300-0 ppm with Bruker
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Avance Ultrashield TM 300 MHz WB instrument with magic angle technique. Solution state 11
B-NMR spectra were recorded Bruker Avance Ultrashield TM 400 MHz WB instrument.
Surface area measurements were recorded by Quantachrome Autosorb IQ. Suitable crystal was selected for data collection which was performed on a D8-QUEST diffractometer equipped with a graphite-monochromatic Mo-Kα radiation at 296 K. The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97 [21] from within the WINGX [22] suite of software. All non-hydrogen
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atoms were refined with anisotropic parameters. The water H atoms were located from different maps and then treated as riding atoms with C-H distances of 0.93 Å. All other H atoms were located in a difference map refined subject to a DFIX restraint. Molecular diagrams were created using MERCURY (Mercury). Supramolecular analyses were made
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and the diagrams were prepared with the aid of PLATON [23]. Hydrogen gas adsorption measurements were performed using Sievert-type adsorption equipment Quantachrome,
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AutosorbIQ at 77 K up to 1 (P/Po) relative pressure. RESULTS AND DISCUSSION The binding properties of synthesized compounds were characterized by the FT-IR spectroscopy. FT-IR analyzes were performed to obtain information on the manner in which ligands bind to sodium and boron. The FT-IR spectra of the starting materials and the resulting complex were compared. As shown in Figure 1a for sodium trimesate-boron complex, the broad peak observed at 3600-3300 cm-1 is attributed to the hydrogen bonds. The peak at 1197 cm-1 corresponds to vibration of B-O group in boric acid and it observed in complex at 1253 cm-1. Asymmetric and symmetric carbonyl stretching peaks were 1621-1570 cm-1 and 1436-1373 cm-1 [24] for sodium trimesate and 1615-1573 cm-1 and 1439-1373 cm-1 3
ACCEPTED MANUSCRIPT for sodium trimesate-boron complex. As shown in Figure 2a compared to the sodium terephthalate-boron complex and the starting materials, it was seen that there are band shifts and new bands are formed. The change in the values indicates that the boron entered the structure. . The p-XRD patterns were shown in Figure 1b and Figure 2b that they were not contained any peaks belong to starting materials. The comparison of p-XRD for each material indicates
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the formation of complexes in accordance with the results of FT-IR.
The thermal behavior of sodium trimesate and sodium trimesate-boron complex was studied using termogravimetric analysis and differential thermal analysis as shown in Figure 1c and 1d. Weight loss in the sodium trimesate-boron complex occurs in six steps. The weight loss
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of 22.5 % in the range of 25-148 °C is due to the e limination of hydrates and crystal waters. The weight loss of 5.1 % in the range of 148-315 °C is due to removal of –OH groups in boric acid as water. The weight loss of 7.2 % at 315-510 °C and the weight loss of 12.2 % at 510-
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613 °C are due to the breakdown of the trimesate gr oup as a result of the removal of carbon dioxide and carbon monoxide. The weight loss of 9.8 % at 613-720 °C and the weight loss of 6.3 % at 720-1000 °C are due to the complete remova l of the organic molecule and the formation of sodium and boron oxide phases. At 1000 °C, comparing the sodium trimesate and complex termograms, it was indicated that the complex included boron as boron oxide in addition to sodium oxide.
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The thermal behavior of sodium terephthalate and sodium terephthalate-boron complex was studied using termogravimetric analysis and differential thermal analysis as shown in Figure 2c and 2d. Weight loss in the sodium terephthalate-boron complex occurs in four steps. First weight loss of 34.4 % at 25-116 °C is due to the se paration of hydrates, second weight loss
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of 10.2 % at 116-380 °C is due to the separation of crystal waters, third weight loss of 18.3 % at 380-680 °C is due to the removal of organic liga nd and last weight loss of 12.2 % at 6801000 ° C is due to the burning of the last remain o rganic residues and the formation of
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sodium and boron oxide phases.
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Fig 1. a) FT-IR spectra b) p-XRD patterns c) TGA and d) DTA curves of sodium trimesate-
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boron complex and starting materials
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C-MAS NMR spectra of the sodium trimesate and sodium trimesate-boron complex
displayed in Figure 3a. This indicated that the peaks of carbon atoms at 128.45 and 125.95 ppm in the aromatic ring of the sodium salt of trimesic acid were changed with addition boron
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and the peaks were observed at 131.09, 128.46, 126.96 and 125.58 ppm as quaternary peaks and the presence of four different carbons in the aromatic ring by binding a ligand. The difference is that the different trimesic acid molecules present different symmetry. Carboxylic acid carbon in the trimesic acid observed at 170.01 and 168.67 ppm in sodium trimesate and at 168.448 and 167.150 ppm in complex. The presence of two different trimesic acid ligands
single crystal X-rays. When the
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in the asymmetric unit confirms the NMR results when compared to the results obtained with 13
C-MAS NMR spectra (Figure 3b) of sodium terephthalate-
boron complex and sodium terephthalate salt were examined, it was seen that three different
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carbon atoms of terephthalic acid were preserved. The carbons found in the aromatic ring were found in sodium terephthalate at 131.33 and 122.87 ppm, while the complexes formed by the addition of boron were found at 129.32, 123.13 and 121.66 ppm. When the carboxyl carbon of sodium terephthalate (170.46 ppm) examined, it gave a single peak indicated that sodiums were linked to the oxygens of carbonyl on both sides and were identical. The carboxyl carbon in the complex was at 168.01 ppm and when compared to sodium complex formation. 11
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terephthalate, the chemical environment changed and the carboxyl carbons were shifted by
B-NMR spectrum of sodium trimesate-boron complex (Figure 4a) was observed a single 11
B-NMR spectrum of sodium terephthalate-boron complex (Figure
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peak at 19.47 ppm and
4b) was observed a single peak at 19.45 ppm. Boric acid [B(OH)3] peak at 18.97 ppm is considered to be shifted relative to the peak of borate esters [B(OH)2L] peak at 19.70 ppm
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[25]. This verified that the boron was trigonal boron geometry in both complex.
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Fig 3. a)
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C-MAS NMR of sodium trimesate and sodium trimesate-boron complex b)
13
C-
Fig 4. a)
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MAS NMR of sodium terephthalate and sodium terephtalate-boron complex
B-NMR of sodium trimesate-boron complex b)
B-NMR of sodium terephthalate-
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boron complex
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Experimental elemental analysis results have similarity with the calculated percentages of C, H, B and Na amounts from single crystal measurement results. The sodium trimesate-boron complex contains 25.35 (25.89) % C, 3.82 (3.95) % H, 3.59 (2.64) % B and 12.20 (13.79) % Na where the calculated values are in brackets. The sodium terephthalate-boron complex contains 20.74 (20.87) % C, 5.19 (5.22) % H, 3.46 (4.69) % B and 9.82 (9.99) % Na where the calculated values are in brackets. Single crystal results of sodium trimesate-boron complex showed that the molecule formula is C18H33B2Na5O28 and molecular weight of compound is 834.01 g/mole. The molecular structure was represented in Figure 5. The crystallographic data and structure properties were summarized in Table 1. The asymmetric unit of compound consists of two boric acids, 7
ACCEPTED MANUSCRIPT two 1,3,5-benzenetricarboxylic ligands, five Na+ cations and ten coordinated water molecules. The 1,3,5-benzenetricarboxylic ligands exhibit two distinct coordination modes, namely, µ4-bridging and µ5-bridging coordination modes, respectively. The Na+ cations are of three coordination types. In the first of these coordination types, the Na1 and Na2 cations coordination by four oxygen atoms from water molecules, one oxygen atom from boric acid and one oxygen atom from carboxylic group. In the second coordination types, the Na3 and
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Na4 cations coordinated by three oxygen atoms from water molecules and three oxygen atoms from three carboxylic groups. Finally, cation Na5 is coordinated by four oxygen atoms from water molecules and one oxygen atom from carboxylic group. Adjacent Na+ cations are linked together by two oxygen bridges to form a four-membered ring with a Na2O2 core.
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Adjacent Na2O2 binuclear motifs are further joined by 1,3,5-benzenetricarboxylic ligands, generating 3D coordination polymer, with the Na···Na distances are 3.321 Å, 3.334 Å, 3.459 Å, 3.745 Å and 3.802 Å (Figure 6). Better insight of this 3D architecture can be achieved by
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topology analysis. As shown in Figure 6, each Na+ cation is linked to another Na+ cations with Schlafli vertex symbol of {4.14.15} for Na1, {4.182} for Na2, {32.4.5.63.74.83.9} for Na3, {32.62.73.82.9} for Na4 and {4.14.15} for Na5; this connected node was analyzed using OLEX. The bond distances of B-O ranged between 1.352(3)-1.375(3) Å and that of Na-O ranged between 2.3195(18)-2.6809(19) Å.
Single crystal results of sodium terephthalate-boron complex showed that the molecule
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formula is C8H24B2Na2O17 and molecular weight of compound is 459.87 g/mole. The molecular structure was represented in Figure 7. The crystallographic data and structure properties were summarized in Table 1. The asymmetric unit of complex consists of one Na(I) ion, one terephthalic acid ligand, one boric acid ligand, one non-coordinated water
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molecule and three coordinated water molecules. The Na1 atom is coordinated by one oxygen atom from terephthalic acid ligand, one oxygen atom from boric acid ligand and four oxygen atoms from water molecules. The Na(I) ions and water molecules produce
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[Na2(H2O)2] metalloligand, with the Na···Na separation is 3.503 Å. The combination of [Na2(H2O)2] metalloligands and terephthalic acid ligands produces 1D coordination polymer. Adjacent 1D coordination polymers are further joined by O-H···O hydrogen bonds to forming 3D supramolecular network (Fig 8). The BET surface area of sodium trimesate-boron complex was found 1.581 m2/g and the BET surface area of sodium terephthalate-boron complex was found 7.037 m2/g. At last hydrogen storage capacity of compounds were measured. Sodium trimesate-boron complex could uptake hydrogen with the capacity 0.047 wt.% and sodium terephthalate-boron complex could uptake hydrogen with the capacity 0.124 wt.% experimentally at 77 K and 1 bar pressure. The pore volumes and internal surface area of complex were relatively small, 8
ACCEPTED MANUSCRIPT thus the hydrogen storage capacities were also decrease. The low hydrogen storage capacity is due to the large number of hydrogen bonds and the inhibition of gas entry into the cavities.
Table 1. Crystallographic Data and Structure Refinement Details C18H33B2Na5O28
C8H24B2Na2O17
Formula weight
834.01
459.87
Crystal system
Triclinic
Monoclinic
Space group
P-1
C2/c
a (Å)
7.5459 (5)
18.1127(17)
b (Å)
11.4438 (9)
c (Å)
19.9539 (16)
α (º)
104.076 (3)
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90.00
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β (º)
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Empirical formula
98.819 (4)
90.304(3)
96.074 (3)
90.00
1633.1 (2)
1986.5
2
4
1.696
1.538
0.21
0.18
θ range (º)
3.1-28.3
28.3
Measured refls.
74213
30735
Independent refls.
6406
2476
Rint
0.034
0.034
S
1.07
1.06
R1/wR2
0.054/0.160
0.041/0.106
∆ρmax/∆ρmin (eÅ-3)
1.28/-0.53
0.39/-0.31
γ (º) V (Å3) Z -3
-1
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µ (mm )
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Dc (g cm )
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Fig. 5. The molecular structure of sodium trimesate-boron complex showing the atom
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numbering scheme
Fig. 6. An infinite 3D network of sodium trimesate-boron complex
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Fig. 7. The molecular structure of sodium terephthalate-boron complex showing the atom
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numbering scheme
Fig. 8. An infinite 3D network of sodium terephthalate-boron complex 11
ACCEPTED MANUSCRIPT CONCLUSIONS In summary, we have successfully synthesized a novel sodium-boron-organic framework based on trimesic acid and terephthalic acid using one-pot self-assembly reaction. Boric acid is relatively cheap boron source compared to the other boron sources. Boric acid mediated metal organic framework synthesized for the first time. Our study is a kind of guiding study for this type studies with contained many analysis details. The single crystal data explain the 13
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details of structural properties. The obtained evidences from FT-IR,
C-NMR, p-XRD results
support to our hetero-element structure. The results obtained from the single crystal data show that the structures carried out many hydrogen bond interactions on the boric acids -OH groups and the hydrate/crystal waters -OH groups. While hydrogen bonds increase the
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resulting in reductions in adsorption capacities.
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stability of structures, they accumulate electron densities in front of molecular cavities,
Supporting Information: Crystallographic data of the complexes have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 1055272 and 1455135. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: [email protected] or www:
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http://www.ccdc.cam.ac.uk).
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[21] G. M. Sheldrick, A short history of SHELX, Acta Cryst., A64, 112, 2008. [22] L. J. Farrugia, WinGX suite for small-molecule single-crystal crystallography, J. Apply. Cryst., 32, 837, 1999. [23] L. Spek, PLATON-a multipurpose crystallographic tool, Utrecht University, Utrecht, 2005. [24] K. Nakamoto, Applications in Coordination, Organometallic and Bioinorganic Chemistry, 6. Edition, John Wiley & Sons, 2009. [25] J. D. Kennedy, Multinuclear NMR, New York, USA: Plenum Press, 1987.
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Two new boron containing metal organic frameworks were succesfully synthesized. Structural, thermal and surface properties of complexes were investigated. Hydrogen storage capacity of complexes were determined.
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• • •
S0022-2860(17)30426-X
DOI:
10.1016/j.molstruc.2017.03.120
Reference:
MOLSTR 23616
To appear in:
Journal of Molecular Structure
Received Date: 28 January 2017 Revised Date:
30 March 2017
Accepted Date: 31 March 2017
Please cite this article as: D. Ozer, D.A. Köse, O. Şahin, N.A. Oztas, Synthesis and characterization of boric acid mediated metal-organic frameworks based on trimesic acid and terephthalic acid, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.03.120. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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ACCEPTED MANUSCRIPT Synthesis and Characterization of Boric Acid Mediated Metal-Organic Frameworks Based On Trimesic Acid and Terephthalic Acid Demet Ozera*, Dursun A. Köseb, Onur Şahinc, Nursen Altuntas Oztasa a
Hacettepe University, Department of Chemistry, Ankara, Turkey Hitit University, Department of Chemistry, Corum, Turkey
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b
Sinop University, Scientific and Technological Research Application and Research Center, Sinop, Turkey
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ABSTRACT
The new metal-organic framework materials based on boric acid reported herein. Sodium
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and boron containing metal-organic frameworks were synthesized by one-pot self-assembly reaction in the presence of trimesic acid and terephthalic acid in water/ethanol solution. Boric acid is a relatively cheap boron source and boric acid mediated metal-organic framework prepared mild conditions compared to the other boron source based metal-organic framework. The synthesized compounds were characterized by FT-IR, p-XRD, TGA/DTA, elemental analysis,
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C-MAS NMR,
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B-NMR and single crystal measurements. The
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molecular formulas of compounds were estimated as C18H33B2Na5O28 and C8H24B2Na2O17 according to the structural analysis. The obtained complexes were thermally stable. Surface properties of inorganic polymer complexes were investigated by BET analyses and hydrogen storage properties of compound were also calculated.
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Keywords: Boric acid, Sodium, Trimesic acid, Terephthalic acid, B-MOF INTRODUCTION
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In recent years, metal-organic frameworks have attracted great attention because of their structural diversity, changeable surface area and pore size, optical, electrical and magnetic properties [1]. The metal-organic frameworks with high surface area used in different type of catalytic reactions [2]. Nanocrystalline metal-organic frameworks used to produce a thin film [3] and membrane [4]. Metal-organic frameworks are widely studied in gas storage, magnetic resonance imaging [5], the lithium ion battery [6] and drug delivery systems [7]. Metal-organic frameworks were modified according to reaction conditions (synthesis method, reaction time, reaction temperature, pressure) and reaction compositions (solvent, type of ligand, amount of starting materials, pH etc.) [8a-j]. One of their key advantages is possible to tune up their composition easily by changing the metal and organic linker sources [9]. Possible linkers are ranging from carboxylates, phosphonates, sulfonates, imidazolates, 1
ACCEPTED MANUSCRIPT amines, pyridyl and phenolates [10]. The preparation of metal-organic frameworks includes several methods: hydrothermal method, solvothermal method [11], microwave synthesis [12], electrochemical [13] and mechanochemical synthesis [14]. Compared with traditional porous materials,
metal-organic
frameworks
synthesize
under
mild
conditions
and
allow
modifications to synthesize new molecules. The first synthesis of boron containing metal-organic framework was prepared using boronic
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acid by El-Kader et.al. in 2007 [15]. They used tetra(4-dihydroxyborylphenyl)methane (TBPM) as boron source. Liu and coworkers reported examples of boron containing metalorganic frameworks are based on tris(4-pyridyl)durylborane as linker [16a-b]. Triarylboron functionalized metal complexes have contributed significantly to the development of organic
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light emitting diodes, sensors and florescence materials [17]. Blight et al synthesized the first example of a triarylboron-functionalized carboxylate metal organoboron framework in 2013 [18]. Metal-organic frameworks made from carboranes have advantages compared to aryl-
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based boranes with regard to structural rigidity, thermal and chemical stability [19]. Kennedy and coworkers reported metallocarborane-based metal organic framework [20a-b] because of their different chemical properties and exceptional thermal stability. In this work, metal-organic framework based on sodium, boron, trimesic acid and terephthalic acid were prepared by one-pot self-assembly reaction at 90 °C. We have successfully synthesized the first boric acid functionalized metal-organic frameworks. We used two
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different ligand that contain dicarboxylate and tricarboxylate. The complexes were characterized with FT-IR, p-XRD, TGA/DTA, elemental analysis,
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C-MAS NMR,
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B-NMR
and single crystal XRD (sc-XRD) measurements. The BET surface area was measured and
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hydrogen storage capacity was experimentally determined at 77 K and 1 bar pressure.
EXPERIMENTAL SECTION
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Reagents: All the reagents were analytical grade and were used as commercially obtained without further purification. Sodium bicarbonate (NaHCO3) (Merck, % 99.5), trimesic acid (C9H6O6) (Aldrich, % 95), terephthalic acid (C8H6O4) (Aldrich, % 98), boric acid (H3BO3) (Sigma, % 99.5) and ethanol (C2H5OH) (Sigma, % 99.8) were used to prepared metalorganic framework.
Synthesis of C18H33B2Na5O28: NaHCO3 (3 mmol) and trimesic acid (1 mmol) were dissolved in 20 mL deionized water at 90°C. Boric acid (3 mmo l) was added to solution and completely dissolved. The resulting solution was stirred and 20 mL ethanol was added. 17 days later white crystals were obtained.
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ACCEPTED MANUSCRIPT Synthesis of C8H24B2Na2O17: NaHCO3 (2 mmol) and terephthalic acid (1 mmol) were dissolved in 20 mL deionized water at 90°C. Boric a cid (2 mmol) was added to solution and completely dissolved. The resulting solution was stirred and 20 mL ethanol was added. 23 days later colourless crystals were obtained. Characterization of Complexes: C, H contents were determined by CHNS-932 LECO
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model elemental analysis instrument. Na, B contents were determined by Perkin Elmer DRC II model ICP-MS instrument. Thermal behaviour and stability were performed by Shimadzu DTG-60H system in a dynamic nitrogen atmosphere over the interval 25-1000 °C at a heating rate of 10 °C/min. FT-IR spectra were recor ded in 4000-400 cm-1 range with PerkinElmer Spectrum One instrument by KBr pellet technique. Powder X-ray diffraction
(λ=1.5418) radiation. Solid-state
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measurements were obtained on a Rigaku DMAX-2200 X-ray diffractometer with Cu Kα 13
C-NMR spectra were recorded in 300-0 ppm with Bruker
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Avance Ultrashield TM 300 MHz WB instrument with magic angle technique. Solution state 11
B-NMR spectra were recorded Bruker Avance Ultrashield TM 400 MHz WB instrument.
Surface area measurements were recorded by Quantachrome Autosorb IQ. Suitable crystal was selected for data collection which was performed on a D8-QUEST diffractometer equipped with a graphite-monochromatic Mo-Kα radiation at 296 K. The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97 [21] from within the WINGX [22] suite of software. All non-hydrogen
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atoms were refined with anisotropic parameters. The water H atoms were located from different maps and then treated as riding atoms with C-H distances of 0.93 Å. All other H atoms were located in a difference map refined subject to a DFIX restraint. Molecular diagrams were created using MERCURY (Mercury). Supramolecular analyses were made
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and the diagrams were prepared with the aid of PLATON [23]. Hydrogen gas adsorption measurements were performed using Sievert-type adsorption equipment Quantachrome,
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AutosorbIQ at 77 K up to 1 (P/Po) relative pressure. RESULTS AND DISCUSSION The binding properties of synthesized compounds were characterized by the FT-IR spectroscopy. FT-IR analyzes were performed to obtain information on the manner in which ligands bind to sodium and boron. The FT-IR spectra of the starting materials and the resulting complex were compared. As shown in Figure 1a for sodium trimesate-boron complex, the broad peak observed at 3600-3300 cm-1 is attributed to the hydrogen bonds. The peak at 1197 cm-1 corresponds to vibration of B-O group in boric acid and it observed in complex at 1253 cm-1. Asymmetric and symmetric carbonyl stretching peaks were 1621-1570 cm-1 and 1436-1373 cm-1 [24] for sodium trimesate and 1615-1573 cm-1 and 1439-1373 cm-1 3
ACCEPTED MANUSCRIPT for sodium trimesate-boron complex. As shown in Figure 2a compared to the sodium terephthalate-boron complex and the starting materials, it was seen that there are band shifts and new bands are formed. The change in the values indicates that the boron entered the structure. . The p-XRD patterns were shown in Figure 1b and Figure 2b that they were not contained any peaks belong to starting materials. The comparison of p-XRD for each material indicates
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the formation of complexes in accordance with the results of FT-IR.
The thermal behavior of sodium trimesate and sodium trimesate-boron complex was studied using termogravimetric analysis and differential thermal analysis as shown in Figure 1c and 1d. Weight loss in the sodium trimesate-boron complex occurs in six steps. The weight loss
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of 22.5 % in the range of 25-148 °C is due to the e limination of hydrates and crystal waters. The weight loss of 5.1 % in the range of 148-315 °C is due to removal of –OH groups in boric acid as water. The weight loss of 7.2 % at 315-510 °C and the weight loss of 12.2 % at 510-
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613 °C are due to the breakdown of the trimesate gr oup as a result of the removal of carbon dioxide and carbon monoxide. The weight loss of 9.8 % at 613-720 °C and the weight loss of 6.3 % at 720-1000 °C are due to the complete remova l of the organic molecule and the formation of sodium and boron oxide phases. At 1000 °C, comparing the sodium trimesate and complex termograms, it was indicated that the complex included boron as boron oxide in addition to sodium oxide.
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The thermal behavior of sodium terephthalate and sodium terephthalate-boron complex was studied using termogravimetric analysis and differential thermal analysis as shown in Figure 2c and 2d. Weight loss in the sodium terephthalate-boron complex occurs in four steps. First weight loss of 34.4 % at 25-116 °C is due to the se paration of hydrates, second weight loss
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of 10.2 % at 116-380 °C is due to the separation of crystal waters, third weight loss of 18.3 % at 380-680 °C is due to the removal of organic liga nd and last weight loss of 12.2 % at 6801000 ° C is due to the burning of the last remain o rganic residues and the formation of
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sodium and boron oxide phases.
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Fig 1. a) FT-IR spectra b) p-XRD patterns c) TGA and d) DTA curves of sodium trimesate-
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boron complex and starting materials
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ACCEPTED MANUSCRIPT Fig 2. a) FT-IR spectra b) p-XRD patterns c) TGA and d) DTA curves of sodium terephthalate-boron complex and starting materials 13
C-MAS NMR spectra of the sodium trimesate and sodium trimesate-boron complex
displayed in Figure 3a. This indicated that the peaks of carbon atoms at 128.45 and 125.95 ppm in the aromatic ring of the sodium salt of trimesic acid were changed with addition boron
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and the peaks were observed at 131.09, 128.46, 126.96 and 125.58 ppm as quaternary peaks and the presence of four different carbons in the aromatic ring by binding a ligand. The difference is that the different trimesic acid molecules present different symmetry. Carboxylic acid carbon in the trimesic acid observed at 170.01 and 168.67 ppm in sodium trimesate and at 168.448 and 167.150 ppm in complex. The presence of two different trimesic acid ligands
single crystal X-rays. When the
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in the asymmetric unit confirms the NMR results when compared to the results obtained with 13
C-MAS NMR spectra (Figure 3b) of sodium terephthalate-
boron complex and sodium terephthalate salt were examined, it was seen that three different
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carbon atoms of terephthalic acid were preserved. The carbons found in the aromatic ring were found in sodium terephthalate at 131.33 and 122.87 ppm, while the complexes formed by the addition of boron were found at 129.32, 123.13 and 121.66 ppm. When the carboxyl carbon of sodium terephthalate (170.46 ppm) examined, it gave a single peak indicated that sodiums were linked to the oxygens of carbonyl on both sides and were identical. The carboxyl carbon in the complex was at 168.01 ppm and when compared to sodium complex formation. 11
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terephthalate, the chemical environment changed and the carboxyl carbons were shifted by
B-NMR spectrum of sodium trimesate-boron complex (Figure 4a) was observed a single 11
B-NMR spectrum of sodium terephthalate-boron complex (Figure
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peak at 19.47 ppm and
4b) was observed a single peak at 19.45 ppm. Boric acid [B(OH)3] peak at 18.97 ppm is considered to be shifted relative to the peak of borate esters [B(OH)2L] peak at 19.70 ppm
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[25]. This verified that the boron was trigonal boron geometry in both complex.
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Fig 3. a)
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13
C-MAS NMR of sodium trimesate and sodium trimesate-boron complex b)
13
C-
Fig 4. a)
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MAS NMR of sodium terephthalate and sodium terephtalate-boron complex
B-NMR of sodium trimesate-boron complex b)
B-NMR of sodium terephthalate-
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boron complex
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Experimental elemental analysis results have similarity with the calculated percentages of C, H, B and Na amounts from single crystal measurement results. The sodium trimesate-boron complex contains 25.35 (25.89) % C, 3.82 (3.95) % H, 3.59 (2.64) % B and 12.20 (13.79) % Na where the calculated values are in brackets. The sodium terephthalate-boron complex contains 20.74 (20.87) % C, 5.19 (5.22) % H, 3.46 (4.69) % B and 9.82 (9.99) % Na where the calculated values are in brackets. Single crystal results of sodium trimesate-boron complex showed that the molecule formula is C18H33B2Na5O28 and molecular weight of compound is 834.01 g/mole. The molecular structure was represented in Figure 5. The crystallographic data and structure properties were summarized in Table 1. The asymmetric unit of compound consists of two boric acids, 7
ACCEPTED MANUSCRIPT two 1,3,5-benzenetricarboxylic ligands, five Na+ cations and ten coordinated water molecules. The 1,3,5-benzenetricarboxylic ligands exhibit two distinct coordination modes, namely, µ4-bridging and µ5-bridging coordination modes, respectively. The Na+ cations are of three coordination types. In the first of these coordination types, the Na1 and Na2 cations coordination by four oxygen atoms from water molecules, one oxygen atom from boric acid and one oxygen atom from carboxylic group. In the second coordination types, the Na3 and
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Na4 cations coordinated by three oxygen atoms from water molecules and three oxygen atoms from three carboxylic groups. Finally, cation Na5 is coordinated by four oxygen atoms from water molecules and one oxygen atom from carboxylic group. Adjacent Na+ cations are linked together by two oxygen bridges to form a four-membered ring with a Na2O2 core.
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Adjacent Na2O2 binuclear motifs are further joined by 1,3,5-benzenetricarboxylic ligands, generating 3D coordination polymer, with the Na···Na distances are 3.321 Å, 3.334 Å, 3.459 Å, 3.745 Å and 3.802 Å (Figure 6). Better insight of this 3D architecture can be achieved by
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topology analysis. As shown in Figure 6, each Na+ cation is linked to another Na+ cations with Schlafli vertex symbol of {4.14.15} for Na1, {4.182} for Na2, {32.4.5.63.74.83.9} for Na3, {32.62.73.82.9} for Na4 and {4.14.15} for Na5; this connected node was analyzed using OLEX. The bond distances of B-O ranged between 1.352(3)-1.375(3) Å and that of Na-O ranged between 2.3195(18)-2.6809(19) Å.
Single crystal results of sodium terephthalate-boron complex showed that the molecule
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formula is C8H24B2Na2O17 and molecular weight of compound is 459.87 g/mole. The molecular structure was represented in Figure 7. The crystallographic data and structure properties were summarized in Table 1. The asymmetric unit of complex consists of one Na(I) ion, one terephthalic acid ligand, one boric acid ligand, one non-coordinated water
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molecule and three coordinated water molecules. The Na1 atom is coordinated by one oxygen atom from terephthalic acid ligand, one oxygen atom from boric acid ligand and four oxygen atoms from water molecules. The Na(I) ions and water molecules produce
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[Na2(H2O)2] metalloligand, with the Na···Na separation is 3.503 Å. The combination of [Na2(H2O)2] metalloligands and terephthalic acid ligands produces 1D coordination polymer. Adjacent 1D coordination polymers are further joined by O-H···O hydrogen bonds to forming 3D supramolecular network (Fig 8). The BET surface area of sodium trimesate-boron complex was found 1.581 m2/g and the BET surface area of sodium terephthalate-boron complex was found 7.037 m2/g. At last hydrogen storage capacity of compounds were measured. Sodium trimesate-boron complex could uptake hydrogen with the capacity 0.047 wt.% and sodium terephthalate-boron complex could uptake hydrogen with the capacity 0.124 wt.% experimentally at 77 K and 1 bar pressure. The pore volumes and internal surface area of complex were relatively small, 8
ACCEPTED MANUSCRIPT thus the hydrogen storage capacities were also decrease. The low hydrogen storage capacity is due to the large number of hydrogen bonds and the inhibition of gas entry into the cavities.
Table 1. Crystallographic Data and Structure Refinement Details C18H33B2Na5O28
C8H24B2Na2O17
Formula weight
834.01
459.87
Crystal system
Triclinic
Monoclinic
Space group
P-1
C2/c
a (Å)
7.5459 (5)
18.1127(17)
b (Å)
11.4438 (9)
c (Å)
19.9539 (16)
α (º)
104.076 (3)
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90.00
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β (º)
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Empirical formula
98.819 (4)
90.304(3)
96.074 (3)
90.00
1633.1 (2)
1986.5
2
4
1.696
1.538
0.21
0.18
θ range (º)
3.1-28.3
28.3
Measured refls.
74213
30735
Independent refls.
6406
2476
Rint
0.034
0.034
S
1.07
1.06
R1/wR2
0.054/0.160
0.041/0.106
∆ρmax/∆ρmin (eÅ-3)
1.28/-0.53
0.39/-0.31
γ (º) V (Å3) Z -3
-1
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µ (mm )
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Dc (g cm )
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Fig. 5. The molecular structure of sodium trimesate-boron complex showing the atom
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numbering scheme
Fig. 6. An infinite 3D network of sodium trimesate-boron complex
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Fig. 7. The molecular structure of sodium terephthalate-boron complex showing the atom
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numbering scheme
Fig. 8. An infinite 3D network of sodium terephthalate-boron complex 11
ACCEPTED MANUSCRIPT CONCLUSIONS In summary, we have successfully synthesized a novel sodium-boron-organic framework based on trimesic acid and terephthalic acid using one-pot self-assembly reaction. Boric acid is relatively cheap boron source compared to the other boron sources. Boric acid mediated metal organic framework synthesized for the first time. Our study is a kind of guiding study for this type studies with contained many analysis details. The single crystal data explain the 13
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details of structural properties. The obtained evidences from FT-IR,
C-NMR, p-XRD results
support to our hetero-element structure. The results obtained from the single crystal data show that the structures carried out many hydrogen bond interactions on the boric acids -OH groups and the hydrate/crystal waters -OH groups. While hydrogen bonds increase the
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resulting in reductions in adsorption capacities.
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stability of structures, they accumulate electron densities in front of molecular cavities,
Supporting Information: Crystallographic data of the complexes have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 1055272 and 1455135. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: [email protected] or www:
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http://www.ccdc.cam.ac.uk).
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Two new boron containing metal organic frameworks were succesfully synthesized. Structural, thermal and surface properties of complexes were investigated. Hydrogen storage capacity of complexes were determined.
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