Syntheses, Structures, and Sorption Properties of MetalâOrganic

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Syntheses, Structures and Sorption Properties of Metal-Organic Frameworks with 1,3,5-Tris(1-imidazolyl)benzene and Tricarboxylate Ligands Yu-Ling Li, Yue Zhao, Yan-Shang Kang, Xiao-Hui Liu, and Wei-Yin Sun Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01352 • Publication Date (Web): 11 Nov 2016 Downloaded from http://pubs.acs.org on November 16, 2016

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Crystal Growth & Design

Syntheses, Structures and Sorption Properties of Metal-Organic Frameworks with 1,3,5-Tris(1-imidazolyl)benzene and Tricarboxylate Ligands Yu-Ling Li,†,‡ Yue Zhao,† Yan-Shang Kang,† Xiao-Hui Liu,† and Wei-Yin Sun*,† †

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School

of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, China ‡

School of Chemistry & Pharmaceutical Engineering, Nanyang Normal University,

Nanyang 473061, Henan, China

ABSTRACT:

Seven

new

frameworks

[Co3(tib)2(BPT)2(H2O)2]·DMF·3H2O [Ni3(tib)2(BPT)2(H2O)6]·2H2O [Ni3(tib)2(BTB)2(H2O)2]·14H2O

(2),

(4), (6)

and

[Co3(tib)2(BPT)2(H2O)2]·DMA·2.5H2O

(1),

[Ni3(tib)2(BPT)2(H2O)2]·DMF·1.5H2O

(3),

[Mn(tib)(H2O)3]·HBPT·DMF·2H2O

(5),

[Co3(tib)2(BTB)2]·2DMF·6H2O

(7)

[tib

=

1,3,5-tris(1-imidazolyl)benzene, H3BPT = biphenyl-3,4′,5-tricarboxylic acid, H3BTB = 4,4′,4″-benzene-1,3,5-triyl-tribenzoic

acid,

DMA=N,N-dimethylacetamide,

DMF=

N,N-dimethylformamide] were achieved and structurally characterized. 1, 2 and 3 are (3,3,4,4)-connected 3D frameworks with point symbol of {83}4{85·12}{86}2, while 4, 6 and 7 are also (3,3,4,4)-connected 3D nets but with different framework structures and topologies. 5 is a 2D network, which is further joined together by hydrogen bonds to generate a 3D supramolecular framework. Gas, vapor and dye adsorption properties of the frameworks were examined, and 1 - 7 exhibit hysteretic and selective adsorption of CO2 over N2. Furthermore, 7 is a potential adsorbent for removing methylene blue (MB) in the aqueous solution.

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INTRODUCTION The so-called metal-organic frameworks (MOFs) are constructed by coordination of metal centers with multi-organic connectors and own structural diversity, functional property as well as potential application, accordingly have drawn remarkable attention in the past years.1-9 Together with the development crystal engineering, MOF compounds can be readily achieved by varied methods.10-12 Nevertheless, the use of organic linkers is crucial for formation of MOFs with definite framework structures and desired properties. To achieve porous MOFs with permanent porosity, rigid organic ligands are usually employed since they can lead to formation of robust frameworks with metal centers.13-16 In our group, we are particularly interested in utilizing rigid N-donor ligand together with multicarboxylic acid for fabrication of MOFs. The previously reported results demonstrate that 1,3,5-tris(1-imidazolyl)benzene (tib) is versatile in construction of MOFs.17-20 On the other hand, the rigid multicarboxylate ligands are of special interests due to the varied coordination modes of carboxylate groups. Therefore, systematic studies were carried out by using mixed N-donor ligands and multicarboxylic acids.21-24 In this work, seven new Co(II), Ni(II)

and

Mn(II)

MOFs

of

[Co3(tib)2(BPT)2(H2O)2]·DMF·3H2O [Ni3(tib)2(BPT)2(H2O)6]·2H2O

(4),

[Ni3(tib)2(BTB)2(H2O)2]·14H2O

(6)

(2),

[Co3(tib)2(BPT)2(H2O)2]·DMA·2.5H2O

(1),

[Ni3(tib)2(BPT)2(H2O)2]·DMF·1.5H2O

(3),

[Mn(tib)(H2O)3]·HBPT·DMF·2H2O

(5),

and

[Co3(tib)2(BTB)2]·2DMF·6H2O

(7)

[H3BPT=biphenyl-3,4′,5-tricarboxylic acid, H3BTB=4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid (Scheme 1), DMA=N,N-dimethylacetamide, DMF=N,N-dimethylformamide] were synthesized. Structural characterization revealed that 1, 2 and 3 are (3,3,4,4)-connected three-dimensional (3D) frameworks with point symbol of {83}4{85·12}{86}2, while 5 is a 2D network, which is further connected together by hydrogen bonds to form a 3D supramolecular framework. 4, 6 and 7 are also (3,3,4,4)-connected 3D nets but with different


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framework structures and topologies. Gas, vapor and dye adsorption properties of the frameworks were examined. 1 - 7 show selective and hysteretic sorption of CO2 over N2, while 7 is a potential adsorbent for removing methylene blue (MB) in the aqueous solution.

Scheme 1. Ligands tib, H3BPT and H3BTB.

EXPERIMENTAL SECTION Synthesis of [Co3(tib)2(BPT)2(H2O)2]·DMA·2.5H2O (1). Reaction of tib (13.8 mg, 0.05 mmol), H3BPT (14.3 mg, 0.05 mmol) and Co(NO3)2·6H2O (29.1 mg, 0.1 mmol) in DMA/H2O (8 mL, v/v, 3:1) was performed at 90 °C for 72 h in a glass vial. Purple block crystals of 1 were obtained in 85% yield (based on tib) after the reaction mixture was cooled down to ambient temperature. Anal. Calcd for 1 (C64H56N13O17.5Co3): C, 52.51; H, 3.86; N, 12.44%. Found: C, 52.47; H, 3.91; N, 12.41%. IR (KBr pellet, cm-1): 3440 (m), 3143 (w), 1621 (s), 1557 (m), 1508 (m), 1397 (s), 1287 (m), 1238 (m), 1181 (m), 1073 (s), 1015 (s), 939 (m), 868 (m), 774 (s), 735 (m), 654 (m), 477 (m). Synthesis of [Co3(tib)2(BPT)2(H2O)2]·DMF·3H2O (2). 2 was achieved by the procedure used for fabrication of 1, except that mixed solvent of DMF/H2O (8 mL, v/v, 3:1) was employed in place of DMA/H2O. Purple block shaped crystals of 2 were isolated in 80% yield (based on tib). Anal. Calcd for 2 (C63H55N13O18Co3): C, 51.86; H, 3.80; N, 12.48%. Found: C, 51.81; H, 4.40; N, 12.44%. IR (KBr pellet, cm-1): 3445 (m), 3142 (w), 1619 (s), 1556 (m), 1508 (m), 1397 (s), 1288 (m), 1239 (m), 1173 (m), 1073 (s), 1015 (s), 939 (m), 868



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(m), 773 (s), 735 (m), 655 (m), 477 (m). Synthesis of [Ni3(tib)2(BPT)2(H2O)2]·DMF·1.5H2O (3). 3 was made by using Ni(NO3)2·6H2O (29.1 mg, 0.1 mmol) rather than Co(NO3)2·6H2O following the procedure used for synthesis of 2. Green block shaped crystals of 3 were isolated in 80% yield (based on tib). Anal. Calcd for 3 (C63H52N13O16.50Ni3): C, 52.87; H, 3.66; N, 12.72%. Found: C, 52.81; H, 3.71; N, 12.67%. IR (KBr pellet, cm-1): 3400 (m), 3128 (w), 1618 (s), 1545 (m), 1508 (m), 1399 (s), 1288 (m), 1238 (m), 1182 (m), 1073 (s), 1015 (s), 939 (m), 868 (m), 775 (s), 744 (m), 654 (m), 478 (m). Synthesis of [Ni3(tib)2(BPT)2(H2O)6]·2H2O (4). A mixture of tib (27.6 mg, 0.1 mmol), H3BPT (28.6 mg, 0.1 mmol), Ni(NO3)2·6H2O (58.2 mg, 0.2 mmol), NaOH (12.0 mg, 0.3 mmol) in H2O (10 mL) was used to react in a hydro/solvothermal reactor (18 mL) at 180 °C for 72 h. Green block shaped crystals of 4 were formed in 85% yield (based on tib). Anal. Calcd for 4 (C60H50N12O18Ni3): C, 51.36; H, 3.59; N, 11.98%. Found: C, 51.31; H, 4.65; N, 11.93%. IR (KBr pellet, cm-1): 3448 (m), 3128 (w), 1620 (s), 1545 (m), 1509 (m), 1394 (s), 1283 (m), 1238 (m), 1182 (m), 1063(s), 1014 (s), 932 (m), 857 (m), 769 (s), 725 (m), 646 (m), 479 (m). Synthesis of [Mn(tib)(H2O)3]·HBPT·DMF·2H2O (5). 5 was prepared following the procedure used in fabrication of 2, using MnCl2·4H2O (19.8 mg, 0.1 mmol) in place of Co(NO3)2·6H2O. The yield of 5 was 75% based on tib. Anal. Calcd for 5 (C33H37N7O12Mn): C, 50.90; H, 4.79; N, 12.59%. Found: C, 50.85; H, 4.86; N, 12.53%. IR (KBr pellet, cm-1): 3350 (m), 3126 (m), 1695 (m), 1663 (s), 1615 (s), 1561 (m), 1502 (s), 1438 (m), 1361 (m), 1253 (m), 1105 (m), 1071 (s), 1012 (m), 926 (m), 765 (s), 713 (m), 657 (m), 521 (m). Synthesis of [Ni3(tib)2(BTB)2(H2O)2]·14H2O (6). 6 was achieved under the same conditions as for the formation of 4, using H3BTB (43.9 mg, 0.1 mmol) in place of H3BPT. Green block shaped crystals of 6 were generated with a yield of 80% based on tib. Anal.


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Calcd for 6 (C84H86N12O28Ni3): C, 53.45; H, 4.59; N, 8.90%. Found: C, 53.40; H, 4.62; N, 8.84%. IR (KBr pellet, cm-1): 3385 (s), 3130 (m), 1612 (s), 1582 (s), 1512 (s), 1417 (s), 1389 (s), 1246 (m), 1184 (m), 1108 (m), 1073 (s), 1017 (s), 852 (m), 784 (s), 680 (m), 657 (m), 469 (m). Synthesis of [Co3(tib)2(BTB)2]·2DMF·6H2O (7). The formation of 7 was realized under the conditions for synthesis of 2, using H3BTB (22.0 mg, 0.05 mmol) rather than H3BPT. Purple block shaped crystals of 7 were isolated with a yield of 85% based on tib. Anal. Calcd for 7 (C90H80N14O20Co3): C, 58.29; H, 4.35; N, 10.57%. Found: C, 58.23; H, 4.38; N, 10.55%. IR (KBr pellet, cm-1): 3431 (s), 3217 (m), 1661 (m), 1614 (s), 1512 (s), 1389 (s), 1247 (m), 1173 (m), 1109 (m), 1074 (m), 1015 (m), 857 (m), 782 (s), 655 (m), 479 (m).



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Table 1. Crystallographic Data for 1-7. 1

2

3

4

Formula

C64H56N13O17.5Co3

C63H55N13O18Co3

C63H52N13O16.50Ni3

C60H50N12O18Ni3

Formula weight

1464.00

1458.99

1431.30

1403.25

T (K)

293(2)

293(2)

293(2)

293(2)

Crystal system

Monoclinic

Monoclinic

Monoclinic

Triclinic

Space group

C2/c

C2/c

C2/c

P-1

a (Å)

24.028(9)

23.9792(7)

23.4092(16)

11.4733(6)

b (Å)

13.413(5)

13.3721(4)

13.3865(9)

12.1548(7)

c (Å)

24.048(5)

24.2227(9)

25.2954(19)

12.5986(7)

α (º)

90

90

90

102.0950(10)

β (º)

113.111(13)

112.7060(10)

114.823(2)

109.4060(10)

γ (º)

90

90

90

109.4300(10)

V (Å3)

7128(4)

7165.1(4)

7194.4(9)

1458.07(14)

Z

4

4

4

1

Dcalc (g cm-3)

1.364

1.353

1.321

1.598

F(000)

3008

2996

2948

722

θ for data collection (°)

1.776-24.997

2.1550-25.000

2.18-26.31

2.96-23.04

no. of unique reflns

6284

6311

6312

5114

no. of obsd reflns

4845

5331

4785

4337

Goodness-of-fit on F2

0.964

1.027

1.097

1.099

R1a [I > 2σ (I)]

0.0393

0.0380

0.0478

0.0376

wR2b [I > 2σ (I)]

0.0959

0.1043

0.1249

0.1026


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5

6

7

Formula

C33H37N7O12Mn

C84H86N12O28Ni3

C90H80N14O20Co3

Formula weight

778.63

1887.77

1854.47

T (K)

293(2)

293(2)

293(2)

Crystal system

Monoclinic

Monoclinic

Orthorhombic

Space group

P21/n

P21/c

Pbcn

a (Å)

11.675(2)

8.3661(6)

29.507(5)

b (Å)

14.562(3)

29.139(2)

19.224(3)

c (Å)

20.851(4)

18.8583(13)

16.462(3)

α (º)

90

90

90

β (º)

90.091(4)

94.3070(10)

90

γ (º)

90

90

90

V (Å3)

3544.9(12)

4584.3(6)

9338(3)

Z

4

2

4

Dcalc (g cm-3)

1.459

1.368

1.319

F(000)

1620

1964

4007

θ for data collection (°)

1.706-27.538

2.17-24.90

2.326-20.372

no. of unique reflns

8136

8050

8221

no. of obsd reflns

5935

6353

4788

Goodness-of-fit on F2

1.050

1.068

1.069

R1a [I > 2σ (I)]

0.0474

0.0477

0.0664

wR2b [I > 2σ (I)]

0.1223

0.1358

0.1860

a

R1 =Σ||Fo| - |Fc||/Σ|Fo|.

b

wR2 = |Σw(|Fo|2 - |Fc |2)|/Σ|w(Fo)2|1/2, where w =

1/[σ2(Fo2) +(aP)2+bP]. P = (Fo2 + 2Fc2)/3



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RESULTS AND DISCUSSION Frameworks 1, 2 and 3 have the same structure ensured by crystal structure determination as summarized in Table 1. Thus, the crystal structures of 1 and 4 - 7 are presented here in detail. Crystal Structure of [Co3(tib)2(BPT)2(H2O)2]·DMA·2.5H2O (1). As illustrated in Figure 1a, the repeat unit of 1 has two crystallographically independent Co(II) atoms, one of which is locating at the specific position, one tib, one BPT3-, and one coordinated aqua molecule. Co1 is surrounded by two imidazole N atoms (N1, N1A) from two different tib ligands and two carboxylate O ones (O1, O1A) from two distinct BPT3-, forming a distorted tetrahedral coordination geometry, with Co1-N bond distance of 2.042(2) Å and the Co1-O one of 1.959(2) Å. The coordination angles around Co1 are in the scope of 60.20(7)°-122.43(9)° (Table S1). While Co2 is six-coordinated with distorted octahedral coordination geometry by two imidazole N atoms (N3, N5D) from two different tib, three carboxylate O atoms (O3B, O4B, O5C) from two BPT3- and one terminal water molecule (O1W). The bond distances and coordination angles around Co2 are in normal range (Table S1). In 1, each tib connects three Co(II) atoms to give a 2D network (Figure 1b). Meanwhile, each BPT3- ligand acts as a µ3-bridging linker using its carboxylate groups with (κ1)-(κ1)-(κ2)-µ3-BPT coordination mode (Scheme S1I) to connect three Co(II) atoms to produce a 3D framework (Figure 1c). The combination of 2D network of Co-tib and 3D framework of Co-BPT generates the final 3D structure of 1 (Figure 1d). The solvent accessible volume for 1 calculated by PLATON is 1054.8 Å3 per 3564.0 Å3 unit cell volume (29.6% of the total crystal volume).32 The corresponding values for 2 and 3 are 2126.9 Å3 per 7165.1 Å3 unit cell volume (29.7% of the total crystal volume) and 2153.4 Å3 per 7194.4 Å3 unit cell volume (29.9% of the total crystal volume), respectively. To simplify the 3D structure of 1, topological analysis was performed. As shown in


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Figure 1e, Co1, Co2, tib and BPT3- can be regarded as four-, four-, three- and three-connectors, respectively. According to the simplification method,33 the resulting framework of 1 is an unusual (3,3,4,4)-connected 4-nodal 3D net with point symbol of {83}4{85·12}{86}2 (Figure 1f).

(b)

(c)

(d)



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(e)

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(f)

Figure 1. (a) Crystal structure of 1 with the ellipsoids drawn at the 30% probability level. Hydrogen atoms and free solvent molecules are omitted for clarity. (b) 2D network of Co-tib. (c) 3D structure of Co-BPT. (d) 3D structure of 1. (e) Simplified nodes of Co1, Co2, tib and BPT3-. (f) Topology of 1.

Crystal Structure of [Ni3(tib)2(BPT)2(H2O)6]·2H2O (4). When NaOH/H2O was used as reaction medium instead of DMF/H2O, framework 4 was obtained. As shown in Figure 2a, there are two crystallographically independent Ni atoms in the asymmetric unit of 4, one of which is on the inversion center. Both Ni1 and Ni2 are six-coordinated with distorted octahedral geometry, but different coordination environments. In addition to two N atoms from two different tib and two (for Ni1) or three (for Ni2) O ones from two BPT3- ligands, there are two (for Ni1) or one (for Ni2) coordinated water molecules. The Ni–N and Ni–O bond distances and coordination angles around Ni have usual values (Table S1). Each tib in 4 joins three Ni(II) to generate an infinite one-dimensional (1D) chain (Figure 2b), rather than the 2D network observed in 1 - 3 (Figure 1b). BPT3- in 4 also acts as a tridentate bridging ligand to link three Ni(II) using its carboxylate groups with (κ1)-(κ1)-(κ2)-µ3-BPT coordination mode (Scheme S1I) to form another 1D chain (Figure S1). Accordingly, the Ni-tib 1D chains are further connected together by BPT3- to form a 3D structure of 4 (Figure

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2c). The solvent accessible volume is 80.8 Å3 per 1458.1 Å3 unit cell volume (5.5% of the total crystal volume). Furthermore, from topological view, Ni1, Ni2, tib and BPT3- can be considered as four-, four-, three- and three-connectors, respectively (Figure S2), and 4 is a (3,3,4,4)-connected 4-nodal 3D net with point symbol of {4·82}2{4·85}2{83}2{85·12}2 (Figure 2d).

(a)

(b)

(c)

(d)

Figure 2. (a) The coordination around Ni(II) in 4 with ellipsoids drawn at the 30% probability level. Hydrogen atoms and non-coordinated molecules are omitted for clarity. (b) 1D chain of Ni-tib. (c) 3D structure of 4. (d) Topology of 4.



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Figure 3. (a) Coordination around Mn(II) in 5 with the ellipsoids drawn at the 30% probability level. Hydrogen atoms and free solvent molecules are omitted for clarity. (b) 2D (4, 4) grid structure of Mn-tib. (c) Side view of 2D layer structure of 5 with HBPT2- between two adjacent layers. (d) 3D supramolecular structure of 5 with hydrogen bonds indicated by dashed lines.

Crystal Structure of [Mn(tib)(H2O)3]·HBPT·DMF·2H2O (5). When metal salt was changed from Co(NO3)2·6H2O used in 2 or Ni(NO3)2·6H2O used in 3 to MnCl2·4H2O, 5 was isolated. As shown in Figure3a, Mn1 is surrounded by three imidazole N atoms (N1, N3A, N5B) from three distinct tib and three terminal water molecules (O1W, O2W, O3W) in a distorted octahedral arrangement. Each tib joins three Mn(II) atoms using its three imidazole groups and in turn each Mn(II) connects three tib ligands to generate a 2D network with typical (4, 4) grid structure (Figure 3b). It is worthy to note that partially deprotonated


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HBPT2- acts as counter anion and locates between two adjacent layers (Figure 3c). There are hydrogen bonds between the coordinated water molecules and the counter anions (Table S2), and eventually a 3D supramolecular structure of 5 is achieved (Figure 3d). Crystal structure of [Ni3(tib)2(BTB)2(H2O)2]·14H2O (6). When H3BTB was used to replace of H3BPT, MOFs 6 and 7 were obtained. As exhibited in Figure 4a, the asymmetric unit of 6 contains two Ni(II), one of which locates at an inversion center, one tib, one BTB3and one coordinated aqua molecule. The coordination environments for the six-coordinated Ni1 and Ni2 are different. In addition to two N atoms from two different tib and two (for Ni1) or four (for Ni2) O ones from two BTB3- ligands, there are two coordinated water molecules for Ni1. The Ni-N bond distances are from 2.021(3) Å to 2.068(3) Å, and the Ni-O ones range from 2.041(3) to 2.154(3) Å. In addition, the coordination angles around Ni are in the range of 61.55(9)-159.73(11)° (Table S1). Each tib links three Ni(II) atoms to form a 2D layer structure (Figures 4b and 4c). BTB3- acts as a tridentate ligand to bridge three Ni(II) atoms using its carboxylate groups adopting (κ1)-(κ2)-(κ2)-µ3-BTB coordination mode (Scheme S1II). Finally, the Ni-tib 2D layer structure is further linked by BTB3- to form a 3D structure of 6 (Figure 4d). The solvent accessible volume is 1146.8 Å3 per 4584.3 Å3 unit cell volume (25.0% of the total crystal volume). The results of topological analysis show that 6 is a (3,3,4,4)-connected 4-nodal 3D net with point symbol of {83}4{84·102}2{84·122} (Figure 4e) by considering Ni1, Ni2, tib and BTB3- as four-, four-, three- and three-connectors (Figure S3).



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(a)

(b)

(c)

(d)

(e)

Figure 4. (a) The coordination around Ni(II) in 6 with the ellipsoids drawn at the 30% probability level. Hydrogen atoms and non-coordinated water molecules are omitted for clarity. (b) 2D network of Ni-tib. (c) Schematic drawing of Ni-tib 2D network. (d) 3D structure of 6. (e) Topology of 6.


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Crystal Structure of [Co3(tib)2(BTB)2]·2DMF·6H2O (7). There are also two crystallographically independent Co(II) atoms in the asymmetric unit of 7, one of which was found at a specific position (Figure 5a). Co1 with distorted octahedral coordination geometry is coordinated by two N atoms (N3B, N5C) from two different tib, four carboxylate O (O1, O2, O5D, O6D) from two distinct BTB3-. The Co1-N bond distances have a range of 2.052(4)-2.077(4) Å and the Co1-O ones are from 2.035(3) to 2.315(3) Å. The coordination angles around Co1 are in the scope of 59.18(12)-159.01(14)° (Table S1). The coordination around Co2 is two imidazole N atoms (N1, N1A) from two different tib and two carboxylate O ones (O3, O3A) from two distinct BTB3-, generating a distorted tetrahedral coordination geometry. The Co2-N bond length is 2.003(5) Å and the Co2-O one is 1.942(5) Å (Table S1). In 7, Co(II) atoms and tib ligands are constructed into 2D network (Figure 5b). Meanwhile, each BTB3- ligand acts as a µ3-bridging linker with (κ1)-(κ2)-(κ2)-µ3-BTB coordination mode (Scheme S1II) to connect three Co(II) atoms to form a 3D framework (Figure 5c). The combined Co-tib and Co-BTB connections generate the final 3D structure of 7 (Figure 5d viewed along c axis and Figure S4 viewed along b axis). The solvent accessible volume of 7 is 2860.1 Å3 per 9338.0 Å3 unit cell volume (30.6% of the total crystal volume). Co1, Co2, tib and BTB3- can be treated as four-, four-, three- and three-connectors, respectively (Figure 5e), and the topology of 7 is a (3,3,4,4)-connected 4-nodal 3D net with point symbol of {82·103·12}{82·10}4{84·102}2 ( Figure 5f).

(a)



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(b)

(c)

(d)

(e)

(f)

Figure 5. (a) The coordination of Co(II) in 7 with the ellipsoids drawn at the 30% probability level. Hydrogen atoms and non-coordinated solvent molecules are omitted for clarity. (b) 2D network of Co-tib. (c) 3D framework of Co-BTB. (d) 3D structure of 7. (e) Simplified nodes of Co1, Co2, tib and BTB3-. (f) Topology of 7.


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Comparison of the Structures. Frameworks 1 - 7 were obtained by using mixed organic ligands under hydro/solvothermal conditions. The complete deprotonation of the tricarboxylic acid to the tricarboxylate of BPT3- and BTB3- in 1 - 4, 6 and 7 was confirmed by their IR spectral data as well as crystallographic analysis (vide infra). The partial deprotonation of H3BPT to HBPT2- in 5 was also evidenced by IR spectral and crystallographic data since vibration bands from -COOH were observed at 1695 and 1663 cm-1, and the H atom of -COOH was found from the fourier map directly. Different framework structures and topologies of 2 and 7 as well as 4 and 6 are ascribed to the different tricarboxylate ligands. Furthermore, 2, 3 and 5 were prepared by the same procedures and conditions except for the different metal salts. The results suggest the subtle influence of metal centers since 2 and 3 have the same 3D frameworks, however, 5 is a 2D network. The results of present work suggest that an approach to tune the structural diversity of MOFs can be achieved by modifying the organic carboxylate ligands and choosing suitable metal centers. PXRD and TGA. The purity for the bulky sample of synthesized 1 - 7 was checked by PXRD measurements and the results are provided in Figure S5. Well consistent of the PXRD pattern of the as-synthesized sample with the corresponding simulated one confirms the phase purity of the complexes. Thermogravimetric analysis (TGA) was involved in evaluating the thermal stability of the frameworks and TG curves of 1 - 7 are shown in Figure 6. 1 displays weight loss of 11.8% from room temperature to 255 °C, owing to the loss of free and coordinated H2O molecules as well as free DMA (calc. 11.5 %). The residue is stable up to about 335 °C. For 2, weight loss of 11.0% was observed in the temperature range of 30-280 °C, which is caused by the removal of three free and two coordinated H2O and one free DMF (calc. 11.2 %) and



further weight loss was observed at about 320 °C, implying the collapse of the framework of 2. TG curve of 3 gives weight loss of 10.2% from room temperature to 260 °C, originating from the loss of one and a half of free and two coordinated water and one free DMF (calc. 9.5 wt.%), and the framework is stable up to about 350 °C. For 4, weight loss of 7.3% was detected in the temperature range of 50-210 °C, which is consistent with the loss of free and coordinated water molecules (calc. 7.7 wt.%), and further weight loss occurred at about 370 °C, due to the decomposition of the framework of 4. The TG curve of 5 shows a weight loss of 20.7% before 290 °C, implying the release of two free and three coordinated H2O and one free DMF (calc. 20.9%). After that, the residue starts to decompose at about 350 °C. Weight loss of 14.7% from 30 to 140 °C was observed for 6, corresponding to the loss of 14 free and two coordinated water molecules (calc. 15.2 wt.%), and the decomposition of the framework was found at about 400 °C. In the case of 7, 13.3% weight loss was detected between the temperatures 30 and 210 °C, which is close to the value of 13.7% calculated by the loss of six free water and two free DMF molecules, and further weight loss was detected at about 370 °C, indicating the collapse of the framework of 7. 100

1 2 3 4 5 6 7

80 Weight (%)

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60

40

20 200

400 Temperature (oC)

600

Figure 6. TGA curves of 1 - 7.


800

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Adsorption Properties Gas and Vapor Adsorption. The porosity of the frameworks encourages us to examine their sorption behavior. 1, 2 and 3 have the same framework structures and similar porosity, thus the sorption performances of the activated samples 1′ and 4′ - 7′ for N2 at 77 K, CO2 at 195 K, CH3OH and CH3CH2OH at 298 K were discussed here. The desolvated samples 1′, 5′ and 7′ were achieved by immersing the as-synthesized complexes 1, 5 and 7 in tetrahydrofuran (THF) for 3 days, changing THF solvent every 8 h, and then heating the solvent-exchanged samples at 353 K under a dynamic high vacuum for 10 h. In the case of 4 and 6, the activated samples 4′ and 6′ were got by directly heating the fresh as-synthesized samples at 180 oC for 10 h under high vacuum. The removal of free solvent molecules in 1 and 4 - 7 was evidenced by TGA (Figure S6). The observed weight losses for 1 and 4 - 6 are caused by the release of coordinated water molecules. The PXRD patterns of activated samples imply their good crystallinity (Figure S7). The results show that 1 and 4 - 7 have good stability and the desolvated samples 1′ and 4′ - 7′ maintained the framework structures without destroying. The sorption isotherms for 1' suggest only surface adsorption of N2 at 77 K,34 while the adsorption of CO2 at 195 K, CH3OH and CH3CH2OH at 298 K of 1' was detected. The CO2 adsorption of 78.82 cm3·g-1 at P = 0.99 atm corresponds to about 4.7 CO2 molecules per formula unit for 1' (Figure 7a). The hysteresis and incomplete desorption suggest the strong interactions between the adsorbate and adsorbent.35 Based on the CO2 adsorption isotherm, the Brunauer-Emmett-Teller (BET) surface area and pore volume of 1' are found to be 187.65 cm2·g-1 (Langmuir surface area 231.66 cm2·g-1) and 0.143 cm3·g-1, respectively. As for CH3OH and CH3CH2OH adsorption of 1' at 298 K (Figure 7b), the final values of 62.69 cm3·g-1 (95.15 mg·g-1) and 34.47 cm3·g-1 (73.86 mg·g-1) at P = 0.99 atm are corresponding to ca. 4.9 CH3OH and 2.1 CH3CH2OH molecules per formula unit for 1'.



80

-1

Amount adsorpted (cm3g -1(STP) )

Amount adsorpted (cm g (STP) )

CO2 at 195 K

80

3

60

MeOH at 298 K

60

40

20

N2 at 77 K

40

EtOH at 298 K 20

0

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0.4 0.6 Relative pressure (p/p0)

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1.0

0.2


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15

CO2 at 195 K 10

N2 at 77 K

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EtOH at 298 K

10 5 0

1.0

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(c)

CO2 at 195 K 30

3

-1

1.0

40 MeOH at 298 K

Amount adsorpted (cm3g-1(STP) )

Amount adsorpted (cm g (STP) )

0.4 0.6 0.8 Relative pressure (p/p0)

(d)

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20

10 N2 at 77 K

30

0.2


EtOH at 298 K

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10

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(e)

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CO2 at 195 K

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MeOH at 298 K

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N2 at 77 K 0 0.0

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Relative pressure (p/p0)

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(a)


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0.2

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EtOH at 298 K

0 0.0

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Relative pressure (p/p0)



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(g) 140

(h)

CO2 at 195 K



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120 100 80 60

N2 at 77 K

40 20 0 0.0

0.2


0.8

1.0

MeOH at 298 K

60

40

20

EtOH at 298 K

0 0.0

0.2

(i)


1.0

(j)

Figure 7. Adsorption isotherms of N2 at 77 K, CO2 at 195 K, MeOH and EtOH at 298 K for 1' (a) and (b), 4' (c) and (d), 5' (e) and (f), 6' (g) and (h), 7' (i) and (j) (Filled shape, adsorption; open shape, desorption).

As for 4', almost no N2 adsorption was observed at 77 K and 1.0 atm, while limited CO2 adsorption at 195 K and 1.0 atm was detected (Figure 7c). The value of 19.61 cm3·g-1 at 195 K and 0.99 atm shows about 1.2 CO2 molecules per formula unit for 4', and the BET surface area and pore volume are 37.53 cm2·g-1 (Langmuir surface area 54.66 cm2·g-1) and 0.03 cm3·g-1, respectively. 4' shows less amount adsorption of CH3OH and CH3CH2OH at 298 K (Figure 7d) compared with those of 1' (Figure 7b): 27.96 cm3·g-1 (39.9 mg·g-1) and 12.18 cm3·g-1 (25.01 mg·g-1) at P = 0.99 atm corresponding to about 1.7 CH3OH and 0.75 CH3CH2OH molecules per formula unit for 4'. 5' exhibits similar sorption behavior with those of 1' as shown in Figure 7e and 7f: surface adsorption of N2 at 77 K; 32.17 cm3·g-1 of CO2 at 195 K corresponding to about 0.97 CO2 molecules per formula unit for 5', and BET surface area and pore volume of 29.46 cm2·g-1 (Langmuir surface area 46.54 cm2·g-1) and 0.027 cm3·g-1, 18.64 cm3·g-1 (28.29 mg·g-1) of CH3OH and 14.12 cm3·g-1 (30.26 mg·g-1) of CH3CH2OH at 298 K corresponding to ca. 0.56 CH3OH and 0.42 CH3CH2OH molecules per formula unit for 5' (Figure 7f).



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It is noteworthy that almost no adsorption of N2 at 77 K and CH3CH2OH at 298 K was found for 6' (Figure 7g and 7h). The final value of CO2 adsorption at 195 K is 124.49 cm3·g-1 at P = 0.99 atm corresponding to about 9.4 CO2 molecules per formula unit for 6'. The BET surface area and pore volume are 331.01 cm2·g-1 (Langmuir surface area 440.53 cm2·g-1) and 0.23 cm3·g-1, respectively. As for the CH3OH adsorption of 6' at 298 K (Figure 7h), 228.5 cm3·g-1 (346.8 mg·g-1) at P = 0.99 atm corresponds to about 16.7 CH3OH molecules per formula unit for 6'. As for 7', the up-takes of 58.69 cm3·g-1 N2 at 77 K and 131.07 cm3·g-1 CO2 at 195 K around 1 atm correspond to ca. 4.2 N2 and 9.4 CO2 molecules per formula unit (Figure 7i). The BET surface area and pore volume based on the CO2 adsorption are 358.02 cm2·g-1 (Langmuir surface area 499.6 cm2·g-1) and 0.24 cm3·g-1, respectively. The larger CO2 uptake than N2 observed for 7' may be due to the smaller kinetic diameter of CO2 (3.30 Å) than that of N2 (3.64 Å).36 The final values of 61.43 cm3·g-1 (93.24 mg·g-1) for CH3OH and 27.28 cm3·g-1 (58.46 mg·g-1) for CH3CH2OH at P = 0.99 atm correspond to about 4.4 CH3OH and 1.95 CH3CH2OH molecules per formula unit for 7' (Figure 7j). From the above adsorption results, the larger CO2 uptake than N2 observed for 1' and 4' 7' may be ascribed to the different molecular sizes since CO2 has smaller kinetic diameter compared to that of N2. In addition, the quadrupole-dipole interactions between CO2 and framework may be beneficial to the adsorption.37 The observed hysteretic adsorption behavior suggests that the strong interactions between the adsorbed CO2 and the framework.38 Dyes Adsorption. With increasing industrial development, high selectivity to different dye molecules becomes more and more important in treatment of waste water.

7,39-41

Accordingly, it is essential to explore the selective dye adsorption for the frameworks. Methylene blue (MB), methyl orange (MO) and rhodamine B (RhB) (Scheme S2) are


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common dyes. To examine the adsorption of 1 and 7 for dyes, 10 mg of the activated samples 1′ and 7′ were suspended into an aqueous solution of MO, MB and RhB (10 ppm, 20 mL) at 25 °C under the dark condition, and UV-vis absorption spectroscopy was used to monitor the dye adsorption. As shown in Figure 8, 7' exhibits better adsorption ability than 1' for MB compared with MO and RhB. MB was effectively removed after 24 h from aqueous solution in 7' as evidenced by the color change from the blue MB solution to nearly colorless. However, no obvious color variation was observed for MB solution in 1' (Figure 8a and Table S3). Therefore, comparing with 7', the adsorption capacity of 1' for MB is much weaker. Furthermore, no significant color change was found for the yellow MO solution, and the MO concentration in aqueous solution changed little from the initial 10 ppm to 9.86 ppm for 1 and 9.73 ppm for 7' (Figure 8b and Table S4). In addition, there are almost no color changes for the rose RhB solution, and the RhB concentration in water reduced from the 10 ppm to 9.46 ppm for 1' and 9.28 ppm for 7' (Figure 8c and Table S5). The results show that 7' has high selectivity for adsorption of MB in aqueous solution. There are factors in determining the selective adsorption of dye molecules.42 One is the size fittingness between the channel of the framework and the dye molecule. The better adsorption ability of 7′ than 1′ to MB may be attributed to the appropriate pore size of 7'. Furthermore, selective removal of MB over RhB in aqueous solution for 7′ may be ascribed to the different molecular sizes of the MB and RhB (Scheme 2). However, the selective adsorption of MB over MO may be caused by another important factor, since MB and MO have similar size (Scheme S2), namely the interactions between the framework and dye molecule. Electrostatic interactions between the carbonyl groups of BTB in 7' and the cationic dye MB may helpful for adsorption, on the contrary, electrostatic repulsion between the carbonyl and anionic MO dye can exclude the adsorption. Furthermore, PXRD patterns



indicate the maintain of framework structures of 1′ and 7′ after the dye adsorption (Figure S8), implying that 7′ can be used for selective removal of MB dye from the waste water. 2.0

MB 1′′ + MB after 24 h 7′′ + MB after 24 h

Absorbance

1.5

1.0

0.5

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500

600 Wavelength/nm

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(a) 0.8 MO 1′ + MO after 24 h 7′ + MO after 24 h

Absorbance

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(b) 1.6

RhB 1′′ + RhB after 24 h 7′′ + RhB after 24 h

1.2 Absorbance

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0.8

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(c) Figure 8. Adsorption capability of 1' and 7' toward MB (a), MO (b) and RhB (c).

CONCLUSIONS


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In summary, we have sucessfully synthesized seven new MOFs with mixed tib and tricarboxylate ligands. By varying metal salts and tricarboxylate ligands, 2D and 3D frameworks with different topology have been achieved. Adsorption properties of 1 - 7 were investigated and the results show that the frameworks have hysteretic and selective adsorption of CO2 over N2, suggesting a possible application in selective adsorption and separation. In addition, activated 7 was suggested as a potential adsorbent for removal MB in aqueous solution. This study provides further insights into the rational design of MOF-based functional materials.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental Section, tables for slected bond lengths and angles, hydrogen bonding and adsorption of dye molecules, schemes for coordination modes of carboxylate ligands and structure of dye molecules, structure figures, PXRD patterns and TG (PDF).

Accession Codes CCDC 1504234-1504240 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

AUTHOR INFORMATION Corresponding Author



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* Tel: +86 25 89683485. E-mail: [email protected]. (W.-Y.S.).

ACKNOWLEDGMENTS We gratefully acknowledge the National Natural Science Foundation of China (grant nos. 21331002 and 21573106) for financial support of this work. This work was also supported by a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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Syntheses, Structures and Sorption Properties of Metal-Organic Frameworks with 1,3,5-Tris(1-imidazolyl)benzene and Tricarboxylate Ligands Yu-Ling Li, Yue Zhao, Yan-Shang Kang, Xiao-Hui Liu, and Wei-Yin Sun

Seven new MOFs with mixed organic ligands have been obtained and found to show selective adsorption property, furthermore, 7 is a potential adsorbent to capture methylene blue (MB) in the aqueous solution.


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Syntheses, Structures, and Sorption Properties of MetalâOrganic

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