Carboxylate-Assisted Assembly of Zinc and Cadmium Coordination

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Carboxylate-Assisted Assembly of Zinc and Cadmium Coordination Complexes of 1,3,5-Tri-4-pyridyl-1,2-ethenylbenzene: Structures and Visible Light-Induced Photocatalytic Degradation of Congo Red in Water Jian-Guo Zhang, Wei-Jie Gong, Yu-Song Guan, Hong-Xi Li, David James Young, and Jian-Ping Lang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01040 • Publication Date (Web): 27 Aug 2018 Downloaded from http://pubs.acs.org on August 28, 2018

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Crystal Growth & Design

Carboxylate-Assisted Assembly of Zinc and Cadmium Coordination Complexes of 1,3,5-Tri-4-pyridyl-1,2-ethenylbenzene: Structures and Visible Light-Induced Photocatalytic Degradation of Congo Red in Water

Jian-Guo Zhang,†,‡ Wei-Jie Gong,† Yu-Song Guan,† Hong-Xi Li,*,† David James Young,§ and Jian-Ping Lang*,†,‡

†

State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials,

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People’s Republic of China. ‡

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,

Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China §

Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast,

Maroochydore DC, Queensland 4558 Australia

ACS Paragon Plus Environment

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Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT Solvothermal reactions of zinc and cadmium nitrates with 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene (tpeb) in the presence of various carboxylic acids including 4-iodobenzoic acid (4-HIBA), benzene-1,4-dicarboxylic acid (1,4-H2BDC), 2,5-furandicarboxylic acid (2,5-H2FDC), 2,5dibromoterephthalic acid (2,5-H2DBTPA), 1,2-cyclohexanedicarboxylic acid (1,2-H2CHDC) and 1,5-pentanedioic acid (1,5-H2PDC) gave rise to eight coordination complexes, viz, [Zn(tpeb)2(4IBA)2]·2H2O (1), {[Cd(NO3)(tpeb)(4-IBA)]·H2O}n (2), {[Cd2(NO3)2(tpeb)2(1,4-BDC)]}n (3), {[Cd2(tpeb)2(2,5-FDC)2]·2H2O}n (4), [Cd(tpeb)(2,5-DBTPA)2]n (5), {[Cd2(H2O)2(tpeb)2(1,2CHDC)2]·H2O}n (6), [Zn(tpeb)(1,2-CHDC)]n (7) and {[Zn(tpeb)(1,5-PDC)]·H2O}n (8). Compound 1 is a discrete mononuclear complex with its Zn(II) center coordinated by two pairs of tpeb and 4-IBA ligands. Compound 2 has a 2D waterfall-like network constructed from bridging [Cd(NO3)(4-IBA)] units with tpeb ligands. Compounds 3, 4 and 5 contain similar 1D [Cd(tpeb)]n chains, which are linked by 1,4-BDC, 2,5-FDC and 2,5-DBTPA bridges, respectively, forming either 2D (2 and 3) networks or a 3D (4) framework. Compound 6 holds a 2D wave-like layer structure in which dimeric [Cd2(H2O)2(1,2-CHDC)2] fragments are connected by two couples of tpeb ligands. Compounds 7 and 8 contain similar 2D fish-scale networks assembled from 1D chains of [Zn(1,2-CHDC)]n or [Zn(1,5-PDC)]n bridged by tpeb ligands. Compound 6, as a representative sample, has larger absorption in visible light region, and can be employed to efficiently degrade Congo Red (CR) in water without additional oxidizing or reducing reagents upon visible light irradiation. This photocatalyst could be recycled at least five times without evident loss of its catalytic efficiency.


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INTRODUCTION

Coordination polymers (CPs) have been developed for catalysis,1-3 gas storage and capture,4-7 photoluminescence,8-12 drug delivery,13-15 molecule sensing16-17 and other applications. However, it is still a challenge to synthesize CPs with specific structures and properties. Fortuitously, CPs have the advantage of adjustability and designability relative to other materials because their structures can be finely controlled by choosing different organic linkers, metal centers/metal clusters and reaction conditions. Most CPs have been assembled from metal ions with N-donor ligands or carboxylates. In this regard, the nature,18-21 the number of coordination sites,22-24 the substituent groups25-27 and the flexibility28-31 of carboxylate and N-donor ligands, and metal centres32 play an important role in directing the various structures and properties of the resulting CPs. So far, the most commonly employed N-donor ligands are mono- and bis-pyridyl ligands.3336

Tris-/poly-pyridyl bridging ligands have been less used for the construction of CPs. For

example, Zheng and co-workers reported a Fe-based CP of the tripyridyl ligand 1,3,5-tris(4pyridyl)benzene (1,3,5-TPB) that showed selective gas adsorption and guest-dependent spincrossover behavior.37 Boskovic used 1,2,4,5-tetra(4-pyridyl)benzene (1,2,4,5-TPB) to construct one-dimensional (1D) chain and ribbon cobalt−dioxolene CPs that exhibited thermally induced, valence tautomeric transition properties.38 On the other hand, Congo red (sodium salt of 3,3′-([1,1′-biphenyl]-4,4′-diyl)bis(4aminonaphthalene-1-sulfonic acid) as a representative azo dye was used extensively in microscopy for staining elastic fibers and bacteria, silk, textile, paper, rubber and plastic manufacturing.39-43 These dyes are toxic and can pollute water-ways around textile factories, particularly in developing countries. Methods for removing dye pollutants from wastewater


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include various physical,44 chemical,45 and biological46 approaches. Among these, photocatalytic degradation has the advantage of high-efficiency and recyclability, although some procedures involve using extra reagents such as NaBH4 or H2O2, and ultraviolet light.47-51 M N

N

N

N

N

N

M

M

Type I (1)

Type II (6, 7, 8)

M

M

N

N

N

N M

N

N

M

M

M

Type III (2)

Type IV (3, 4, 5)

Scheme 1. Coordination modes and conformations of the tpeb ligands in 1-8.

Recently we have been interested in the assembly of functional CPs bearing multidentate pyridyl conjugated ligands for special chemical and/or physical applications. For instance, one tripyridyl ligand with three olefinic bonds, 1,3,5-tris(-2-(pyridin-4-yl)vinyl)benzene (tpeb), was employed to produce three zinc CPs, which exhibited highly selective photoluminescent sensing of Cr(III) and Cr(VI) in water.52 As an extension of this project, we herein report the


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solvothermal reaction of zinc and cadmium salts with tpeb and a choice of six carboxylic acid ligands (Scheme 1) bearing different coordinating functionality, viz, 4-iodobenzoic acid (4HIBA), benzene-1,4-dicarboxylic acid (1,4-H2BDC), 2,5-furandicarboxylic acid (2,5-H2FDC), 2,5-dibromoterephthalic acid (2,5-H2DBTPA), 1,2-cyclohexanedicarboxylic acid (1,2-H2CHDC) and 1,5-pentanedioic acid (1,5-H2PDC). These combinations of metal salts and ligands resulted in the isolation of [Zn(tpeb)2(4-IBA)2]·2H2O (1), {[Cd(NO3)(tpeb)(4-IBA)]·H2O}n (2), {[Cd2(NO3)2(tpeb)2(1,4-BDC)]}n (3), {[Cd2(tpeb)2(2,5-FDC)2]·2H2O}n (4), [Cd(tpeb)(2,5DBTPA)2]n (5), {[Cd2(H2O)2(tpeb)2(1,2-CHDC)2]·H2O}n (6), [Zn(tpeb)(1,2-CHDC)]n (7) and {[Zn(tpeb)(1,5-PDC)]·H2O}n (8). These compounds show very rich structure varieties along with various coordination modes of tpeb ligands (Scheme 1). In addition, the representative complex 6 proved to be a highly efficient and conveniently recyclable photo-catalyst for degrading CR in water under visible light irradiation.

EXPERIMENTAL SECTION

General Procedure. All reagents were commercially available and employed without further purification. The ligand tpeb was prepared according to the literature method.53 The corresponding measurements were carried out on the same instruments we reported before.45,52,54 Synthesis of [Zn(tpeb)2(4-IBA)2]·2H2O (1). A mixture of 14.9 mg of Zn(NO3)2·6H2O (0.05 mmol), 24.8 mg of 4-HIBA (0.1 mmol), 38.8 mg of tpeb (0.1 mmol), 2 mL of H2O, and 1 mL of MeCN was added to a Pyrex glass tube (length: 14 cm, diameter: 7mm). Then the glass tube was sealed and put in an electric oven, heating for 2 days at 150 °C and cooling to ambient temperature at a rate of 6 °C per hour to give light yellow block crystals of 1 (This procedure was similar to the following cases only with difference in starting materials). The crystals were


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then washed with MeCN, EtOH and Et2O, and dried in vacuo. Yield: 14.2 mg (21% based on tpeb). Anal. Calcd for C68H52I2N6O5Zn: C, 60.39; H, 3.88; N, 6.21%; found: C, 59.69; H, 4.20; N, 6.07%. IR (KBr disc): 3423 (m), 3028 (w), 1927 (w), 1630 (s), 1549 (m), 1504 (m), 1431 (m), 1413 (m), 1389 (s), 1367 (m), 1208 (m), 1171 (m), 1131 (m), 1069 (m), 1027 (m), 1007 (m), 963 (m), 845 (s), 799 (m), 765 (m), 679 (m), 570 (s), 533 (m), 521 (m), 474 (m) cm−1. Synthesis of {[Cd(NO3)(tpeb)(4-IBA)]·H2O}n (2). Light yellow blocks of 2 were generated with starting materials: 15 mg of Cd(NO3)2·4H2O (0.05mmol), 12.4 mg of 4-HIBA (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 14.1 mg (34% based on tpeb). Anal. Calcd for C34H26CdIN4O5.5: C, 49.93; H, 3.20; N, 6.85%; found: C, 49.50; H, 3.36; N, 7.32%. IR (KBr disc): 3442 (m), 3032 (w), 1636 (w), 1605 (s), 1584 (m), 1534 (m), 1501 (m), 1425 (m), 1399 (s), 1384 (m), 1301 (m), 1222 (m), 1205 (m), 1176 (m), 1010 (s), 960 (m), 849 (s), 801 (m), 768 (m), 671 (m), 541 (s), 524 (m), 479 (m) cm−1. Synthesis of {[Cd2(NO3)2(tpeb)2(1,4-BDC)]}n (3). Yellow blocks of 3 were obtained with starting materials: 15 mg of Cd(NO3)2·4H2O (0.05 mmol), 4.2 mg of 1,4-H2BDC (0.025 mmol), 19.3 mg of tpeb (0.05 mmol), 1.5 ml of H2O and 1.5 mL of MeCN. Yield: 11.9 mg (37% based on tpeb). Anal. Calcd for C31H23CdN4O5: C, 57.82; H, 3.60; N, 8.60%; found: C, 57.92; H, 3.52; N, 8.53%. IR (KBr disc): 3447 (m), 1630 (m), 1605 (s), 1562 (m), 1500 (w), 1456 (m), 1420 (w), 1385 (s), 1279 (m), 1219 (w), 1205(m), 1096 (m), 1012 (w), 981 (m), 960 (w), 872 (m), 856 (m), 851 (m), 836 (m), 809 (m), 753 (m), 689 (m), 539 (m), 527 (m) cm−1. Synthesis of {[Cd2(tpeb)2(2,5-FDC)2]·2H2O}n (4). Light yellow blocks of 4 were produced with starting materials: 15 mg of Cd(NO3)2·4H2O (0.05 mmol), 7.8 mg of 2,5-H2FDC (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 15.6 mg (46%


6

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based on tpeb). Anal. Calcd for C66H50Cd2N6O12: C, 58.98; H, 3.75; N, 6.25%; found: C, 59.45; H, 3.73; N, 6.16%. IR (KBr disc): 3445 (m), 3061 (w), 1607 (s), 1562 (m), 1500 (m), 1420 (m), 1371 (s), 1218 (m), 1204 (w), 1065 (w), 1011 (m), 971 (m),870 (m), 857 (m), 843 (m),815 (m), 788 (m), 689 (m),540 (m) cm−1. Synthesis of [Cd(tpeb)(2,5-DBTPA)]n (5). Yellow blocks of 5 were obtained with starting materials: 15 mg of Cd(NO3)2·4H2O (0.05 mmol), 16.2 mg 2,5-H2DBTPA (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 14.7 mg (36% based on tpeb). Anal. Calcd for C35H23Br2CdN3O4: C, 51.15; H, 2.82; N, 5.11%; found: C, 50.76; H, 3.12; N, 4.94%. IR (KBr disc): 3423 (m), 3011 (w), 1606 (s), 1499 (m), 1453 (m), 1423 (m), 1376 (s), 1306 (m), 1221 (m), 1203 (m), 1054 (s), 1013 (m), 959 (m), 918 (m), 843 (m), 836 (m), 815 (m), 798 (m), 686 (m), 540 (s), 523 (m) cm−1. Synthesis of {[Cd2(H2O)2(tpeb)2(1,2-CHDC)2]·H2O}n (6). Light yellow block crystals of 1 were isolated with starting materials: 15 mg of Cd(NO3)2·4H2O (0.05 mmol), 8.6 mg of 1,2H2CHDC (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 23.6 mg (69% based on tpeb). Anal. Calcd for C70H67Cd2N6O11: C, 60.31; H, 4.92; N, 6.03%; found: C, 60.63; H, 4.94; N, 6.05%. IR (KBr disc): 3287 (m), 3030 (w), 2925 (w), 2843 (w), 1635 (w), 1607 (s), 1575 (s), 1502 (m), 1415 (m), 1345 (m), 1191 (m), 1068 (m), 1013 (m), 969 (m), 890 (m), 847 (m), 803 (m), 679 (m), 534 (m) cm−1. Synthesis of [Zn(tpeb)(1,2-CHDC)]n (7). Light yellow blocks of 7 were separated with starting materials: 14.9 mg of Zn(NO3)2·6H2O (0.05 mmol), 8.6 mg of 1,2-H2CHDC (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 15.2 mg (49% based on tpeb). Anal. Calcd for C35H31N3O4Zn: C, 67.47; H, 5.02; N, 6.74%; found: C, 67.12; H,


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5.43; N, 6.64%. IR (KBr disc): 3420 (m), 3029 (w), 2927 (w), 2842 (w), 1611 (s), 1503 (m), 1429 (m), 1384 (m), 1340 (m), 1285 (m), 1223 (m), 1206 (m), 1066 (m), 1026 (m), 973 (m), 846 (m), 802 (m), 773 (m), 679 (m), 547 (m), 534 (m), 522 (m) cm−1. Synthesis of {[Zn(tpeb)(1,5-PDC)]·H2O}n (8). Light yellow blocks of 8 were produced with starting materials: 14.9 mg of Zn(NO3)2·6H2O (0.05 mmol), 6.6 mg of 1,5-H2PDC (0.05 mmol), 19.3 mg of tpeb (0.05 mmol), 2 mL of H2O and 1 mL of MeCN. Yield: 8.1 mg (27% based on tpeb). Anal. Calcd for C32H27N3O5Zn: C, 64.17; H, 4.54; N, 7.02%; found: C, 63.87; H, 4.28; N, 6.78%. IR (KBr disc): 3441 (m), 3031 (w), 1611 (s), 1503 (m), 1431 (m), 1383 (s), 1225 (m), 1207 (m), 1068 (m), 1027 (m), 975 (m), 865 (m), 846 (s), 803 (m), 733 (m), 679 (m), 548 (s), 523 (m), 423 (m) cm−1. X-ray Crystallography. Single crystals of 1-8 appropriate for X-ray analysis were obtained directly from the above syntheses. Each single crystal was mounted on a glass fiber at 223 K (1, 2, 3, 4, 5, 6 and 7) and 193 K (8). The crystal data of 1-7 were collected on an Agilent Xcalibur and 8 was collected on a Bruker D8-Quest diffractometer equipped with Mo Kα radiation (graphite monochromated, λ = 0.71073 Å) or Cu Kα radiation (graphite monochromated, λ = 1.54178 Å). Programs CrysAlisPro (Agilent Technologies, CrysAlis171. NET, Ver. 1.71.36.28) and SAINT (Bruker) were used to process the data of 1-8. An absorption correction (multiscan) was applied in each case. The crystal structures of 1-8 were solved by direct methods.55-56 For 1 and 4, the theta values of the missing reflections were less than 3.3350° and 3.0350°, and these reflections were excluded. All non-hydrogen atoms were refined anisotropically on F2 by fullmatrix least-square method. For 6, the hydrogen atoms on O11 of the uncoordinated water molecule were not included in the model. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms. Crystallographic data have been


8

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deposited with the Cambridge Crystallographic Data Center (CCDC) as supplementary publication numbers 1849516-1849523. These data can be either obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif or from the Supporting Information. A summary of key crystallographic data for 1-8 were presented in Table 1. Their selected bond lengths and angles were listed in Table S1.

Table 1. Crystal Data and Structure Refinement Parameters for 1-8. 1

2

3

4

5

6

7

8

empirical formula

C68H52I2N6O5Zn

C68H52Cd2I2N8O11

C31H23CdN4O5

C66H50Cd2N6O12

C35H23Br2CdN3O4

C70H68Cd2N6O11

C35H31N3O4Zn

C32H27N3O5Zn

formula weight

1352.35

1635.80

643.94

1343.94

821.77

1392.08

623.02

598.96

crystal system

Triclinic

Monoclinic

Triclinic

Triclinic

Triclinic

Monoclinic

Monoclinic

Monoclinic

space group

Pī

P21/n

Pī

Pī

Pī

P21/c

P21/c

P21/n

a/Å

8.2517(4)

10.1117(6)

9.2392(8)

9.8990(3)

10.0864(7)

11.3337(2)

8.5925(8)

8.0930(6)

b/Å

13.7261(7)

22.4124(10)

11.3245(8)

16.6148(7)

11.7284(6)

21.9124(5)

28.771(3)

27.2017(18)

c/Å

25.7126(16)

14.6705(8)

14.4393(13)

18.1067(5)

14.8470(11)

26.0606(4)

12.2672(10)

12.6574(9)

α (deg)

89.206(4)

77.271(7)

91.099(3)

90.268(5)

β (deg)

87.843(4)

79.593(7)

95.843(2)

99.392(6)

95.516(1)

104.983(9)

92.318(2)

γ (deg)

88.094(4)

71.133(7)

99.739(3)

102.962(5)

3

93.485(5)

V/Å

2908.4(3)

3318.6(3)

1384.6(2)

2917.83(17)

1687.1(2)

6442.1(2)

2929.5(5))

2784.2(3)

ρcalc/g cm-3

1.544

1.637

1.545

1.530

1.618

1.435

1.413

1.429

Z

2

2

2

2

2

4

4

4

µ/mm

1.541

1.636

0.837

0.799

3.057

5.819

0.884

0.929

F(000)

1356.0

1612.0

650.0

1360.0

808.0

2848.0

1296.0

1240.0

0.0720

0.0463

0.0435

0.0475

0.0677

0.0515

0.0858

0.0510

0.1341

0.1272

0.0912

0.1606

0.1439

0.1554

0.3139

0.1524

1.012

1.016

0.995

0.940

1.003

0.956

0.914

1.066

–1

R1

a

wR2b GOF

c

a R1= Σ||Fo|-|Fc||/Σ|Fo|. bwR2= {Σw(Fo2-Fc2)2/Σw(Fo2)2}1/2. cGOF = {Σw((Fo2-Fc2)2)/(n-p)}1/2, where n =number of reflections and p = total number of parameters refined.


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Photocatalytic Experiments. Photocatalytic degradation of CR was assessed under visible white light (xenon lamp 196 W, CEL-HXUV300, Aulight) with a UV-cut off filter (λ < 400 nm). Solutions of CR were prepared by stirring the powder in deionized water until clear. A wellground sample of 6 (12 mg) was dispersed in 50 mL of dye solution (200.0 mg L-1) and magnetically stirred in the dark for ca. 120 min to ensure the adsorption–desorption equilibrium. The solution was then exposed to visible white light irradiation at 25 °C. Samples were periodically taken out and immediately centrifuged to separate any suspended solids and the UVvis spectrum of the resulting solution was measured.

RESULTS AND DISCUSSION

Synthetic, Spectral and Thermal Analysis Aspects. Solvothermal treatment of Zn(NO3)2·6H2O or Cd(NO3)2·4H2O with tpeb and 4-HIBA, 1,4-H2BDC, 2,5-H2FDC, 2,5H2DBTPA, 1,2-H2CHDC, or 1,5-H2PDC with an optimized molar ratio of 1:1:1 (1, 2, 4, 5, 6 and 7), 2:2:1 (3) and 1:2:2 (1) in H2O/MeCN (v/v = 2/1 for 1, 2, 4, 5, 6, 7 and 8) and (v/v = 1/1 for 3) at 150 °C for 48 h followed by a standard workup afforded crystals of 1-8 in various yields (21% for 1, 34% for 2, 37% for 3, 46% for 4, 36% for 5, 69% for 6, 49% for 7 and 27% for 8) (Scheme 2). When the molar ratios of the starting materials changed, 1-8 were the only products The change of the reaction temperature to lower (e.g. 130 ºC) or higher (e.g. 170 ºC), the products 18 were obtained in lower yields. However, analogous reactions in other solvent systems (DMF/MeCN, H2O/EtOH and H2O/DMF) produced neither 1-8, nor other identifiable products.


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Scheme 2. Reactions of tpeb with zinc and cadmium nitrates and various carboxylic acids. Complexes 1-8 are air and moisture stable and insoluble in common organic solvents such as CHCl2, CHCl3, MeOH, MeCN, DMF and DMSO. The elemental analyses were consistent with their chemical formula. The IR spectra of 1-8 had a strong band at 1605-1630 cm-1 corresponding to the stretching vibrations of the coordinated carboxyl groups. The identities of 1-8 were confirmed by X-ray crystallography. The PXRD patterns of 1-8 agreed with those simulated from the corresponding single-crystal X-ray structures, indicating their phase purity (Figure S1). Their thermogravimetric analysis revealed 2.3% loss of weight at 220 °C (1), 0.4% loss of weight at 210 °C (2) and 2.2% loss of weight at 240 °C (4), corresponding to loss of water molecules (Figure S2). The thermogravimetric analysis of 6 revealed a weight loss of 3.1% at ca. 250 °C, ascribed to the removal of three H2O molecules per chemical formula. All these complexes exhibited good thermal stability with no significant decomposition below 300 °C (Figure S2).


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Crystal Structure of 1. As shown in Figure 1, Zn1 is tetrahedrally coordinated by two O atoms from two 4-IBA ligands and two N atoms from two tpeb ligands. The average Zn–N and Zn–O bond lengths (2.038(5) Å vs 1.950(5) Å) are comparable to those found in {[Zn2(H2O)(1,4ndc)2(tpcb)]}n (2.046(5) Å vs 1.952(4) Å, tpcb = tetrakis(4-pyridyl)cyclobutane).57 The carboxylate group of 4-IBA coordintes to Zn1 in a monodentate mode. Each tpeb ligand follows Type I coordination mode (Scheme 1) where one pyridinyl binds to Zn1 while the other two remain intact.

Figure 1. Molecular structure of 1. The teal, red, blue and black spheres represent Zn, O, N and C atoms, respectively. All H atoms and solvent molecules have been omitted for clarity. Crystal Structure of 2. Compound 2 crystallizes in the monoclinic space group P21/n and the asymmetric unit contains one independent [(Cd(NO3)(tpeb)(4-IBA)] unit and half a water molecule. Each Cd(II) has a distorted pentagonal bipyramidal coordination geometry (Figure 2a), coordinated by two O atoms from one 4-IBA ligand, two O atoms from one nitrate anion and three N atoms from three different tpeb ligands which follows a Type III coordination mode (Scheme 1). The average Cd–N and Cd–O bond lengths (2.324(4) Å vs 2.471(3) Å) are comparable to those found in seven-coordinated complex [Cd(fdc)(bipy)1.5] (2.368(2) Å vs


12

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2.432(3) Å).58 Three [(Cd(NO3)(4-IBA)] fragments are bridged by three tpeb ligands to form a [Cd(NO3)(tpeb)(4-IBA)]3 ring. Such a ring is further fused with others by sharing tpeb ligands to yield a 2D waterfall-like layer (Figure 2b). The water solvent molecules are squeezed in-between the two layers.

(a)

(b)


13


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Figure 2. (a) View of the Cd(II) coordination environment of 2 with a labeling scheme. Symmetry codes: A: -0.5 - x, -0.5 + y, 0.5 - z; B: 0.5 - x, -0.5 + y, -0.5 - z. (b) View of the 2D network of 2. The turquoise, red, blue and black spheres represent Cd, O, N and C atoms, respectively. Crystal Structures of 3 and 4. Compounds 3 and 4 crystallize in the triclinic space group Pī and the asymmetric unit contains one independent [Cd2(NO3)2(tpeb)2(1,4-BDC)] (3) or one [Cd(tpeb)(2,5-FDC)] unit and one water solvent molecule (4). For 3, each Cd(II) adopts a distorted pentagonal bipyramidal coordination geometry (Figure 3a), coordinated by two O atoms from one 1,4-BDC ligand, two O atoms from one nitrate anion and three N atoms from three tpeb ligands (Type IV). Each Cd(II) in 4 holds a slightly different seven-coordination surrounding (Figure 3b), coordinated by four O atoms from two 2,5-FDC ligands and three N atoms from three tpeb ligands (Type IV, Scheme1). The average Cd–N and Cd–O bond lengths of 3 (2.492(4) Å vs 2.357(3) Å) and 4 (2.378(4) Å vs 2.426(3) Å) are analogous to those of 2. Each 1,4-BDC (3) or 2,5-FDC (4) bind to two Cd(II) atoms in a chelating/bridging mode. For 3 or 4, Cd(II) atoms are bridged by tpeb ligands to form one a 1D ladder-type [Cd(tpeb)]n chain (Figure S3a). Such a chain in 3 is further interconnected by 1,4-BDC forming a 2D wave-like network extending approximately along the ab plane (Figure 3c). However, such two chains in 4 are bridged by 2,5-FDC ligands to yield a rare 1D channel extending along the c axis. These channels are further interlinked by 2,5-FDC ligands to form a unique 2D double-layer structure extending along the ac plane (Figure 3d). These structural differences of 3 and 4 may be ascribed to the fact that each [Cd(tpeb)]n chain is staggered (3) or aligned (4) and that each 1,4-BDC linker in 3 is linear while each 2,5-FDC linker in 4 is angular.


14

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(a)

(b)

(c)


15


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(d) Figure 3. (a) and (b) View of the coordination environments of Cd in 3 and 4. Symmetry codes: A: 3 - x, 1 - y, 3 - z; B: 2 - x, -y, 2 - z; C: 3 - x, -1 - y, 3 - z (3); A: x, y, 1 + z; B: -1 + x, y, z (4). (c) View of the 2D wave-like network of 3 expanding nearly along the ab plane. (d) View of the 2D double-layer network of 4 expanding roughly along the ac plane. The atom color codes are the same as those in Figure 2. Crystal Structure of 5. Compound 5 crystallizes in the triclinic space group Pī and the asymmetric unit consists of independent [Cd(tpeb)(2,5-DBTPA)] units. Each Cd(II) is sevencoordinated by four O atoms from two 2,5-DBTPA ligands and three N atoms from three tpeb ligands (Type IV, Scheme 1) (Figure 4a). The average Cd–N and Cd–O bond lengths (2.366(4) Å vs 2.404(3) Å) are similar to those of 5. These Cd(II) atoms are bridged by 2,5-DBTPA to form one 1D [Cd(2,5-DBTPA)]n chain (Figure S3b). Each chain is interconnected to its


16

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equivalent ones by two pyridyls of each tpeb, forming the 2D network extending along the ac plane (Figure 4b). This 2D layer is linked by the third pyridyl of each tpeb to form one 3D net (Figure 4c). Such four 3D nets are interpenetrated to afford a 4-fold interpenetrating structure (Figure 4d).

(a)

(b)

(c)

(d)

Figure 4. (a) View of the coordination environment of the Cd center in 5. Symmetry codes: A: 1 - x, -1 + y, -1 + z; B: -1 - x, -1 - y, -2 - z; C: -2 - x, -2 - y, -1 – z ; D: -2 - x, -y, -1 – z. (b) View of


17


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the 2D network in 5. (c) View of the 3D network in 5 looking down the b axis. (d) Schematic view of the four-fold interpenetrating net of 5. The atom color codes are the same as those in Figure 2. Crystal Structure of 6. Compound 6 crystallizes in the monoclinic space group P21/c and the asymmetric unit contains one [Cd2(H2O)2(tpeb)2(1,2-CHDC)2] unit and one water solvent molecule. Each Cd(II) is seven-coordinated by five O atoms from two 1,2-CHDC ligands and one water and two N atoms from two tpeb ligands (Figure 5a). The mean Cd–N and Cd–O bond lengths (2.330(4) Å vs 2.418(3) Å) are close to those of 2. Two Cd(H2O) units are bridged by a pair of chelating 1,2-CHDC ligands to form a dimeric [Cd2(H2O)2(1,2-CHDC)2] fragment. Such a fragment is interlinked to its equivalent ones via binding two Cd(II) centres with two pairs of tpeb ligands to form a 2D wave-like network extending approximately along the ab plane (Figure 5b). In this case, each tpeb has Type II coordination mode (Scheme1) with one of the three pyridyl groups uncoordinated.

(a)


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(b) Figure 5. (a) View of the coordination environments of Cd centers in 6. Symmetry codes: A: 4 x, 2 - y, 1 - z; B: x, 2 - y, z. (b) View of the 2D wave-like network of 6. The atom color codes are the same as those in Figure 2. Crystal Structures of 7 and 8. Compounds 7 and 8 crystallize in the monoclinic space group P21/c and P21/n, respectively, and the asymmetric unit contains one independent [Zn(tpeb)(1,2CHDC)] (7) or [Zn(tpeb)(1,5-PDC)] unit (8). Since their structures are similar, only the structure of 8 is given in Figure 6. Each Zn(II) is tetrahedrally coordinated by two O atoms from two carboxylate ligands and two N atoms from two tpeb ligands (Figure 6a and Figure S3c). Each tpeb takes a Type II coordination mode (Scheme 1) with one of its three pyridyls remaining intact and the other two being linked to two Zn(II) atoms. The average Zn–N and Zn–O bond lengths for 7 (2.076(4) Å vs 1.994(4) Å) and 8 (2.041(3) Å vs 1.977(4) Å) are normal. Each Zn(II) is associated with a couple of 1,2-CHDC (or 1,5-PDC) ligands to yield a 1D [Zn(1,2CHDC)]n or [Zn(1,5-PDC)]n chain (Figures S3d and S3e). Each pair of tpeb ligands acting as


19


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fish-scales link the neighboring [Zn(1,2-CHDC)]n or [Zn(1,5-PDC)]n chains to generate 2D fishscale-like networks (Figures 6b and Figure S3d). In the structures of 7 and 8, the separation between neighboring Zn atoms and the corresponding N-Zn-N angle in 7 (7.732(4) Å vs 115.40(2)°) are greater than those of the corresponding ones in 8 (6.193(4) Å vs 104.29(3)°). Relative to 1,2-CHDC, 1,5-PDC has more flexibility, which is presumably responsible for such differences. In the structures of 2-7, the distances of the nearest vinyl bonds (for 2, parallel, 4.78 Å; for 3, parallel, 4.37 Å; for 4, parallel, 4.89 Å; for 5, parallel, 5.98 Å; for 6, parallel, 4.65 Å; for 7, crisscross, 4.30 Å/4.87 Å;) are longer than 4.2 Å, which exceeds Schmidt’s topochemical criteria for a photodimerization reaction. However, the two C=C bonds in the structure of 8 adopts a crisscross manner and the distances are 3.66 Å and 4.13 Å, which are within the range of Schmidt's rule. However, the cycloaddition reaction did not take place even under UV irradiation for more than 72h.

(a)

(b)


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Figure 6. (a) View of the coordination environment of Zn1 in 8. Symmetry code: A: 0.5 + x, 1.5 - y, -0.5 + z. (b) View of the 2D fish-scale-like network of 8. The atom color codes are the same as those in Figure 1. Photoluminescent Properties. Upon excitation at 350 nm (tpeb), 350 nm (1), 380 nm (2), 360 nm (3), 350 nm (4), 420 nm (5), 370 nm (6), 390 nm (7) and 350 nm (8) at room temperature, these compounds exhibited solid-state photoluminescence with emission maxima at 453 nm (tpeb), 489 nm (1, 2, 7), 412 nm (3), 432 nm (4), 503 nm (5), 486 nm (6), and 491 nm (8) (Figure S4). The emissions for 1, 2, 5, 6, 7 and 8 were red shifted relative to that for free ligand, which was assigned to ligand-to-ligand charge transfer (LLCT)59-61 between the carboxylate and tpeb that are constrained by their coordination to Zn2+/Cd2+ with shorter distances.62 The emission maxima of the free carboxylate acids used in 3 and 4 were 385 nm and 363 nm (Figure S4) while the acids used in other compounds did not show any photoluminescence. The slight blue-shifting for the emissions of 3 and 4 may be due to the proximity of these photoactive ligands. Optical Properties. The band gap energy (Eg) of the representative complex 6 was measured by the Kubelka−Munk method63-64 to be 2.23 eV based on its solid-state diffusion-reflection spectrum recorded at room temperature (Figure 7), much smaller than those observed for tpeb (2.52 eV) and 1,2-H2HDC (3.15 eV). Complex 6 had evident absorbance in the visible light region (Figure S5), which encouraged us to explore its potential for photocatalytic degradation of CR as a model dye under visible white light irradiation.


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Figure 7. Solid-state diffusion−reflection spectra of 6, tpeb and 1,2-H2CHDC at ambient temperature. Photocatalytic Activity. The photochemical catalytic decomposition of CR was monitored by a decrease in the characteristic absorption band at 496 nm (Figure S6). The photo-bleaching of CR was negligible in the absence of catalyst 6. However, in the presence of 6, 90% of CR was degraded upon visible light irradiation for 90 min. Some degradation was observed in the presence of tpeb alone (Figure 8). Likewise, 1,2-H2CHDC could not decompose CR in water (Figure S7). However, when 1 mg of catalyst 6 was used without changing other conditions, only 45% of CR was degraded at 90 min. The photocatalytic degradation of CR with 6 followed a zero-order kinetics (Figure 8) and was comparable or superior to those known photocatalysts in terms of reaction time and efficiency (Table 2). Photocatalytic degradation of CR using 6, required more time than Cu/Chi-CC, but the latter needed UV light and NaBH4 to maintain a reductive atmosphere. Complex 6 was superior to the other three visible light photocatalysts which need larger catalyst loading and longer reaction time (Table 2).


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Figure 8. Photodegradation of CR under visible light irradiation with 6 or tpeb or without 6. Table 2. Comparison of degradation time and efficiency for the photocatalytic degradation of CR for 6 and other known photocatalysts. Photocatalysts

Amount of cat.

Amount of CR

Condition

Time

Efficiency

Ref.

Cu/Chi-CC

3 × 2 cm2

0.1 mg

UV light/NaBH4

12 min

96%

47

CuS20BT

25 mg

7 mg

visible light/H2O2

20 min

95%

48

ZnO–Zn

2 × 2 cm2

0.28 mg

UV light

120 min

100%

49

BiGdWO6 NP

50 mg

1.4 mg

visible light

90 min

90%

50

Fe-doped SnS2

6 mg

17 mg

visible light

180 min

93%

51

6

12 mg

10 mg

visible light

90 min

90%

this work

Noted: Chi (chitosan), CC (cotton cloth), BT (Bi2WO6), NP (nanoparticle).

The recycling performance of a photocatalyst is one of the most important factors in its usability. In this work, 6 could be readily recovered from the catalytic system via centrifugation and washing with deionized water. Reuse of the catalyst was then investigated (Figure S8) and PXRD examinations of 6 were undertaken after each photodegradation run. The PXRD patterns


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of the photocatalyst (Figure 9) did not change significantly even after five rounds of recycling, demonstrating that it retained the original structure of 6 during the catalytic photodecomposition of CR in aqueous solution. Concomitant inductively coupled plasma (ICP) analysis of the degradation solution indicated only 3% leaching of cadmium ions in the final run (Table S2).

Figure 9. PXRD patterns for 6 and the samples after each of the five rounds of degradation experiments.

Scheme 3. Schematic illustration of the photocatalytic degradation of CR in water.


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Proposed Mechanism. The mechanism for the above photocatalytic degradation reaction is proposed as follows (Scheme 3).65 Upon irradiation by visible light, electrons (e−) in the valence band (VB) are excited to the conduction band (CB) while the same number of holes (h+) are left in the VB. The photogenerated electrons reduce O2 to ·O2− that reacts with water to give hydroxyl radicals (·OH). Simultaneously, interaction of holes (h+) with hydroxyl (OH−) may also produce hydroxyl radicals, which are known to be able to rapidly oxidize organic dyes.66-68 Examination of the degradation solution (Table S3) by ion chromatography confirmed the existence of NO3- and SO42- ions, which were consistent with those observed in the previous works.69-73 The narrow band gap energy of 6 is ideal for such an excellent photocatalytic degradation performance under visible light irradiation. Benzene-1,4-dicarboxylic acid (1,4H2BDC)

was

chosen

to

capture

the

proposed

radicals

to

yield

2-hydroxy-1,4-

benzenedicarboxylic acid.74-76 A 20 mL of solution with 5 × 10−4 mol L−1 of 1,4-H2BDC and 2 × 10−3 mol L−1 of NaOH with or without 6 (12 mg) was irradiated with visible light. Then the photoluminescent (PL) was used for detection of the corresponding 2-hydroxy-1,4benzenedicarboxylic acid at 425 nm. An increase in the emission at 425 nm was noticed in the presence of 6 (Figure S9a) but no increase in the emission at this wavelength was observed in the absence of 6 (Figure S9b). These results indicate that ·OH radicals were yielded by irradiating 6 in

dilute

aqueous

NaOH

and

captured

by

1,4-H2BDC

to

yield

2-hydroxy-1,4-

benzenedicarboxylic acid.

CONCLUSIONS

Eight Zn(II) and Cd(II) coordination complexes and polymers based on tpeb and various carboxylates were successfully constructed under solvothermal conditions. The number of


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coordination modes of the carboxylate and tpeb ligands, their substituent groups, the flexibility of the carboxylate linkers and the coordination numbers of the metal atoms all influenced the final structure outcomes (mononuclear complex, 2D or 3D coordination polymers). Among these compounds, the representative sample 6 exhibited good stability in water and the good performance for catalyzing the photodegradation of CR in water under visible light without the need for additives. This photocatalyst could be reused five times without losing catalytic efficiency. It is anticipated that more efficient visible light-driven CP-based catalysts for degradation of organic pollutants in water would be developed and screened out when multivinyl pyridyl ligands are assembled with various metal ions in the presence of suitable carboxylic acids. ASSOCIATED CONTENT Supporting Information. A detailed synthetic procedure for tpeb, PXRD patterns of 1-8, TGA curves for 1-8, selected bond distances for 1-8, emission spectra for 1-8, UV-DRS absorbance spectra for compound 6 in PDF format, plus crystallographic data in CIF format is available free of charge at http://pubs.acs.org. Accession Codes CCDC 1849516-1849523 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 CB21EZ, UK; fax: +44 1223 336033.


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AUTHOR INFORMATION Corresponding Author * e-mail: [email protected]. Tel: 86-512-65883569 * e-mail: [email protected]: 86-512-65880328; Tel: 86-512-65882865 Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We thank financial supports from the National Natural Science Foundation of China (Grant No. 21531006, 21771131 and 21773163), the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry (Grant No. 2018kf-05), the "Priority Academic Program Development" of Jiangsu Higher Education Institutions and the Project of Scientific and Technologic Infrastructure of Suzhou (SZS201708). We highly appreciate the useful comments of the editor and the reviewers. REFERENCES (1) Li, F. L.; Shao, Q.; Huang, X.; Lang, J. P. Nanoscale Trimetallic Metal–Organic Frameworks Enable Efficient Oxygen Evolution Electrocatalysis. Angew. Chem. Int. Ed. 2018, 57, 1888−1892. (2) Jagadeesh, R. V.; Murugesan, K.; Neumann, A. A. H.; Pohl, M. M.; Radnik, J.; Beller, M. MOF-Derived Cobalt Nanoparticles Catalyze a General Synthesis of Amines. Science 2017, 358, 326–332.


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For Table of Contents Use Only

Carboxylate-Assisted Assembly of Zinc and Cadmium Coordination Complexes of 1,3,5-Tri-4-pyridyl-1,2-ethenylbenzene: Structures and Visible Light-Induced Photocatalytic Degradation of Congo Red in Water Jian-Guo Zhang,†,‡ Wei-Jie Gong,† Yu-Song Guan,† Hong-Xi Li,*,† David James Young,§ and Jian-Ping Lang*,†,‡

Eight mixed-ligand coordination complexes based on the tris-pyridyl ligand tpeb were constructed. The coordination modes of carboxylate and tpeb ligands, the flexibility/rigidity of carboxylate linkers and the coordination numbers of center atoms were responsible for the structural varieties. Among them, 6 showed excellent catalytic performance in photodegradation of CR in water upon visible light irradiation.


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Carboxylate-Assisted Assembly of Zinc and Cadmium Coordination

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