N,N-Bis(diphenylphosphanylmethyl)-3

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Assembly of Silver(I)/N,N-Bis(diphenylphosphanylmethyl)-3aminopyridine/Halide or Pseudohalide Complexes for Efficient Photocatalytic Degradation of Organic Dyes in Water Chun-Yu Liu, Lin-Yan Xu, Zhi-Gang Ren, Hui-Fang Wang, and Jian-Ping Lang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00766 • Publication Date (Web): 24 Jul 2017 Downloaded from http://pubs.acs.org on July 24, 2017

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Crystal Growth & Design

Assembly of Silver(I)/N,N-Bis(diphenylphosphanylmethyl)3-aminopyridine/Halide or Pseudohalide Complexes for Efficient Photocatalytic Degradation of Organic Dyes in Water

Chun-Yu Liu,† Lin-Yan Xu,† Zhi-Gang Ren,*,† Hui-Fang Wang,*,† 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

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) __________________________ †

Soochow University

‡

Shanghai Institute of Organic Chemistry

ACS Paragon Plus Environment

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ABSTRACT:

Treatment

of

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N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine

(3-

bdppmapy) with AgX (X = Br, I, CN, SCN, dicyanamide (dca)) under different reaction conditions afforded seven mononuclear, dinuclear and polymeric coordination complexes including [Ag4I4(3-bdppmapy)2]n (1), [Ag2I2(3-bdppmapy)3]·CH3OH (2·CH3OH), [Ag2Br(3bdppmapy)3]Br·4CH3OH [Ag(3-bdppmapy)2]SCN

(3·4CH3OH), (5),

[Ag4(CN)4(3-bdppmapy)3]·2CH3OH

[Ag(3-bdppmapy)2](dca)

(6)

and

(4·2CH3OH), {[Ag4(dca)4(3-

bdppmapy)2]·4DMF}n (7). Compound 1 contains a unique two-dimensional (2D) network in which chair-like [Ag4I4] units are interconnected by µ3-3-bdppmapy bridges. Compounds 2 and 4 hold a similar centrosymmetric framework in which two [(3-bdppmapy)AgI] (2) or [(3bdppmapy)Ag2(CN)2] (4) units are linked by a µ-3-bdppmapy. Compound 3 has a bat-like cationic structure in which two Ag/3-bdppmapy units are joined by a pair of µ-Br and µ-3bdppmapy bridges. Compounds 5 and 6 have a similar cationic mononuclear structure in which the Ag(I) center is chelated by two 3-bdppmapy ligands. Compound 7 possesses a 2D layer structure in which each one-dimensional (1D) chain [Ag4(dca)4(3-bdppmapy)2]n is connected to its equivalent ones by µ3-dca bridges. Compound 1 as a representative example exhibited excellent catalytic activity towards the photodecomposition of a spectrum of eleven organic dyes in water under UV light irradiation and can be reused five times without noticeable decay of its catalytic efficiency.

INTRODUCTION

In our previous studies, we have been engaged in the design and synthesis of some P-N hybrid ligands due to their diversiform coordination modes arising from the combination of both N and P ends.1,2 A number of Ag(I) coordination polymers (CPs) of these P-N ligands with interesting


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structures have been isolated. For instance, the assembly of N,N-diphenylphosphanylmethyl-2aminopyridine (bdppmapy) with AgX (X = Cl, Br, I, SCN and CN) yielded several 1D CPs and a unique three-dimensional (3D) anionic [Ag10(CN)12]n2n- net.3 In these examples, the N atom from pyridyl group remains intact due to the large steric effect, which limits their abundance of the structure. Therefore, we slightly modified bdppmapy by replacing 2-pyridyl with 3-pyridyl to prepare N,N-bis-(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy), which may use the pyridyl N atom to further bind to the metal ions, yielding complicated coordination polymers. As reported previously,4 this ligand could react Ag(I) oxysalts to yield a family of polynuclear Ag(I)/3-bdppmapy/oxyanion complexes. Some of these compounds were not robust enough to survive in water, though they exhibited good catalytic performances in the photodegradation of Rhodamine B (RhB). Compared to Ag(I) oxysalts, silver halides or pseudohalides are known to form different [AgaXb]-based structural motifs when exposed to P and/or N donor ligands and polar solvents and exhibit better stability.5-10 Thus, the reactions between 3-bdppmapy and silver halide or pseudohalide are anticipated to form a set of [AgaXb]/ 3-bdppmapy coordination compounds with unique structure and better stability. On the other hand, many research groups in the world are involved in employing CPs as photocatalysts for the degradation of toxic organic pollutants including organic dyes11-21 and nitro aromatics22, 23 in water. In the case of organic dyes, literatures have been concerned about several model dyes such as Methyl Orange (MO), Methyl Blue (MB) and RhB.24, 25 Very few are engaged in using CPs-based catalysts for photo-degrading a big scope of organic dyes due to the instability of CPs in water and their relatively low photocatalytic efficiency. To this end, we would like to perform the reactions of 3-bdppmapy with AgX (X = Br, I, SCN, CN and dicyanamide (dca)) and screen out some Ag(I)/3-bdppmapy/X complexes with good stability in


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water and high photocatalytic efficiency. A family of mononuclear, dinuclear and polymeric coordination complexes comprising [Ag4I4(3-bdppmapy)2]n (1), [Ag2I2(3-bdppmapy)3]·CH3OH (2·CH3OH),

[Ag2Br(3-bdppmapy)3]Br·4CH3OH

(3·4CH3OH),

[Ag4(CN)4(3-

bdppmapy)3]·2CH3OH (4·2CH3OH), [Ag(3-bdppmapy)2]SCN (5), [Ag(3-bdppmapy)2](dca) (6) and {[Ag4(dca)4(3-bdppmapy)2]·4DMF}n (7). were isolated.

Under UV light irradiation,

compounds 1-5 exhibited good stability and desirable catalytic activity towards the photodegradation of RhB. Having the highest catalytic efficiency among them, 1 was used as a representative sample for evaluating its photocatalytic efficiency in destroying other 10 organic dyes including MO, Orange I (OI), Orange II (OII), Orange IV (OIV), Orange G (OG), Amino Black (AB), Amaranth Red (AR), Sunset Yellow (SY), Acid Chrome Blue K (ACBK) and Eriochrome Black T (EBT). It did a good job and showed its strong capacity in destroying a broad spectrum of organic dyes in water. Herein we report their syntheses, structures, and photocatalytic performances.

EXPERIMENTAL SECTION

General Procedure.

The ligand 3-bdppmapy was synthesized as reported before.4 All

solvents were pre-dried over activated molecular sieves and refluxed over suitable drying agents under N2. The analytical instruments, the method for the photocatalytic activity study and the density functional theory (DFT) calculations engaged in this work were the same as those used in our previous works.3,4 Synthesis of [Ag4I4(3-bdppmapy)2]n (1). A solution containing AgI (47 mg, 0.2 mmol) and 3bdppmapy (49 mg, 0.1 mmol) in CH3CN (5 mL) was stirred for 5 h at ambient temperature. After filtration, the white solid of 1 was isolated in 87% yield (84 mg based on Ag). Anal. Calcd


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for C31H28Ag2I2N2P2: C, 38.75; H, 2.92; N, 2.92%; found: C, 39.32; H, 2.78; N, 2.75%. IR (KBr disk): 3440 (s), 3049 (s), 2980 (w), 2920 (w), 1588 (m), 1571 (m), 1495 (m), 1434 (s), 1384 (s), 1243 (s), 1224 (w), 1128 (w), 1098 (w), 998 (w), 856 (s), 835 (w), 787 (w), 750 (s), 695 (s), 505 (w) cm-1. Synthesis of [Ag2I2(3-bdppmapy)3]·CH3OH (2·CH3OH). Compound 2·CH3OH was prepared as an off-white solid by a procedure similar to that of 1, from AgI (23.5 mg, 0.1 mmol) and 3bdppmapy (74.5mg, 0.15 mmol) in CH3OH (5 mL). Yield: 74 mg (74% based on Ag). Anal. Calcd for C94H88Ag2I2N6OP6: C, 57.17; H, 4.46; N, 4.26%; found: C, 56.52; H, 4.73; N, 4.05%. IR (KBr disk): 3441 (s), 3049 (w), 2171 (w), 1627 (m), 1579 (m), 1482 (m), 1433 (s), 1400 (s), 1385 (vs), 855 (w), 740 (s), 694 (s), 617 (s), 509 (w) cm-1. Synthesis of [Ag2Br(3-bdppmapy)3]Br·4CH3OH (3·4CH3OH). A mixture containing AgBr (18.8 mg, 0.1mmol) and 3-bdppmapy (74.5 mg, 0.15 mmol) in CH3OH (5 mL) was stirred for 30 min at ambient temperature to form a clear colorless solution. Slow diffusion of Et2O into the solution afforded colorless blocks of 3·4CH3OH after 3 days, which were collected by filtration, washed with Et2O and dried in vacuo. Yield: 22 mg (38% based on Ag). Anal. Calcd for C97H100Ag2BrN6O42P6: C, 58.94; H, 8.67; N, 7.28%; found: C, 59.72; H, 8.23; N, 7.45%. IR (KBr disk): 3431 (s), 3050 (w), 1578 (m), 1484 (m), 1432 (s), 1384 (w), 1278 (w), 1221 (w), 1127 (s), 1097 (w), 1026 (w), 854 (w), 789 (w), 743 (s), 693 (s), 505 (w) cm-1. Synthesis of [Ag4(CN)4(3-bdppmapy)3]·2CH3OH (4·2CH3OH). A suspension of AgCN (13 mg, 0.1 mmol) in CH3OH (2.5 mL) was stirred for 1 h. To this suspension was dropwise added a solution of 3-bdppmapy (36.75 mg, 0.075 mmol) in CH3CN. The mixture was further stirred for 4h to yield a clear colorless solution. Similar workup to that used in the isolation of 3·4CH3OH


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generated colorless blocks of 4·2CH3OH. Yield: 46.9 mg (91% based on Ag). Anal. Calcd for C99H92Ag4N10O2P6: C, 57.36; H, 4.44; N, 6.76%; found: C, 57.98; H, 4.37; N, 6.75%. IR (KBr disk): 3052 (w), 2126 (w), 1633 (w), 1580 (s), 1483 (s), 1434 (s), 1375 (w), 1310 (w), 1222 (w), 1123 (m), 1097 (m), 1025 (w), 852 (m), 739 (s), 695 (s), 507 (m) cm-1. Synthesis of [Ag(3-bdppmapy)2]SCN (5). A mixture of AgSCN (8.3 mg, 0.05 mmol) and 3bdppmapy (49 mg, 0.1 mmol) in CH3OH/H2O (2 mL, v/v = 1 : 2) was sealed in a glass tube and then heated at 70 °C for 24 h. After that, smoothly cooling the solution to room temperature (−5 °C·h−1) produced colorless blocks of 5, which were collected by filtration, washed with Et2O, and dried in air. Yield: 39 mg (68% based on Ag). Anal. Calcd for C63H56AgN5P4S: C, 65.91; H, 4.88; N, 6.10%; found: C, 65.04; H, 5.05; N, 6.54%. IR (KBr disk): 3431 (s), 3051 (w), 2075 (s), 1627 (s), 1580 (m), 1484 (m), 1434 (s), 1384 (s), 1220 (s), 1185 (w), 1126 (w), 1098 (w), 998 (w), 851 (w), 741 (s), 695 (s), 507 (w) cm-1. Synthesis of [Ag(3-bdppmapy)2](dca) (6). Colorless crystals of 6 were prepared by a route analogous to that used for the isolation of 5, starting from Agdca (8.5 mg, 0.05 mmol) and 3bdppmapy (49 mg, 0.1 mmol) in 2 mL of CH3CN/H2O (v/v = 1 : 2) at 85 °C for 24 h. Yield: 31 mg (54% based on Ag). Anal. Calcd for C64H56AgN7P4: C, 66.50; H, 4.85; N, 8.48%; found: C, 65.36; H, 4.93; N, 8.65%. IR (KBr disk): 3440 (s), 2241 (m), 2143 (vs), 1584 (m), 1495 (m), 1435 (s), 1384 (s), 1312 (s), 1130 (w), 1096 (w), 1002 (w), 912 (w), 854 (w), 784 (w), 743 (s), 694 (s), 503 (w) cm-1. Synthesis of {[Ag4(dca)4(3-bdppmapy)2]·4DMF}n (7). A suspension containing Agdca (34 mg, 0.2 mmol) and 3-bdppmapy (49 mg, 0.1 mmol) in DMF (5 mL) was stirred for 30 min at ambient temperature. Analogous workup to that used in the isolation of 3·4CH3OH afforded


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colorless block crystals of 7.

Yield: 76 mg (77% based on Ag).

Anal. Calcd for

C41H42Ag2N10O2P2: C, 49.97; H, 4.27; N, 14.20%; found: C, 50.03; H, 4.33; N, 13.95%. IR (KBr disk): 3441 (s), 3053 (m), 2930 (w), 2285 (s), 2214 (s), 2143 (vs), 1584 (m), 1569 (m), 1499 (m), 1435 (s), 1383 (s), 1289 (s), 1128 (w), 1098 (w), 998 (w), 858 (w), 787 (w), 745 (s), 695 (s), 509 (w) cm-1. X-ray Crystallography. Single crystals suitable for X-ray diffraction were gained by slow diffusion of diethyl ether into the filtrate in the synthesis of 1 and 2·CH3OH, or directly from the above preparations (3·4CH3OH, 4·2CH3OH, and 5-7). The measurements of 1, 2·CH3OH, 3·4CH3OH, 4·2CH3OH and 5-7 were performed on an Agilent Xcalibur (1, 4·2CH3OH, 6 and 7), a Bruker APEX-II (2·CH3OH and 3·4CH3OH), or a Rigaku Mercury (5) CCD X-ray diffractometer employing graphite monochromated Mo Kα (λ = 0.71073 Å) radiation at 223 K (1, 2·CH3OH, 3·4CH3OH, 4·2CH3OH, 6) or 298 K (5 and 7).

The programs including

CrysAlisPro (Agilent Technologies, Ver. 1.171.36.28, for 1, 4·2CH3OH, 6-7), Bruker SAINT (2·CH3OH and 3·4CH3OH) and CrystalClear (Rigaku and MSc, Ver. 1.3, for 5) were employed for the refinement of cell parameters and the reduction of collected data, while absorption corrections (multi-scan) were applied. The reflection data were corrected for Lorentz and polarization effects. The crystal structures of 1, 2·CH3OH, 3·4CH3OH, 4·2CH3OH, and 5-7 were solved by direct methods and refined on F2 by full-matrix least-squares methods with SHELXS-2013 and SHELXS-2016 programs.26

For 2·CH3OH, the phenyl group containing C44-C48 adopts a

rotational disorder and the ratio of the disordered components was refined to be 0.58/0.42. I1 was also disordered over two sites with an occupancy ratio of 0.58/0.42. The methanol solvate also was disordered over two sites with occupancy ratio refined to 0.6/0.4. For 3·4CH3OH, the


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methanol solvate (C50 and O2) was disordered over two sites with an occupancy factor of 0.6/0.4. For 4·2CH3OH, Ag2 was disordered over two sites with occupancy factors 0.53/0.47. The methanol solvate (C51 and O1) was disordered over four sites with an occupancy ratio of 0.35/0.20/0.30/0.15. For 2·CH3OH, 3·4CH3OH, and 4·2CH3OH, C34 and N3 in the metapositions of 3-pyridyl cannot be clearly assigned. These atoms were thus considered as a positional disorder and the C34/N3 ratio was fixed to be 0.5/0.5. The EXYZ, EADP instructions were subsequently applied to the C/N pair at the same atom site. For 5, the SCN- anion was split over two positions with an occupancy factor of 0.5/0.5. For 6, the phenyl group (C51-C56) was refined as a rigid hexagon with AFIX 66. All non-H atoms were refined anisotropically except for those of the disordered methanol (in 2·CH3OH, 3·4CH3OH, and 4·2CH3OH) and the DMF molecules (in 7). The H atoms of the disordered methanol molecules in 2·CH3OH, 3·4CH3OH, and 4·2CH3OH were not found. All other H atoms were put in the geometrically idealized positions and constrained to ride on their parent atoms. The important crystallographic data for 1, 2·CH3OH, 3·4CH3OH, 4·2CH3OH and 5-7 was summarized in Table 1. Their selected bond lengths and angles were listed in Table S1.


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Table 1. Crystal Data and Structure Refinement Parameters for 1, 2·CH3OH, 3·4CH3OH, 4·2CH3OH and 5-7 1

2·CH3OH

3·4CH3OH

4·2CH3OH

5

6

7

empirical formula

C31H28Ag2I2N2P2

C94H88N6P6OAg2I2

C97H100Ag2Br2N6O4P6

C99H92Ag4N10O2P6

C63H56N5P4AgS

C64H56AgN7P4

C41H42Ag2N10O2P2

formula weight

960.03

1973.03

1975.20

2071.12

1146.94

1154.91

984.52

crystal system

monoclinic

monoclinic

orthorhombic

monoclinic

monoclinic

monoclinic

triclinic

space group

P21/c

C2/c

Pccn

P2/n

Cc

Cc

Pī

a (Å)

13.1628(8)

34.077(4)

15.5984(12)

20.591(4)

11.821(2)

11.7074(9)

10.3365(5)

b (Å)

15.0320(11)

11.3015(15)

22.7501(19)

10.963(2)

23.194(5)

22.945(3)

13.6808(8)

c (Å)

19.666(2)

27.358(4)

25.291(2)

22.713(5)

21.476(4)

21.2089(18)

16.8210(8)

α (deg) β (deg)

73.863(5) 126.242(6)

105.57(3)

120.399(3)

94.78(3)

93.452(7)

γ (deg)

85.720(4) 78.059(4)

V(Å3)

3138.3(5)

9088(2)

8974.8(12)

4939.3(18)

5868(2)

5686.9(9)

2235.1(2)

ρcalc(g cm-3)

2.032

1.442

1.462

1.393

1.298

1.349

1.463

Z

4

4

4

2

4

4

2

-0.009(17)

-0.09(3)

Flack parameter µ (mm–1)

3.341

1.264

1.489

0.930

0.531

0.514

0.993

F(000)

1832

3968

4040

2100

2368

2384

996

R1a

0.0579

0.0749

0.0438

0.0542

0.0516

0.0589

0.0637

wR2b

0.1649

0.2393

0.1235

0.1656

0.1364

0.1016

0.1948

GOFc

1.092

1.078

1.073

1.062

0.975

0.918

1.032

a

R1= Σ||Fo|-|Fc||/Σ|Fo|. b wR2= {Σw(Fo2-Fc2)2/Σw(Fo2)2}1/2. c GOF = {Σw((Fo2-Fc2)2)/(n-p)}1/2, where n =number of reflections and p = total number of

parameters refined.


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RESULTS AND DISCUSSION

Synthetic and Spectral Aspects. Reactions of AgI with 0.5 equiv. of 3-bdppmapy in CH3CN at ambient temperature produced a 2D coordination polymer 1 in 87% yield (Scheme 1). When the molar ratio of AgI and 3-bdppmapy was changed from 2 : 1 to 1 : 1.5, their reactions in CH3OH afforded a dinuclear complex 2·CH3OH in 74% yield. Similar treatment of AgBr with 3-bdppmapy followed by diffusion of Et2O into the solution formed another dinuclear product 3·4CH3OH in 38% yield. In the case of AgCN, its reaction with 0.5 equiv of 3-bdppmapy in CH3OH/CH3CN generated a very small amount of one tetranuclear complex 4·2CH3OH. When their molar ratio was adjusted to be 4 : 3, the yield of 4·2CH3OH was raised up to 91%. When AgCN was replaced by AgSCN, its reaction with 3-bdppmapy failed to give any characterizable products even if their molar ratios and/or solvent systems were changed.

Therefore we

attempted solvothermal reactions of AgSCN with 3-bdppmapy in various solvent systems. Finally, the 1 : 2 AgSCN/3-bdppmapy reaction in CH3CN/H2O at 85 °C produced one mononuclear cationic complex 5 in 68% yield. Similar treatment of Agdca with 3-bdppmapy produced compound 6 (54% yield), which has the same cationic structure as that of 5. Intriguingly, when this reaction was carried out in CH3CN/H2O at ambient temperature, no products could be isolated. However, when the molar ratio of Agdca and 3-bdppmapy was adopted to be 2 : 1, their reactions proceeded well in DMF to give a 2D coordination polymer 7 in 77% yield.

Scheme 1. Reactions of 3-bdppmapy with Ag(I) halides and pseudo-halides


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The assembly of 1-7 is probably completed by cracking the bulky AgX networks with 3bdppmapy and definitely affected by the X- anions. However, the ligand loading also exerts pertinent impacts on their assembly and their final structures. The reactions with a lower 3bdppmapy loading can produce higher dimensional complexes (1 and 7) while those with a higher 3-bdppmapy loading affords lower nuclearity complexes (2 and 3). As discussed later in this paper, the structures of 1 and 7 contain the [Ag4I4] and [Ag2(dca)4] cluster units, which are formed likely due to the incomplete breaking of the AgX networks by low ligand loading. These cluster units offer more Ag(I) sites to coordinate with the pyridyl groups of 3-bdppmapy, yielding the polymeric structures of 1 and 7. However, such units may be further degraded into single silver ions when excess (1.5 equiv) 3-bdppmapy is employed to react with AgI and AgBr, thereby forming dinuclear complexes 2 and 3, respectively. In both cases, no more Ag sites are available for their coordination with the pyridyls of 3-bdppmapy. For AgSCN and Ag(dca), more ligand loading (2 equiv) along with higher reaction temperature (85 °C) led to the complete


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cracking of Ag-X bonds, yielding 5 and 6 composed of the mononuclear [Ag(3-bdppmapy)2]+ cation and the eliminated X- as a counterion. Intriguingly, although the AgCN/3-bdppmapy molar ratio was 4 : 3, it did not form any expected cyanide-bridged coordination polymers but an unusual tetranuclear complex 4. In its structure, it holds a [Ag2(CN)2] cluster species which has one intact cyanide, while the pyridyl groups of 3-bdppmapy remain uncoordinated. Compound 4 thus carries the structural characteristics of higher dimensional complexes (cluster units) and the lower nuclearity complexes (uncoordinated pyridyl groups). Compounds 1-7 are air- and moisture-stable. They can not dissolve in water and common organic solvents such as CH2Cl2, toluene, hexane, CH3OH, and Et2O. The PXRD patterns of 1-7 were consistent with those simulated from their single crystal X-ray data (Figure S1). In the IR spectra of 1-7, bands at 3050, 2990, 1580, and 1490 cm-1 are attributed to the stretching vibrations of the phenyl groups of 3-bdppmapy. The characteristic bands at 2126 cm-1 for CN– (in 4·2CH3OH), 2075 cm-1 for SCN– (in 5) and 2285 cm-1 for dca– (in 6 and 7) were observed. According to the thermogravimetric analysis curves of 1-7 (Figure S2), the first weight loss of 1.6% (2·CH3OH), 3.8% (3·4CH3OH) and 1.0% (4·2CH3OH) in the range of 30-200 °C was ascribed to the removal of all lattice solvent molecules in these compounds.

The overall

frameworks of 1-6 were all stable until 200°C after which they quickly got collapsed. For 7, the first weight loss of 9.3% amounted to 2.5 DMF molecules per formula in the range of 30-200 °C and the remaining 1.5 DMF molecules were also lost at about 350 °C followed immediately by the collapse of its polymeric framework. The structures of 1-7 were further determined by single crystal X-ray diffraction. Crystal Structure of 1. Compound 1 crystallizes in the monoclinic space group P21/c, and its asymmetric unit contains a [Ag4I4] unit and two 3-bdppmapy molecules.


There exists a

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crystallographic inversion center sitting at the center of Ag1···Ag1A contact. Four Ag(I) ions are combined by four iodides to yield a chair-like [Ag4I4] unit in which two iodides take a doubly-bridging mode while the other two a triply-bridging mode (Figure 1a). Ag1 (or Ag1A) is tetrahedrally coordinated by one P, one µ-I, one µ3-I and one N atom, while Ag2 (or Ag2A) is tetrahedrally coordinated by one P, one µ-I, and two µ3-I atoms.

The Ag1···Ag2 and

Ag2···Ag2A separations are 3.311 Å and 4.095 Å, which are too long to include any metal-metal interactions.28, 29 Each 3-bdppmapy works as a µ3-bridging mode, binding at two Ag centers of one [Ag4I4] unit via one PPh2 group and one pyridyl group and one Ag center of another [Ag4I4] unit via its second PPh2 group. Each [Ag4I4] unit is connected to its four equivalent ones via µ33-bdppmapy to form a 2D (4, 4) network extending approximately along the bc plane (Figure 1b).

(a)

(b)

Figure 1. (a) View of the coordination environments of Ag1 and Ag2 centers in 1. (b) View of the 2D network of 1 extending along the bc plane. All H atoms are omitted for clarity. Atom color codes: Ag, turquoise; P, pink; N, blue; C, black; I, purple.


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Crystal Structures of 2·CH3OH and 4·2CH3OH. Compound 2·CH3OH crystallizes in the monoclinic space group C2/c, while 4·2CH3OH crystallizes in the monoclinic space group P2/n. Each asymmetric unit contains half a [Ag2X2(bdppmapy)3] (2·CH3OH: X = I; 4·2CH3OH: X = Ag(CN)2 molecule. These complexes exhibit similar structures in which one two-fold axis is going through C32, C35 and N4 atoms (2) or C32, C35 and N3 atoms (4). Three 3-bdppmapy ligands exhibit two different coordination styles. One is that it chelates at Ag1 via the two P (P1 and P2) ends (η2-3-bdppmapy), whereas the other is that it bridges two Ag atoms via P3 (µ-3bdppmapy) (Figure 2). In both cases, each pyridyl group in 3-bdppmapy remains uncoordinated. Ag1 (or Ag1A) takes a tetrahedral geometry, coordinated by three P atoms from two different 3bdppmapy ligands and one I atom in 2 or one N atom of a cyanide in 4. The structure could be considered as being built of two [(3-bdppmapy)AgI] (2) or [(3-bdppmapy)Ag2(CN)2] (4) units linked by a µ-3-bdppmapy bridge. In 4, Ag2 is linearly coordinated by two C atoms from two cyanides. The structure of 4 along with the Ag2(CN)2 unit is similar to those observed in [(bdppmapy)3Ag4(CN)4 ]·CH2Cl2.3

(a)

(b)

Figure 2. (a) View of the molecular structure of 2. (b) View of the molecular structure of 4. Atom color codes are equal to those in Figure 1.


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Crystal Structure of 3·4CH3OH. Compound 3·4CH3OH crystallizes in the orthorhombic space group Pccn and its asymmetric unit contains a [Ag2Br(3-bdppmapy)3]+ cation, a Br– ion and four CH3OH solvent molecules. Ag1 (or Ag1A) holds a tetrahedral geometry, coordinated by three P atoms from two different 3-bdppmapy ligands and one Br atom (Figure 3a). The cationic structure of 3, having a two-fold axis going through Br1, C32, C35 and N4 atoms, may be viewed as a bat-like structure which has two [(3-bdppmapy)Ag] fragments (wings) bridged by a µ-3-bdppmapy ligand (head) and a Br atom (tail). The three 3-bdppmapy ligands work in two different coordination modes: chelating versus bridging. The pyridyl groups of all these 3bdppmapy ligands keep uncoordinated.

(a)

(b)

Figure 3. (a) View of the cationic structure of 3. (b) View of the cationic structure of 5. Atom color codes are the same as those in Figure 1. Crystal Structures of 5 and 6. Compounds 5 and 6 crystallizes in the monoclinic space group Cc and their asymmetric unit contains a [Ag(3-bdppmapy)2]+ cation and a N(CN)2– (5) or SCN– (6) anion. Because their complex cations are structurally similar, only the view of 5 is


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presented in Figure 3b. In 5 and 6, the central Ag1 is chelated by two 3-bdppmapy ligands to form a tetrahedral coordination geometry. Each 3-bdppmapy keeps its pyridyl intact. Crystal Structure of 7. Compound 7 crystallizes in the triclinic space group Pī and its asymmetric unit contains a [Ag4(dca)4(3-bdppmapy)2] molecule and four DMF solvent molecules. Four Ag(I) centers show two different coordination geometries (Figure 4a). Ag1 exhibits a tetrahedral geometry, coordinated by N3A, N6, and N6A from three different µ3-dca groups and P1 from one µ3-3-bdppmapy, which acts as a bridge to connect Ag1 and Ag2. Ag2 is tetrahedrally coordinated by N5 and N8 from two different µ3-dca groups and N1 and P2 from two different µ3-3-bdppmapy ligands. Each 3-bdppmapy works as a µ3-bridging ligand using one N of the pyridyl group and two P atoms from two PPh2 groups. One [Ag2(dca)4] unit is connected with two Ag2 atoms from two different directions by µ3-3-bdppmapy bridges to yield a 1D chain. Then such 1D chains are further interconnected by µ3-dca bridges to generate a unique 2D network extending the ab plane. (Figure 4b). The DMF solvent molecules are squeezed in-between the 2D layers.

(a)

(b)


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Figure 4. (a) View of the coordination environments of Ag1 and Ag2 centers in 7. (b) View of the 2D network of 7 extending the ab plane. Atom color codes are the same as those in Figure 1. Optical Properties. The band gap energies (Eg) of 1-7 were measured by the Kubelka-Munk method30,31 based on their solid-state diffusion-reflection spectra recorded at ambient temperature (Figure 6). These energies were estimated to be in the range of 3.275~3.405 eV, close to that of TiO2 (Degussa P-25, 3.341 eV), indicating a semiconducting nature of these complexes.31, 32 Complexes 1-7 exhibited strong absorptions in the UV light region (Figure S3), implying that they may be sensitive to UV light and have potential for photocatalysis. Thus their photocatalytic activities were assessed by degrading RhB as a model dye under Hg lamp irradiation (400 W, 365 nm, 40 mW·cm-2).

Figure 5. Solid-state diffusion-reflection spectra of 1-7 and TiO2 obtained from their diffuse reflectance data at room temperature. Photocatalytic Properties. The stabilities of 1-7 in water under UV light irradiation were essential to photocatalysis. Compounds 6 and 7 are quite sensitive to sunlight, which are easily decomposed to form silver mirror when exposed to sunlight, which excludes them as


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photocatalysts. The stabilities of 1-5 in water phase catalysis were estimated by irradiating the suspensions of each catalyst (10 mg) in 15 mL of water for 12 h with magnetic stirring. The degree of Ag+ leaching was measured by the ICP technique, which amounted to 0.20 mol% for 1, 0.13 mol% for 2, 0.13 mol% for 3, 0.25 mol% for 4 or 0.29 mol% for 5, suggesting that 1-5 maintained a high stability during their photocatalysis processes.

Figure 6. The catalytic activity of 1 (red), 2 (lake blue), 3 (yellow), 4 (green) and 5 (pink) in the photodegradation of RhB in water under UV light irradiation. The catalytic performances of 1-5 towards the photodegradation of RhB were examined by exposure the suspension containing a well-ground powder of each of them and a RhB aqueous solution, followed by measuring the residual percentage of RhB (c/c0, c0, and c are the initial and the remaining concentrations of RhB) through monitoring the absorption of RhB at 553 nm on a UV spectrophotometer. As displayed in Figure 6, RhB was almost completely degraded in 75 (1), 120 (2) and 210 (3-5) min. Considering that their Eg values have not obvious differences, we have thus performed density functional theory (DFT) calculations to acquire the HOMO–LUMO


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(H–L) gaps of compounds 1-5, which may help us to explain their different photocatalytic activity.4 The HOMO, LUMO, and HOMO–LUMO (H–L) gap energies were calculated with the Gaussian 09 program33 by using the B3LYP functional (Figure S4).34-36 As listed in Table 2, the H–L gaps of 1-5 were gradually increased from 2.66 eV (1) to 4.31 eV (5), which was in line with their observed photocatalytic activities. The lower H–L gap brought about easier electron excitations upon UV irradiation and thus caused better electron-hole separation, which was the essential step of the ·OH radical intermediate mechanism for the oxidative degradation of dyes. The frontier molecular orbitals (Figure S4) showed that the H–L transits of 1 and 2 were between the pyridyl group of 3-bdppmapy and the [Ag4I4] cluster (for 1) or between the AgI unit and the phenyl group of 3-bdppmapy (for 2), respectively, while those of 3-5 were between the pyridyl and phenyl groups of 3-bdppmapy. The lower H-L gap of 1 was related to the higher nuclearity cluster core [Ag4I4], and thus could more greatly enhance its catalytic performance in the photodecomposition of dyes.4 Compared to the known CPs such as {[Ag4(Ox)4}n (Ox-= NO3-, Bz- (benzoate), Sal- (salicylate)),4 the [Ag4I4] cluster unit in 1 is smaller and tighter than the [Ag4(Ox)4] unit, which is supposed to generate the better stability. Thus the catalytic activity of 1 is greatly improved in comparison to that of {[Ag4(Sal)4}n (4 h to degrade RhB in water). Table 2. HOMO, LUMO, and HOMO–LUMO (H–L) Gap Energies Calculated with the B3LYP DFT Method

Compound 1 2 3 4 5

HOMO (H) energy (eV) -4.94 -4.86 -6.96 -5.58 -7.43

LUMO (L) energy (eV) -2.28 -0.87 -2.82 -1.40 -3.12


H–L energy gap (eV) 2.66 3.99 4.14 4.18 4.31

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Page 20 of 30

Controlled experiments on the photodegradation of RhB were also performed (Figure S5). Under dark conditions, the concentrations of RhB were almost changed in the presence of 1. UV light irradiation in the absence of 1 also did not result in the obvious photocatalytic decomposition of RhB.4

In the presence of photocatalysts and UV irradiation, RhB was

decomposed up to 99.6% within 75 min. This demonstrated that both UV light and photocatalyst are indispensable in the decomposition of RhB.

The catalytic performance of 1 was also

compared with that of TiO2 (BET surface area = 47.5 m2/g) under the same experimental conditions. In the case of TiO2, only 69% of RhB was decomposed within 75 min, suggesting that the catalytic activity of 1 was better than that of TiO2. Considering that compound 1 is treated by hand-grinding, its BET surface area (3.27 m2/g) is much smaller than that of TiO2, which implies that the catalytic performance of 1 could be greatly enhanced if 1 was engineered into nano-particles. For the photocatalytic degradation reactions, the recycled performance of the catalyst is very important for determining its catalytic efficiency. Thus we evaluated the above photocatalytic reaction by recycling 1 five times under the UV light irradiation. After each photocatalytic cycle, compound 1 was separated by centrifugation for next catalytic cycle. As can be seen from Figure 7, the recycled sample exhibited similar photocatalytic performance to that of the first sample of 1. The PXRD patterns of the recycled samples of catalysts were also monitored during the course of photocatalytic reactions, which still matched well with that of 1 after 1 to 5 cycles (Figure S6). The results illustrated that the structure of 1 was retained during the photocatalysis process and no new solid phase, e.g. composite 1@RhB, could be generated during the degradation reaction.


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Figure 7. The repeated catalytic performance of 1 for the photodegradation of RhB in water under UV light irradiation.

Figure 8. UV-Vis spectra of the mixtures containing 1 and each of ten organic dyes in water under UV light irradiation.


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Based on the results described above, we decided to select 1 as a representative photocatalyst for examining its capacity in the degradation of more kinds of organic dyes in water. Through monitoring the absorptions at 465 nm (MO); 476 nm (OI); 485 nm (OII); 442 nm (OIV); 476 nm (OG); 620 nm (AB); 523 nm (AR); 481 nm (SY); 526 nm (ACBK) and 525 nm (EBT), these dyes were found to be degraded within 150~360 min (Figure 8), implying that 1 possesses a big capacity for dye degradation under UV light irradiation (Figure S7). Proposed Mechanism. As the Eg of 1 (3.28 eV) is in the range of semiconductors, we assumed that the photodegradation mechanism in this work was the ·OH radical-mediated route (Figure S8), which was previously reported in the photoreactions catalyzed by semiconductive materials.37-40 The UV irradiation firstly excited the electrons (e−) from 1 and simultaneously generated holes (h+). The subsequent interactions of e− with O2 and h+ with OH− gave rise to ·OH radicals. These high-active ·OH radical oxidized the dyes via an advanced oxidation process (AOP), producing CO2, H2O and other species. This generation of ·OH radical was verified by introducing excess tert-butyl alcohol (TBA, 0.2 mL) as the quenching agent for the ·OH radical

38, 39, 41

into the reaction system containing 1 and RhB. In this case, the

concentration of RhB was reduced by only 9% after 2 h irradiation (Figure 8a), implying that the photodegradation was hindered by TBA, which suggests a ·OH radical-mediated mechanism. To prove the formation of ·OH radicals in the above system, terephthalic acid was used to capture the resulting ·OH radicals to yield 2-hydroxyterephthalic acid.42-45 A solution containing terephthalic acid (5 × 10–4 mol·L–1, 2 mL) and NaOH (2 × 10–3 mol·L–1, 10 mL) in the absence or presence of 1 (10 mg) was irradiated with UV light and then sampled to measure the photoluminescent (PL) responses of the resulting 2-hydroxyterephthalic acid at 425 nm. With prolonging UV irradiation time, the PL intensity of 2-hydroxyterephthalic acid was identically


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increased in the presence of 1 (Figure S8c) but was not changed in the absence of 1 (Figure S8d). These results suggest that the ·OH radicals were generated by irradiating 1 in water, and were captured by terephthalic acid to yield 2-hydroxyterephthalic acid. We also used our previous method22 to collect the final products from the photodegradation to verify the mechanism. During the reaction of 1 with RhB under the O2 atmosphere, the CO2 generated after irradiation was absorbed by Ba(OH)2 to produce BaCO3, which could be used for calculate the yield of CO2. The yield of CO2 (based on RhB) is 92%, indicating that RhB was completely degraded.

CONCLUSIONS

In summary, we have synthesized and characterized a set of mononuclear, dinuclear and polymeric Ag(I)/3-bdppmapy/halide or pseudohalide coordination complexes 1-7.

Their

formation may be due to the different anions, the 3-bdppmapy loading, temperatures and solvent systems.

Compound 1 contains chair-like [Ag4I4] units which are interconnected to its

equivalent ones via µ3-3-bdppmapy ligands to yield a 2D (4,4) layer structure. Compound 2 or 4 has

a

centrosymmetric

structure

in

which

two

[(3-bdppmapy)AgI]

(2)

or

[(3-

bdppmapy)Ag2(CN)2] (4) units are combined by one µ-3-bdppmapy. Compound 3 contains two Ag/3-bdppmapy units that are held together by one µ-Br and one µ-3-bdppmapy bridge to yield a bat-like cationic structure. Compounds 5 and 6 hold a simple cationic mononuclear structure. Compound 7 consists of 1D [Ag4(dca)4(3-bdppmapy)2]n chains that are interlinked by µ3-dca bridges to generate a 2D network. Among these complexes, compound 1 exhibited its good stability in water and the best performance in catalyzing the photodegradation of RhB in water and can be reused for 5 cycles without obvious activity decay. Compound 1 as a representative


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catalyst also demonstrated excellent catalytic performances in the photodegradation of a spectrum of more than ten organic dyes. These results provide us a good insight into the relationship between their structure and catalyst activity, the design and assembly of other Ag/P/N complexes with higher stability and better photocatalytic efficiency in water. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxxx. The PXRD patterns, UV−vis absorption spectra and TGA curves of 1-7, and their selected bond distances (PDF). Accession Codes CCDC 1550724, 1550725, 1550726, 1550727, 1550728, 1550729 and 1550730 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge viawww.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 Authors * (Z.-G. Ren) E-mail: [email protected]. Tel: 86-512-65880328 * (H.-F. Wang) E-mail: [email protected]. Tel: 86-512-65883615


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* (J.-P. Lang) E-mail: [email protected]. Fax: 86-512-65880328; Tel: 86-512-65882865 ORCID Jian-Ping Lang: 0000-0003-2942-7385 Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors thank the research funds from the National Natural Science Foundation of China (21671134, 21373142, 21371126 and 21531006) and the State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry (2015kf-07), and the State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials. J. P. Lang is also thankful for the financial supports from the Priority Academic Program Development of Jiangsu Higher Education Institutions and the “SooChow Scholar” Program of Soochow University. We are grateful to the useful comments of the editor and the reviewers. REFERENCES (1) Li, N. Y.; Ren, Z. G.; Liu, D.; Yuan, R. X.; Wei, L. P.; Zhang, L.; Li, H. X.; Lang, J. P. Dalton trans. 2010, 39, 4213-4222. (2) Sun, S.; Ren, Z. G.; Yang, J. H.; He, R. T.; Wang, F.; Wu, X. Y.; Gong, W. J.; Li, H. X.; Lang, J. P. Dalton trans. 2012, 41, 8447-8454. (3) Yang, J. H.; Wu, X. Y.; He, R. T.; Ren, Z. G.; Li, H. X.; Wang, H. F.; Lang, J. P. Cryst. Growth Des. 2013, 13, 2124-2134. (4) Wang, J. F.; Liu, S. Y.; Liu, C. Y.; Ren, Z. G.; Lang, J. P. Dalton trans. 2016, 45, 9294-9306.


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For Table of Contents Use Only

Assembly

of

Silver(I)/N,N-Bis(diphenylphosphanylmethyl)-3-aminopyridine/Halide

or

Pseudohalide Complexes for Efficient Photocatalytic Degradation of Organic Dyes in Water Chun-Yu Liu,† Lin-Yan Xu,† Zhi-Gang Ren,*,† Hui-Fang Wang,*,† Jian-Ping Lang*,†,‡

Reactions of 3-bdppmapy with AgX (X = Br, I, CN, SCN, dicyanamide) under different reaction conditions gave rise to seven Ag(I)/3-bdppmapy/X coordination compounds with different structures. The representative two-dimensional coordination polymer [Ag4I4(3-bdppmapy)2]n exhibited good stability and excellent catalytic activity towards the photodegradation of a spectrum of eleven organic dyes in water under UV light irradiation.


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N,N-Bis(diphenylphosphanylmethyl)-3

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