Two Types of 2D Layered Iodoargentates Based on Trimeric [Ag3I7

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Two Types of 2D Layered Iodoargentates Based on Trimeric [Ag3I7] Secondary Building Units and Hexameric [Ag6I12] Ternary Building Units: Syntheses, Crystal Structures, and Efficient Visible Light Responding Photocatalytic Properties Xiao-Wu Lei,† Cheng-Yang Yue,*,†,‡,§ Jian-Qiang Zhao,† Yong-Fang Han,† Jiang-Tao Yang,† Rong-Rong Meng,† Chuan-Sheng Gao,† Hao Ding,† Chun-Yan Wang,† Wan-Dong Chen,† and Mao-Chun Hong*,‡ †

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry and Chemical Engineering, Jining University, Qufu, Shandong 273155, People’s Republic of China ‡ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China § Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen, Fujian 361005, People’s Republic of China S Supporting Information *

ABSTRACT: With mixed transition-metal-complex, alkali-metal, or organic cations as structure-directing agents, a series of novel two-dimensional (2D) layered inorganic−organic hybrid iodoargentates, namely, Kx[TM(2,2-bipy)3]2Ag6I11 (TM = Mn (1), Fe (2), Co (3), Ni (4), Zn (5); x = 0.89−1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6 (6), have been solvothermally synthesized and structurally characterized. All the title compounds feature 2D microporous layers composed by [Ag3I7] secondary building units based on AgI4 tetrahedra. Differently, the [Ag3I7] trimers are directly interconnected via corner-sharing to form the 2D [Ag6I11]5− layer in compounds 1−5, whereas two neighboring [Ag3I7] trimers are initially condensed into a hexameric [Ag6I12] ternary building unit as a new node, which further self-assembles, leading to the 2D [Ag6I10]4− layer in compound 6. The UV−vis diffuse-reflectance measurements reveal that all the compounds possess proper semiconductor behaviors with tunable band gaps of 1.66−2.75 eV, which lead to highly efficient photocatalytic degradation activities over organic pollutants under visible light irradiation compared to that of N-dotted P25. Interestingly, all the samples feature distinct photodegradative speeds at the same reaction conditions, and compound 1 features the highest photocatalytic activity among the title phases. The luminescence properties, band structures, and thermal stabilities were also studied.

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and organic components.1−3 Especially the tetrahedral TO4 (T = main group metal) unit constructed microporous zeolites

INTRODUCTION Inorganic−organic hybrid materials have been intensively investigated because of not only fascinating structural diversities for supramolecular chemistry and crystal engineering, but also distinctive properties inherited from the interaction of inorganic © XXXX American Chemical Society

Received: June 14, 2015

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DOI: 10.1021/acs.inorgchem.5b01324 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Intrigued by the rich coordinative flexibilities and potential semiconducting behaviors of these hybrid materials, we undertook systematic studies in exploring new hybrid iodoargentates via mixed incorporation of optically active [TM(2,2-bipy)3]2+ complexes as well as other templates, which have not been studied until now. Fortunately, we prepared two types of 2D layered iodoargentates of Kx[TM(2,2-bipy)3]2Ag6I11 (x = 0.89−1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6 based on new [Ag3I7] trimers and [Ag6I12] hexamers, respectively. The UV−vis diffusereflectance measurements reveal that all the compounds possess proper semiconductor behavior and visible light absorption, which lead to highly efficient photocatalytic activities under visible light irradiation. In this paper, we report their syntheses, crystal structures, band structures, optical and photocatalytic properties.

with open frameworks have been continuously explored with multiple applications in many fields, such as catalysis, ion exchange, selective separation and adsorption, etc.4,5 Subsequently, the study of the design and syntheses of new types of multifunctional microporous materials similar to the zeolites has also attracted extensive interest based on crystal engineering. In 1997, Martin and Zubieta introduced a new type of microporous compound which utilized halide ions instead of the oxygen or chalcogenide anions and used the d10 transition or main group metals (Zn2+, Cd2+, Cu+, Ag+, Pb2+, Bi3+, etc.) as coordination centers.6−10 Among these great families of microporous materials, the hybrid iodoargentates occupy an important position for their abundant structures due to their flexible coordination modes and connection manners.11−20 Structurally, it is well-known that silver(I) features flexible coordination modes, such as linear AgI2, AgI3 triangles, and AgI4 tetrahedra. More interestingly, the tetrahedral AgI4 unit features high self-assembly characterization and diversiform condensation modes including corner-, edge-, and face-sharing as well as short Ag···Ag interactions, termed argentophilicity, which result in many iodoargentate secondary building units (SBUs) of Ag4I8, Ag5I9, Ag5I10, Ag6I12, etc. As new building units, these anionic SBUs can be further assembled into 1D chains, 2D layers, and 3D frameworks.11−15 For example, the cubane-type tetrameric Ag4I8 SBU has four terminal iodine atoms as four-connecting nodes, which are able to self-condense via corner-sharing to form 1D [Ag4I6]2− chains, 2D [Ag2I3]− layers, and 3D [Ag4I6]2− frameworks under different organic templates.16 These hybrid iodoargentates represent non-oxide analogues of microporous zeolites and provide new developments in host−guest chemistry through crystal engineering of chemical framework building units. An effective strategy for the development of novel microporous iodoargentates is to rationally design and construct new SBUs via introduction of new templated agents or structure-directing agents (SDAs). Most of the reported hybrid iodoargentates are charge balanced and space compensated by various organic templates as SDAs, such as quaternary ammonium and arsenic, aliphatic, or heterocyclic amine cations and so on. In recent years, some new templates including rareearth-metal or transition-metal (TM) complexes have started to be introduced into hybrid iodoargentates. Compared with the soft and flexible organic templates, rigid metal complexes afford more stable templated effects for controlling the inorganic microstructure. At the same time, the metal complexes may enhance or improve the electronic, optical, and magnetic properties of hybrid materials resulting from the abundant d orbital electrons. Until now, only a few TM-complex cation directed iodoargentates have been reported compared with those based on organic cations, for example, [Ni(2,2-bipy)(THF)2(H2O)2](Ag10I12)·2DMF, [Cu(2,2-bipy)3]Ag5I7, [Mn(4,4-bipy)(DMF)3(H2O)]Ag5I7·(4,4bipy), [Mn(4,4-bipy)(DMSO)4]2Ag11I15, and Zn(en)3Ag2I4, etc.21 It should be noted that all the above hybrid iodoargentates feature 1D anionic chains except for Zn(en)3Ag2I4 with a 3D framework. Functionally, most of the hybrid iodoargentates feature smaller band gaps ( 2σ(I)) GOF on F2 R1/wR2a (I > 2σ(I)) R1/wR2 (all data) Δρmax (e/Ǻ 3) Δρmin (e/Ǻ 3) a

1

2

3

C60N12H48KMn2Ag6I11 3129.20 R3̅ (No. 147) 14.7159(8) 14.7159(8) 31.5185(17) 5911.1(6) 3 2.637 293(2) 6.173 4278 23155 3021 2392 1.016 0.0275/0.0556 0.0403/0.0606 1.036 −1.323

C60N12H48KxFe2Ag6I11 3128.36 R3̅ (No. 147) 14.5723(13) 14.5723(13) 31.178(3) 5733.7(9) 3 2.720 293(2) 6.410 4280 22469 2935 2611 1.033 0.0266/0.0485 0.0308/0.0500 1.664 −1.821

C60N12H48KxCo2Ag6I11 3132.88 R3̅ (No. 147) 14.6595(16) 14.6595(16) 31.363(5) 5837.0(13) 3 2.677 293(2) 6.353 4283 15212 2952 2552 1.055 0.0272/0.0653 0.0314/0.0671 1.056 −1.482

R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2, x = 0.93 for 2 and 0.89 for 3.

Table 2. Crystal Data and Structure Refinements for Compounds 4−6 chemical formula fw space group a (Å) b (Å) c (Å) β (deg) V (Ǻ 3) Z Dcalcd (g cm−3) temp (K) μ (mm−1) F(000) no. of reflns collected no. of unique reflns no. of reflns (I > 2σ(I)) GOF on F2 R1/wR2a (I > 2σ(I)) R1/wR2 (all data) Δρmax (e/Ǻ 3) Δρmin (e/Ǻ 3) a

4

5

6

C60N12H48KxNi2Ag6I11 3134.04 R3̅ (No. 147) 14.6145(10) 14.6145(10) 31.442(2) 90 5815.7(7) 3 2.687 293(2) 6.431 4292 22495 2991 2733 1.040 0.0255/0.0490 0.0287/0.0503 1.291 −1.656

C60N12H48KZn2Ag6I11 3150.06 R3̅ (No. 147) 14.6293(18) 14.6293(18) 31.621(4) 90 5860.8(13) 3 2.678 293(2) 6.517 4308 22679 2978 2730 1.075 0.0295/0.0704 0.0324/0.0718 1.000 −1.826

C40N8H33NiAg3I6 1769.46 C2 (No. 5) 22.6467(10) 13.5115(6) 16.2150(7) 107.93 4720.8(4) 4 2.490 293(2) 5.581 3264 27730 10720 10153 1.033 0.0224/0.0472 0.0247/0.0479 1.122 −0.926

R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2, x = 0.93 for 4.

Crystallographic Studies. Single crystals of the title compounds were collected on a Bruker SMART charge-coupled-device (CCD)based diffractometer (Mo Kα radiation, λ = 0.71073 Å) at 293(2) K. Data integrations and cell refinements were done by the INTEGRATE program of the APEX2 software, and multiscan absorption corrections were applied using the SCALE program for the area detector. The structures were solved by the direct method and refined on F2 by the fullmatrix least-squares method with the SHELXS-97 program.22 All nonhydrogen atoms were refined with anisotropic thermal parameters, and the hydrogen atoms of organic cations were generated theoretically onto the specific carbon atoms and refined isotropically with fixed thermal factors. It should be noted the I(2) sites show slight disorder over two positions for compounds 2−4, and the I(2a) sites will be used to discuss the crystal structures in the paper due to the larger occupancy values.

Furthermore, it is found that the displacement parameters of K elements are slightly higher than those of other atoms, and we refined their occupancies to be 91.3(7)%, 89.7(1)%, and 93.2(3)%, respectively, for compounds 2−4. The crystallographic data for all the compounds are listed in Tables 1 and 2, and important bond lengths are listed in Tables 3 and 4. More details on the crystallographic studies are given in the Supporting Information. Calculation Details. The densities of states (DOS) of K[Mn(2,2bipy)3]2Ag6I11 and K[Zn(2,2-bipy)3]2Ag6I11 were calculated by density functional theory (DFT) using the crystallographic data with the CASTEP code, which uses a plane-wave basis set for the valence electrons and a norm-conserving pseudopotential for the core electrons.23 The number of plane waves included in the basis was determined by a cutoff energy of 320 eV, and the numerical integration of the Brillouin zone C


Article

Inorganic Chemistry Table 3. Selected Bond Lengths (Å) for Compounds 1−3a Ag(1)−I(3) Ag(1)−I(2)#1 Ag(1)−I(2) Ag(1)−I(1)#1 Ag(1)−Ag(1)#2 Ag(1)−Ag(1)#1 K(1)−I(2)#5 K(1)−I(2)#6 K(1)−I(2)#7 Ag(1)−I(1) Ag(1)-I(2A)#5 Ag(1)-I(2A) Ag(1)−I(3) Ag(1)−Ag(1)#5 K(1)−I(2A)#1 K(1)−I(2A)#2 K(1)−I(2A)#3

Ag(1)−I(1) Ag(1)−I(2A) Ag(1)−I(2A)#2 Ag(1)−I(3) Ag(1)−Ag(1)#2 K(1)−I(2A)#5 K(1)−I(2A)#4 K(1)−I(2A)#1

Compound 1 2.7731(4) Mn(1)−N(1)#3 2.8123(5) Mn(1)−N(1) 2.8732(5) Mn(1)−N(1)#4 2.9799(5) Mn(1)−N(2) 3.0623(6) Mn(1)−N(2)#3 3.0623(6) Mn(1)−N(2)#4 3.6957(4) K(1)−I(2)#8 3.6957(4) K(1)−I(2)#9 3.6957(4) K(1)−I(2)#10 Compound 2 2.9709(5) Fe(1)−N(1)#6 2.8140(11) Fe(1)−N(1)#7 2.8922(12) Fe(1)−N(1) 2.7585(4) Fe(1)−N(2)#7 3.0059(6) Fe(1)−N(2)#6 3.733(3) Fe(1)−N(2) 3.733(3) K(1)−I(2A)#4 3.733(3) K(1)−I(2A)#5 K(1)−I(2A) Compound 3 2.9772(6) Co(1)−N(1)#6 2.867(8) Co(1)−N(1)#7 2.895(5) Co(1)−N(1) 2.7671(4) Co(1)−N(2)#6 3.0283(6) Co(1)−N(2)#7 3.743(5) Co(1)−N(2) 3.743(5) K(1)−I(2A) 3.743(5) K(1)−I(2A)#2 K(1)−I(2A)#3

Table 4. Selected Bond Lengths (Å) for Compounds 4−6a

2.236(4) 2.236(4) 2.236(4) 2.247(3) 2.247(3) 2.247(3) 3.6957(4) 3.6958(4) 3.6958(4)

Ag(1)−I(1) Ag(1)-I(2A) Ag(1)-I(2A)#2 Ag(1)−I(3)#8 Ag(1)−Ag(1)#1 K(1)−I(2A)#3 K(1)−I(2A)#4 K(1)−I(2A)#1

1.968(3) 1.968(3) 1.969(3) 1.982(3) 1.982(3) 1.982(3) 3.733(3) 3.733(3) 3.733(3)

Ag(1)−I(2) Ag(1)−I(3)#1 Ag(1)−I(3) Ag(1)−I(1) Ag(1)−Ag(1)#1 K(1)−I(3)#2 K(1)−I(3)#5 K(1)−I(3)#1

2.119(3) 2.119(3) 2.119(3) 2.133(3) 2.133(3) 2.133(3) 3.743(5) 3.743(5) 3.743(5)

Ag(1)−I(1) Ag(1)−I(2) Ag(1)−I(2)#1 Ag(1)−I(3) Ag(2)−I(3) Ag(2)−I(4) Ag(2)−I(1) Ag(2)−I(5)#2 Ag(3)−Ag(1) Ag(2)−Ag(1) Ag(1)−Ag(1)#1

Symmetry codes for 1: #1, −x + y + 2, −x, z; #2, −y, x − y − 2, z; #3, −y, x − y − 1, z; #4, −x + y + 1, −x, z; #5, y + 2/3, −x + y + 4/3, −z + 1/3; #6, −y − 2/3, x − y − 4/3, z − 1/3; #7, x − 2/3, y + 2/3, z − 1/3; #8, −x + 2/3, −y − 2/3, −z + 1/3; #9, x − y − 4/3, x − 2/3, −z + 1/3; #10, −x + y + 4/3, −x + 2/3, z − 1/3. Symmetry codes for 2: #1, −x + 4/3, −y + 2/3, −z + 2/3; #2, x − y + 1/3, x − 1/3, −z + 2/3; #3, −x + y + 1, −x + 1, z; #4, y + 1/3, −x + y + 2/3, −z + 2/3; #5, −y + 1, x − y, z; #6, −y + 2, x − y, z; #7, −x + y + 2, −x + 2, z. Symmetry codes for 3: #1, −y + 1, x − y, z; #2, −x + y + 1, −x + 1, z; #3, −x + 4/3, −y + 2/3, −z + 2/3; #4, y + 1/3, −x + y + 2/3, −z + 2/3; #5, x − y + 1/3, x − 1/3, −z + 2/3; #6, −x + y, −x + 1, z; #7, −y + 1, x − y + 1, z. a

Compound 4 2.9782(5) Ni(1)−N(1)#6 2.8156(11) Ni(1)−N(1) 2.8877(10) Ni(1)−N(1)#7 2.7652(4) Ni(1)−N(2) 3.0195(6) Ni(1)−N(2)#7 3.752(4) Ni(1)−N(2)#6 3.752(4) K(1)−I(2A)#2 3.752(4) K(1)−I(2A) K(1)−I(2A)#5 Compound 5 2.7640(5) Zn(1)−N(2)#3 2.8083(6) Zn(1)−N(2)#4 2.8772(6) Zn(1)−N(2) 2.9768(6) Zn(1)−N(3) 3.0296(7) Zn(1)−N(3)#4 3.7521(5) Zn(1)−N(3)#3 3.7521(5) K(1)−I(3)#6 3.7521(5) K(1)−I(3)#7 K(1)−I(3) Compound 6 2.9750(6) Ag(3)−I(1) 2.9102(5) Ag(3)−I(2) 2.9384(6) Ag(3)−I(5) 2.8049(5) Ag(3)−I(4) 2.8813(6) Ni(1)−N(1) 2.8018(5) Ni(1)−N(4) 3.0859(6) Ni(1)−N(5) 2.8121(6) Ni(1)−N(6) 3.1544(6) Ni(1)−N(3) 3.3363(7) Ni(1)−N(2) 3.1537(9)

2.082(3) 2.082(3) 2.082(3) 2.098(3) 2.098(3) 2.098(3) 3.752(4) 3.752(4) 3.752(4) 2.150(3) 2.150(3) 2.150(3) 2.171(3) 2.171(3) 2.171(3) 3.7521(5) 3.7521(5) 3.7521(5) 2.8489(5) 3.0052(6) 2.7941(6) 2.8455(6) 2.073(3) 2.073(3) 2.078(3) 2.087(3) 2.088(3) 2.093(3)

a Symmetry codes for 4: #1, −y + 1, x − y, z; #2, −x + y + 1, −x + 1, z; #3, x − y + 1/3, x − 1/3, −z + 2/3; #4, y + 1/3, −x + y + 2/3, −z + 2/3; #5, −x + 4/3, −y + 2/3, −z + 2/3; #6, −y + 1, x − y + 1, z; #7, −x + y, −x + 1, z; #8, −x + 2/3, −y + 1/3, −z + 1/3. Symmetry codes for 5: #1, −y + 1, x − y, z; #2, −x + y + 1, −x + 1, z; #3, −x + y, −x, z; #4, −y, x − y, z; #5, x − y + 1/3, x − 1/3, −z − 1/3; #6, y + 1/3, −x + y + 2/3, −z − 1/3; #7, −x + 4/3, −y + 2/3, −z − 1/3. Symmetry codes for 6: #1, −x, y, −z; #2, −x + 1/2, y + 1/2, −z.

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RESULTS AND DISCUSSION Synthetic Discussion. Solvothermal reaction of AgI, transition-metal salts, 2,2-bipy, and KI in HI and acetonitrile aqueous solution led to two different types of new hybrid iodoargentates, Kx[TM(2,2-bipy)3]2Ag6I11 (x = 0.89−1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6. In the reaction, the transition-metal ions were in situ coordinated to 2,2-bipy into saturated [TM(2,2-bipy)3]2+ cations and the 2,2-bipy molecule was also in situ protonated due to the acidic environment, and similar phenomena have been reported in many inorganic− organic materials.24,25 It should be noted that compounds 1−5 and 6 were prepared in very similar reaction conditions except that more hydroiodic acid was added in the preparation of 6. Detailed experiments suggested that the superfluous hydroiodic acid plays an important role in the generation of compound 6, and its yield will greatly decrease with the reduction of hydroiodic acid, which may be due to the higher acidic environment, which easily leads to the protonation of 2,2-bipy and prevents its coordination action to transition metals. Furthermore, the KI added to the solution was used not only as the source of I− but also to effectively increase the solubility of the AgI.

was performed using a 2 × 2 × 2 Monkhorst−Pack k-point. The other calculating parameters and convergence criteria were set by the default values of the CASTEP code, for example, an eigen-energy convergence tolerance of 1.0 × 10−5 eV. Photocatalytic Activity Measurements. The photocatalytic activities of as-prepared samples 1−6 were evaluated by the degradation of crystal violet (CV), rhodamine B (RhB), and methyl orange (MO) under visible light irradiation from a 50 W Xe lamp. The cutoff filter was used to remove all wavelengths less than 400 nm and more than 780 nm, ensuring irradiation with visible light only. In photocatalytic activity measurements, 15 mg of each sample of the title compounds was added to a 30 mL 1 × 10−5 mol·L−1 solution of CV, and 30 mg of each sample was added to the same solution of MO and RhB. After being dispersed in an ultrasonic bath for 30 min, the suspensions were magnetically stirred in the dark for 10 h before irradiation to ensure absorption equilibrium and uniform dispersity between the catalyst and solution. The solution was then exposed to visible light irradiation. After a given irradiation time, 4 mL of the mixture was continually taken from the reaction cell, and the catalysts were separated from the suspensions by centrifugation. The degradation process was monitored through a wavelength scan on a GBC Cintra 2020 UV/vis spectrophotometer. D


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Inorganic Chemistry Hence, moderate I− ions are able to feature relatively strong solution and coordination abilities, leading to higher yields of the title compounds. However, excess I− ions will lead to the formation of some low-dimensional iodoargentates, such as [TM(2,2-bipy)3]AgI3, etc. In this study, we adopted the proper KI:AgI ratio of 1:4. Description of the Structures. Single-crystal X-ray diffraction analyses revealed that 1−5 belong to isostructural phases; hence, compound 1 is taken as an example to depict the crystal structure. Compound 1 crystallizes in the trigonal system R3̅ (No. 147), and the asymmetric unit consists of one crystallographically independent K, one Mn, one Ag, three I atoms, and three 2,2-bipy ligands. As shown in Figure 1a, the

modes and occupy the 1D channel along the c-axis as charge balance and space filling (Figure 2d). Compound 6 crystallizes in the monoclinic system C2 (No. 5), and the asymmetric unit consists of one nickel atom, three silver(I) ions, five iodines, three coordinated 2,2-bipy ligands, and one protonated 2,2-bipy molecule. As shown in Figure 1b, the Ag(1) atom is coordinated by one μ2-iodine and three μ3-iodines, and Ag(2) is surrounded by one μ3-iodine and three μ2-iodines, whereas Ag(3) is coordinated by two μ2-iodines and two μ3-iodines. All the silver(I) ions adopt tetrahedral coordination environments with I−Ag−I bond angles of 91.082(16)−119.577(19)° and Ag−I bond distances of 2.7940(6)−3.0860(6) Å, which are in accord with those of compounds 1−5. Each Ag(1)I4, Ag(2)I4, and Ag(3)I4 tetrahedron is condensed via edge-sharing to form a trimeric Ag3I7 SBU according to the same connecting manner as that of compound 1. Three Ag centers also form a Ag3 triangle with Ag···Ag distances of 3.1545(6)−3.3892(7) Å, which are slightly longer than the corresponding values of compound 1 but remain shorter than the sum of the van der Waals radii of silver (3.44 Å). It should be noted that the Ag3I7 trimer of compound 1 is composed of one crystallographically independent silver atom with a C3 symmetry axis, whereas it is built up from the three different Ag centers with a C1 symmetry axis in compound 6. Two neighboring Ag3I7 trimers are cross-aggregated via sharing two I(2) atoms as well as a Ag···Ag weak bond (3.1540(9) Å) into a new hexameric [Ag6I10] TBU with four I(5) atoms as terminal junctions (Figure 1c). Such a [Ag6I10] hexamer is similar to that of [Cu6I12] in [De-DABCO]2[Me-DABCO]Cu11I17. Each hexameric Ag6I12 TBU is further interconnected with four neighboring ones via sharing the terminal iodine atoms to form a new 2D [Ag6I10]4− anionic layer parallel to the ab-plane with a (4,4) topological network (Figure 3a). At the same time, the 2D layer features another type of [Ag12I12] 24-membered ring with an approximate quadrangular cross-section of 10.185 × 15.271 Å2, which is occupied by the [H-2,2-bipy]+ cations as spacers. Among the 2D [Ag6I10]4− anionic layer, all the [Ni(2,2bipy)3]2+ complex cations feature a parallel arrangement along the b-axis separated by the isolated I− ions along the a-axis (Figure 3b). It is very interesting to compare the building units and 2D layered structures of compounds 1 and 6. Under the directed actions of the mixed cations, their structures both feature 2D anionic iodoargentate layers based on trimeric [Ag3I7] SBUs condensed by face-sharing of three AgI4 tetrahedra. Differently, the [Ag3I7] SBUs are directly interconnected by sharing external iodine atoms to form the 2D [Ag6I11]5− layer in compound 1, whereas the two neighboring [Ag3I7] units are initially condensed to form a hexameric [Ag6I12] TBU as a new connecting node, finally leading to the 2D [Ag6I10]4− anionic layer in compound 6. It is worth noting that the tetrahedral [AgI4] unit often undergoes a variety of self-condensations to form polyanion units of clusters or oligomers as SBUs, such as [Ag4I8]4−, [Ag5I9]4−, [Ag5I10]5−, and [Ag6I12]6−, etc. However, most of the SBUs are self-condensed to form 1D anionic chains, such as [Ag4I6]2−, [Ag5I7]2−, [Ag6I9]3−, [Ag8I12]4−, [Ag10I12]2−, and [Ag10I14]4−, etc.11−15 Occasionally, these SBUs can also be interlinked to form 2D microporous layers; for example, 2D [Ag2I3]− and [Ag5I8]3− layers are formed by [Ag4I8]4− and [Ag5I10]2− SBUs with approximately quadrangular [Ag8I8] and [Ag8I6] rings, respectively.18a,17b Undoubtedly, the 2D [Ag6I11]5− and [Ag6I10]4− reported here based on trimeric [Ag3I7] and hexameric [Ag6I12] building blocks represent new microporous

Figure 1. Detailed view of the [Ag3I7] SBU in compound 1 (a) and [Ag3I7] SBU (b) and [Ag6I10] TBU (c) in compound 6.

Ag(1) ion is tetrahedrally surrounded by one μ1-iodine, one μ2-iodine, and two μ3-iodine atoms with I−Ag−I bond angles of 100.249(13)−120.910(15)° and Ag−I bond distances of 2.9799(5)−2.9799(5) Å, which are in accord with those of other hybrid iodoargentates, such as [HCP]Ag2I3, [MC]Ag2I3, [BC]2Ag4I6, and [Cu(2,2-bipy)3]Ag5I7, etc.18−21 Three neighboring AgI4 tetrahedra are condensed via sharing I(3) and I(2) atoms to form a triangular [Ag3I7] trimer with three outside I(1) atoms. Such interconnection also leads to a [Ag3] triangle with a weak Ag···Ag distance of 3.0623(6) Å, which is evidently shorter than the sum of the van der Waals radii of AgI (3.44 Å), indicating the presence of a weak argentophilic interaction. A similar trimerical [Cu3I7] unit has been reported in [De-DABCO]2[Me-DABCO]Cu11I17.26 Each [Ag3I7] trimer as a new SBU is further connected to three adjacent ones via sharing I(1) atoms to form a novel 2D [Ag6I11]5− layer along the ab-plane with a (6,3) topological network (Figure 2a). As a result, the 2D layer contains a [Ag12I12] 24-membered ring with a hexagonal cross-section of 12.848 × 12.848 Å2 presented along the c-axis. The 2D [Ag6I11]5− layers feature parallel stacking and are further interconnected by K+ atoms via weak K−I bonds along the c-axis to form a [K@Ag6I11]4− 3D framework with a large 1D channel sized at 11.73 × 11.94 Å2 (Figure 2b,c). The K+ ion is surrounded by eight I(2) atoms in an octahedral coordination environment with a K−I bond distance of 3.6957(4) Å. All the [Mn(2,2-bipy)3]2+ complex cations feature parallel packing E


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Figure 2. View of the 2D [Ag6I11]5− layer (a), the stacking manner of the 2D [Ag6I11]5− layer along the c-axis (b), and the 3D [K@Ag6I11]4− framework (c) and the general view of compound 1 along the b-axis (d). The Ag and I atoms are shown in green and red, respectively. The [AgI4] tetrahedra and [Mn(2,2-bipy)3]2+ complexes are shown in green and purple, respectively, only for clarity.

Figure 3. View of the 2D [Ag6I10]4− layer (a) and packing structure of compound 6 along the b-axis (b).

layers with the largest pore sizes in hybrid iodoargentate chemistry, which further indicate the unique structure-directing effect of transition-metal-complex cations. Thermal Stabilities. Thermal gravimetric behaviors of compounds 1−6 were investigated under a nitrogen atmosphere in the temperature range of 30−800 °C, and the TGA curves are shown in Figure 4. Compounds 1−4 and 6 start to decompose at about 200, 260, 210, 190, and 200 °C, respectively, and continuously lose weight and do not achieve balance to 800 °C, which may be due to the fact that the decomposition of complex and organic cations simultaneously leads to the complete collapse and volatilization of the iodoargentate anionic frameworks. Compound 5 exhibits the first-step weight loss of all 2,2-bipy ligands, one KI, and two ZnI2 molecules per formula in the range of 190−530 °C. The observed weight loss of 54.9% is close to the theoretical value of 55.3%. After the major weight loss, compound 5 continues to slowly lose weight at about 800 °C. Optical Properties. The solid-state optical diffusereflectance spectra of compounds 1−6 were measured at room

Figure 4. Thermogravimetric curves for compounds 1−6. F


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experiments, neither the photolysis experiment without photocatalyst nor the catalytic experiment without light irradiation showed any observable decrease in CV, RhB, and MO concentration with time. After samples 1−6 were added to the solution, the concentrations of the CV, RhB, and MO solutions continuously decreased under visible light irradiation, which is also demonstrated by the change in the color of the solution (Figures S7−S9). Because the CV, RhB, and MO solutions and the sample powders achieved absorption equilibrium under the dark environment before light irradiation, monotonic decreases of the absorbance intensities for CV, RhB, and MO solutions were derived from the photodegradation actions of samples 1−6 under visible light illumination. The X-ray diffraction (XRD) patterns show that there are no obvious changes before and after the photocatalytic process, demonstrating that all the samples are visible light photocatalysts for organic dye destruction (Figure S10). In the photocatalytic reaction, temporal changes of the concentrations for CV and RhB solutions were monitored by examining the variations of the intensities in the maximal absorption in UV−vis spectra at 589 and 552 nm, respectively. The degradation efficiencies are defined as C/C0, where C and C0 represent the remnant and initial concentrations of the organic dyes. In this study, we selected 60 and 180 min as the test times with interval times of 10 and 30 min for the CV and RhB solutions, respectively, to compare their photocatalytic activities (Figures S7 and S8). Under the photodegradation action of compound 1, the degradation ratio of CV reaches 90% upon exposure to visible light for 30 min, and then reaches nearly 100% after 50 min, resulting in complete decolorization (Figure 6a). Relatively, compounds 2, 3, 4, 5, and 6 show slightly slow photodegradation speeds, and about 82%, 31%, 48%, 63%, and 42% of CV is decomposed after irradiation for 30 min, with these values increasing to nearly 93%, 56%, 78%, 85%, and 71% after 60 min, respectively. At the same time, we also studied the photocatalytic property of photocatalyst N-dotted P25 as a benchmark under completely the same conditions, and the results show that more than 84% of CV is still active after visible light irradiation for 60 min. Obviously, all six samples have higher photodegradation activities than N-dotted P25 for CV. The RhB solution also features the same photodegradation activities. Among these phases, compound 1 shows the most excellent photocatalytic activity, and it can completely decompose the RhB within 30 min. Compounds 2, 4, 5, and 6 can also achieve the same effects within 180 min. Compound 3 exhibits the lowest photocatalytic activity, and the degradation ratio of RhB reaches 88% after 180 min (Figure 6c). All the compounds 1−6 feature higher photodegradation activities except for compound 3 compared with the N-doped P25. The experimental results above show the six samples feature different photocatalytic activities in the order of 1 > 2 > 5 > 4 > 6 > 3 for the photodegradation of CV and RhB solutions. To further accurately evaluate the photocatalytic activities of the title compounds, we study the kinetic process of the photodegradation reaction by calculating the relationship between ln(C0/C) and reaction time. Here, it should be noted that the photodegradation reaction of compound 1 over the RhB solution was re-evaluated with an interval time of 10 min only for accuracy. The results show that all the ln(C0/C) values follow the linear relationship over the reaction time; that is, all the photodegradation processes belong to the first-order kinetic reaction (Figure 6b,d). Subsequently, the experimental ln(C0/C) values over the reaction time were determined through a linear

Figure 5. Solid-state optical absorption spectra of compounds 1−6.

temperature. The absorption spectra calculated from the diffusereflectance data by using the Kubelka−Mulk function are plotted in Figure 5. Extrapolation of the linear portion of the absorption edge gives optical band gaps of 2.01, 1.66, 1.75, 1.85, and 2.08 eV for compounds 1−5, respectively, which are in accordance with their colors of orange, dark-red, red, red, and orange. The band gap of compound 6 is estimated as 2.75 eV corresponding to the pink color. Obviously, all the title compounds have smaller band gaps and exhibit a red shift of the absorption edge compared with the bulk β-AgI (2.81 eV), and a similar red shift has also been found in those hybrid iodoargentates, such as (H2dpe)(β-Ag2I4), [Cu(2,2-bipy)3]Ag5I7, [MC]Ag2I3, [EC]Ag2I3, and [PC]2Ag4I6, etc.14a,16,21a Furthermore, the different electronic configurations of the transition metals lead to the evidently different band gaps of compounds 1−5, which demonstrates the opportunity to tune the band gaps of hybrid iodoargentates by introducing different transition-metal complexes into the compounds. The emission spectra of compounds 1−6 in the solid state were investigated at room temperature, with the results shown in Figure S6. Upon excitation at 260 nm, compounds 1−6 give evident emission with λmax = 405, 439, 497, 576, 678, and 480 nm, respectively. These luminescent properties are similar to those found for transition-metal-complex cation directed iodoargentates.21 These emission bands can be assigned to the mixture of metal-to-metal transfer (Ag 5s or 5p to Ag 4d) and iodide-tometal charge transfer (I 5p to Ag 4d) and are affected by the metal−metal interactions, which has been investigated and proved by the molecular orbital calculation for some related hybrid iodoargentates.27 It should be noted that the luminescence spectra of compounds 1−4 and 6 feature some quenching characterizations compared with that of compound 5, which is likely to be ascribed to the quenching effects of open-shell metal ions by means of energy transfer to the d−d absorption band and nonradiative decay. That is, the presence of a fluorescent quenching reagent (Fe2+, Co2+, and Ni2+ ions, etc.) in the lattice leads to the weak emission spectra of compounds 1−4 and 6. Some examples of this phenomenon have been reported in some inorganic materials.28 Photocatalytic Properties. The narrow band gaps of the compounds encourage us to investigate their visible light photocatalytic activities, which were evaluated by the degradation of CV, RhB, and MO as the test pollutant under visible light irradiation at room temperature. Before the photocatalytic G


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Figure 6. Photodegradation of CV (a) and RhB (c) by compounds 1−6 monitored as the normalized change in concentration as a function of the irradiation time, and the linear relationship of ln(C0/C) over the reaction time for CV (b) and RhB (d).

fitted method according to the first-order reaction equation of ln(C0/C) = kt, where k is the rate constant and t represents the reaction time. For the CV photodegradation reaction, the calculated k values of compounds 1−6 are 0.0775, 0.0433, 0.0135, 0.0256, 0.0303, and 0.0209 min−1, respectively, which are evidently larger than that of P25 (0.0061 min−1) (Table 5). The

differences remains unclear at this stage. Furthermore, it should be noted that there are few reports on the photocatalytic properties of hybrid iodoargentates under UV light irradiation, such as [(Hpy)(Ag2I3)]n and [(Hpy)(Ag5I6)]n,30 and the visible light evoked photodegradative activity of hybrid iodoargentate has not been reported. Hence, the title compounds represent the first visible light responding photocatalysts, which may be due to the narrow band gaps derived from the regulation of transition-metalcomplex cations. Possible Photocatalytic Mechanism. As far as we know, the silver halides are seldom independently used as photocalysts due to their instabilities under sunlight. Hence, as stable photocatalysts, the photocatalytic reaction of hybrid iodoargentates requires an effective way of separating the electron−hole pair generated by the visible light absorption to prevent the reduction of Ag+ ions. To gain insight into this question and further study the photocatalytic mechanism, we examined the relationship of the crystal structure and optical property by performing an electronic band structure calculation based on the DFT method. As shown in Figure 7a, the calculated band gaps of 1 and 5 are 1.75 and 1.98 eV, which are smaller than the corresponding experimental values of 2.01 and 2.08 eV, respectively. Such a discrepancy is due to the discontinuity of the exchangecorrelation potential that underestimates the band gap in semiconductors and insulators. On the basis of the total and partial DOS diagrams, the valence bands just below the Fermi level of compound 5 (the top of the valence band) are mainly contributed by the 5p state of I mixed with the 4d state of Ag, and the conduction bands just above the Fermi level in the range of 2−3 eV are mainly derived from the C 2p and N 2p orbitals (Figure 7b). As for compound 1, the highest valence bands are predominately derived from the 5p state of I and the 4d state of Ag as well as the 3d orbital of Mn, and the lowest conduction bands are mainly composed of the C 2p, N 2p, and Mn 3d states.

Table 5. Linear Relationship of ln(C0/C) and Reaction Time for the Photodegradation of CV and RhB CV ln(C0/Ct) = kt 1 2 3 4 5 6 P25

ln(C0/Ct) = 0.0775t ln(C0/Ct) = 0.0433t ln(C0/Ct) = 0.0135t ln(C0/Ct) = 0.0256t ln(C0/Ct) = 0.0303t ln(C0/Ct) = 0.0209t ln(C0/Ct) = 0.0061t

RhB k 0.0775 0.0433 0.0135 0.0256 0.0303 0.0209 0.0061

ln(C0/Ct) = kt ln(C0/Ct) = 0.1037t ln(C0/Ct) = 0.0249t ln(C0/Ct) = 0.0083t ln(C0/Ct) = 0.0155t ln(C0/Ct) = 0.0185t ln(C0/Ct) = 0.0142t ln(C0/Ct) = 0.0092t

k 0.1037 0.0249 0.0083 0.0155 0.0185 0.0142 0.0092

rate constant of compound 1 is found to be nearly 6 and 13 times larger than those of compound 3 and P25, respectively. As for the RhB solution, the k value of compound 1 is nearly 11 and 12 times larger than those of compound 3 and P25, respectively, which further shows the highest photocatalytic activity of 1 among these phases (Table 5). Roughly speaking, the visible light responding photocatalytic activities of the title hybrid iodoargentates are lower than those of Ag-based combined semiconductors, such as Ag@AgX (X = Cl, Br) and AgI@BiOI, etc., and the former still need a great increase via chemical decoration.29 It is very interesting to note that the isostructural compounds 1−5 with different transition-metal complexes feature distinct photocatalytic activities at the same reaction conditions. However, it is a pity that the detailed reason for such H


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Figure 7. Total and partial DOS of compounds 1 (a) and 5 (b).

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Hence, the charge transition of compounds 1−5 mainly occurs between the anionic 2D [Ag6I11]5− layers and [TM(2,2-bipy)2]2+ cations. On the basis of these calculation results as well as the relative reports, we know that the photogenerated electrons are able to be easily transferred from the 2D [Ag6I11]5− layers to the [TM(2,2-bipy)3]2+ complex cations in the photocatalytic reaction.31 At the same time, the hole is transferred to the 2D [Ag6I11]5− layers corresponding to the oxidation of organic pollutants. In general, the photogenerated electrons of [TM(2,2bipy)3]2+ cations are expected to be trapped by O2 in the solution to form superoxide ions (O2−) and other reactive oxygen species.32 The stabilities of hybrid iodoargentates under visible light irradiation most likely arise from the fact that a photon is absorbed by the sample, and then an electron generated from an absorbed photon is transferred to the [TM(2,2-bipy)3]2+ cations rather than to the Ag+ ions of iodoargentate lattices, which can effectively prevent the reduction of Ag+ ions. Hence, [TM(2,2-bipy)3]2+ cations are able to effectively accept and transfer photogenerated electrons to stabilize the iodoargentate networks.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b01324. Luminescence emission spectra, absorption spectra of photodegradative CV, RhB, and MO solution, and XRD powder patterns for 1−6 (PDF) Crystallographic data in CIF format for 1 (CCDC No. 1404647) (CIF) Crystallographic data in CIF format for 2 (CCDC No. 1404656) (CIF) Crystallographic data in CIF format for 3 (CCDC No. 1404658) (CIF) Crystallographic data in CIF format for 4 (CCDC No. 1404651) (CIF) Crystallographic data in CIF format for 5 (CCDC No. 1404659) (CIF) Crystallographic data in CIF format for 6 (CCDC No. 1404652) (CIF)

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AUTHOR INFORMATION

Corresponding Authors

CONCLUSIONS

*E-mail: [email protected]. *E-mail: [email protected].

In conclusion, a series of inorganic−organic hybrid iodoargentates containing two types of novel 2D microporous layers with the largest pore sizes directed by mixed templates have been solvothermally synthesized and structurally and optically characterized. The photocatalytic experiments show that our materials have excellent photodegradative abilities for organic contaminants compared to N-doped P25, demonstrating the visible light responding photocatalytic properties of the transition-metal-complex cation directed iodoargentates. Further studies indicate that the compounds feature distinct photodegradative speeds, and the Mn phase shows the highest photocatalytic activity among these phases. The successful syntheses and visible light responding photocatalytic properties of the title compounds further illustrate the possibilities of constructing new hybrid iodoargentates and evince the tunable abilities of the band structures and physical properties of transition-metal-complex cations. Further studies on the structural regulation and structure−photocatalytic property relationships are in progress in our group.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the National Nature Science Foundation of China (Grant Nos. 21201081 and 21571081) and Fund of State Key Laboratory of Structural Chemistry (Grant No. 20150005) for financial support. We thank Prof. Jiang-Gao Mao at the Fujian Institute of Research on the Structure of Matter (FJIRSM) for help with the electronic structure calculation.

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REFERENCES

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