Low-Dimensional Hybrid Cuprous Halides Directed by Transition

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Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures and 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, and Wandong Chen Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01037 • Publication Date (Web): 09 Oct 2015 Downloaded from http://pubs.acs.org on October 10, 2015

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Crystal Growth & Design

By using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides have been solvothermally synthesized and structurally characterized. The title compounds feature abundant architectures ranging from one-dimensional (1D) chains to two-dimensional (2D) layers built from the self-condensation of [CuX4] tetrahedrons and/or [CuX3] triangles. The UV-vis diffuse-reflectance measurements reveal that the title compounds possesses semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation. 661x495mm (96 x 96 DPI)

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Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures and Photocatalytic Properties Xiao-Wu Lei,a* Cheng-Yang Yue,a,b,c* Jian-Qiang Zhao,a Yong-Fang Han,a Jiang-Tao Yang,a Rong-Rong Meng,a Chuan-Sheng Gao,a Hao Ding,a Chun-Yan Wanga, Wan-Dong Chena a

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry and

Chemical Engineering, Jining University, Qufu, Shandong, 273155, PR China b

Collaborative Innovation Center of Chemistry for Energy Materials (iChEM),

Xiamen

University,

Xiamen, Fujian 361005, PR China c

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,

Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China

*Corresponding author: Xiao-Wu Lei, Cheng-Yang Yue E-mail address: [email protected]; [email protected]

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Abstract By using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides with abundant architectures ranging from one-dimensional (1D) ribbons to two-dimensional (2D) layers have been solvothermally prepared and structurally characterized. Compounds [TM(2,2-bipy)3]Cu5I7 (TM = Fe (1), Co(2) and Ni(3)) feature 1D [Cu5I7]2- chains formed by the interconnection of [Cu5I10] units via edge-sharing. In compounds [TM(2,2-bipy)2I]2Cu7I9 (TM = Mn (4), Cu(5), Ru (6)), the [Cu5I9] units and [Cu2I6] dimers are alternately interlinked via edge-sharing to form the 1D [Cu7I9]2- chains. Compound [Cu(2,2-bipy)2I][(Me)2-2,2-bipy]Cu8I11 (7) contains a new 1D [Cu8I11]3- chain composed of complex [Cu8I13] units based on CuI4 tetrahedra and CuI3 triangles. Compound [Co(2,2-bipy)3]Cu5Br8 (8) features 1D [Cu5Br8]3- anionic chain built form the interconnection of [Cu6Br10] units and linear [Cu4Br8] tetramers. In compound K[Mn(2,2-bipy)3]2Cu6I11 (9), the [Cu3I7] secondary building units (SBUs) are directly interconnected to form 2D [Cu6I11]5- layers, which are further interconnected by K+ ions via weak K-I bonds to generate a 3D [K@Cu6I11]4framework with 1D large channels occupied by [Mn(2,2-bipy)3]2+ complexes. The UV-vis diffusereflectance measurements reveal that the title compounds possess semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and samples 4, 5 and 9 show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation.



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Introduction Inorganic−organic hybrid materials have been intensively investigated because of not only diverse structural topologies for supramolecular chemistry and crystal engineering, but also novel physical properties inherited from the interaction of inorganic and organic components.1-11 Recently, the compounds containing metal halides as inorganic moieties are important family of hybrid functional materials, especially the hybrid sliver (I) and copper(I) halides have received special attention due to the potential applications in photoluminescent, visible-light sensitizers for photovoltaic cell, chromism, etc.12-52 Generally speaking, the Cu(I) ion is able to adopt myriad coordination geometries including linear CuX2, CuX3 triangle and CuX4 tetrahedron (X = Br, I). More interestingly, the tetrahedral CuX4 unit features high self-assembly characterization and diversiform condensation modes including corner- and edge-sharing as well as short Cu···Cu interactions.53-54 To data, numerous [CuxXy](y-x)- anionic clusters or SBUs have been characterized including binuclear [Cu2X3]-, [Cu2X4]2- and [Cu2X6]4-; trinuclear [Cu3X7]4- and [Cu3X8]5-; tetranuclear [Cu4X6]2-, [Cu4I8]4-, [Cu4X9]5- and [Cu4X11]7-; pentanuclear [Cu5X7]2-; hexanuclear [Cu6I10]4- and [Cu6I11]5-, and even more larger [Cu8I13]5- and [Cu36I56]20- units, etc.55-66 Using these clusters or SBUs as building blocks, a large amount of 1D chains including [Cu2X3]-, [Cu2X4]2-, [Cu3X4]-, [Cu3X6]3-, [Cu4X6]2-, [Cu5X7]2-, [Cu6X7]-, etc, and 2D layers of [Cu3I4]-, [Cu4I5]-, [Cu11I17]6-, etc, have also been reported and characterized.67-80 Relatively, three-dimensional (3D) frameworks are rarely documented with limited topological networks. As well as we known, the SDAs represent one of the most important internal factors for rational design of inorganic network although some external factors including pH value, solvent and reaction temperature also play indispensable roles. Hence, an effective strategy for the development of novel hybrid cuprous halides is to introduce unique templates as SDAs. Here, it should be noted that most of the above hybrid cuprous halides are charge balanced and space compensated by various organic 3 Environment ACS Paragon Plus

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templates as SDAs, such as quaternary ammonium and arsenic cations and so on. In recent years, some new templates including rare earth or TM complex cationes are started to be introduced into hybrid cuprous halides. Comparing with the soft and flexible organic templates, rigid metal complex cations are able to afford more stable templated effects for controlling inorganic microstructures. Functionally, the metal complex cations may enhance or improve the electronic, optical and magnetic properties of hybrid materials. Therefore, the controllable syntheses of functional hybrid cuprous halides based on band structure design have become an attractive direction in addition to the crystal engineering. Although a large amount of hybrid cuprous halides have been reported, little attention was devoted to the “functional hybridization”, especially for the visible light responding photocatalytic activity. Intrigued by the rich structural types and potential photoelectronic properties of these hybrid materials, we undertook systematic study in TM complexes directed cuprous halides under solvothermal condition. Until now, only few compounds in this system were reported comparing with those of organic cations directed phases, such as [Co(phen)2(µ-Cl)]2[Cu9I11H2O]n, [Co(phen)3]2Cu11I15, [Ni(phen)3]Cu10H2I16, etc.81-88 In this paper, we adopted in situ formed [TM(2,2-bipy)3]2+/3+ and [TM(2,2-bipy)2I]+ complex cations as mainly SDAs into cuprous iodides and bromides, which is not studied until now. Fortunately, we prepared five different types of low-dimensional hybrid cuprous halides of [TM(2,2-bipy)3]Cu5I7 (TM = Fe (1), Co(2) and Ni(3)), [TM(2,2-bipy)2I]2Cu7I9 (TM = Mn (4), Cu(5), Ru (6)), [Cu(2,2bipy)2I][(Me)2-2,2-bipy]Cu8I11 (7) and [Co(2,2-bipy)3]Cu5Br8 (8), K[Mn(2,2-bipy)3]2Cu6I11 (9). Their structures feature novel 1D chains or 2D layer based on [CuX4] tetrahedra and [CuX3] triangles. In this paper, we report their syntheses, crystal structures, optical and photocatalytic properties.

EXPERIMENTAL SECTION Materials and Instruments. All reagents and solvents were commercially available and used as received without further purification except that [Ru(2,2-bipy)3]Cl2 was synthesized according to the reference.89 Elemental analyses of C, H and N were performed on a PE2400 II elemental analyzer. 4 Environment ACS Paragon Plus


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Powder X-ray diffraction (PXRD) data were measured in a Bruker D8 ADVANCE powder X-ray diffractometer (Cu Kα, λ = 1.5418 Å) in the 2θ range of 5–80º. UV−vis absorption was monitored with a PE Lambda 900 UV/vis spectrophotometer in the wavelength range of 200−800 nm. The thermal behavior (TGA) was studied by a Mettler TGA/SDTA 851 thermal analyzer under a N2 atmosphere with a heating rate of 10 °C min-1. Semi-quantitative elemental analyses for TM, K, Cu, I and Br were recoded on a JSM-6700F scanning electron microscope (SEM) equipped with an energy dispersive spectroscope (EDS) detector. Preparation of Compounds 1-3. A mixture of FeSO4•7H2O (0.5 mmol), 2,2-bipy (1.5 mmol), CuI (3 mmol), KI (2 mmol), acetonitrile (2.0 mL) and HI aqueous solution (47%, 3.0 mL, about 11 mmol) was sealed in a stainless steel reactor with a 15 mL Teflon liner and heated at 140 ºC for 5 days, and then slowly cooled to room temperature. A large amount of dark red and block-shaped crystals of 1 were found in about 61% yield based on Cu and subsequently determined as [Fe(2,2-bipy)3]Cu5I7. Microprobe elemental analyses on clean surfaces of several single crystals of compound 1 gave average Fe/Cu/I molar ratio of 0.92(5) : 4.93(2) : 7.17(7), which was in good agreement with that determined by single crystal X-ray diffraction study. The crystals were easily collected by hand and washed with distilled water and ethanol. Elem. Anal. Calcd for C30N6H24FeCu5I7: C, 20.82; H, 1.39; N, 4.85%; found: C, 20.79; H, 1.45; N, 4.78%. Other two isostructural phases of 2 and 3 were also synthesized in the analogous manners to that of 1 with Co(CH3COO)2•4H2O and Ni(CH3COO)2•4H2O instead of FeSO4•7H2O, respectively. The yields of the crystals of 2 and 3 were 43% and 37%, respectively. Elem. Anal. Calcd for C30N6H24CoCu5I7 (2): C, 20.82; H, 1.39; N, 4.85%; found: C, 20.77; H, 1.49; N, 4.72%; C30N6H24NiCu5I7 (3): C, 20.82; H, 1.39; N, 4.85%; found: C, 20.88; H, 1.46; N, 4.82%. Preparation of Compounds 4-6. A mixture of Mn(CH3COO)2•4H2O (0.5 mmol), 2,2-bipy (1.5 mmol), CuI (2 mmol), KI (2 mmol), HI aqueous solution (47%, 1.0 mL, about 3.7 mmol) and ethanol (4.0 mL) was sealed in a stainless steel reactor with a 15 mL Teflon liner and heated at 140 ºC for 5 days, and then slowly cooled to room temperature. Dark red and block-shaped crystals of 4 were found in about 30% yield based on CuI and subsequently determined as [Mn(2,2-bipy)2I]2Cu7I9. The crystals 5 Environment ACS Paragon Plus

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were collected by hand and washed with distilled water and ethanol. Elem. Anal. Calcd for C40N8H32Mn2Cu7I11: C, 18.65; H, 1.25; N, 4.35%; found: C, 18.69; H, 1.37; N, 4.40%. Compound 5 was synthesized in the analogous manner to that of 4 with CuSO4•5H2O instead of Mn(CH3COO)2•4H2O with yield of 28%. Elem. Anal. Calcd for C40N8H32Cu9I11 (5): C, 18.53; H, 1.24; N, 4.32%; found: C, 18.58; H, 1.32; N, 4.38%. Compound 6 was synthesized by the reaction of [Ru(2,2bipy)3]Cl2, CuI, KI, HI aqueous solution (1.0 mL, 47%) and ethanol (4.0 mL) at the same condition. The red crystals were obtained with low yield of 9% based on Cu. Microprobe elemental analyses on clean surfaces of several single crystals of compound 6 gave average Ru/Cu/I molar ratio of 1.93(6) : 7.05(6) : 11.11(3), which was in good agreement with that determined by single crystal X-ray diffraction study. Elem. Anal. Calcd for C40N8H32Ru2Cu7I11: C, 18.01; H, 1.21; N, 4.20%; found: C, 18.10; H, 1.27; N, 4.25%. Preparation of Compound 7. CuSO4•5H2O (0.5 mmol), 2,2-bipy (2 mmol), CuI (4.5 mmol), KI (2 mmol), HI aqueous solution (47%, 1.0 mL), and ethanol (4.0 mL) was sealed in a stainless steel reactor, and the mixture was reacted on similar condition as that of compounds 1-6. Subsequently, dark red crystals of 7 were obtained and washed with ethanol with yield of 35%. Elem. Anal. Calcd for C32N6H30Cu9I12: C, 14.82, H, 1.17, N, 3.24%; found: C, 14.93, H, 1.23, N, 3.15%. Preparation of Compound 8. The mixture of Co(CH3COO)2•4H2O (0.5 mmol), 2,2-bipy (1.5 mmol), CuBr (3 mmol), KBr (2 mmol), HBr aqueous solution (48%, 1.0 mL, about 6 mmol) and ethanol (4.0 mL) was reacted on the same conditions of 1-7. Dark red and block-shaped crystals of compound 8 were obtained with yield of 35% based on CuBr. Elem. Anal. Calcd for C30N6H24CoCu5Br8: C, 24.27 H, 1.63, N, 5.66%; found: C, 24.35, H, 1.69, N, 5.57 %. Preparation of Compound 9. A mixture of KI (0.5 mmol), Mn(CH3COO)2•4H2O (0.5 mmol), CuI (2 mmol), 2,2-bipy (1.5 mmol), HI aqueous solution (47%,1 mL) and acetonitrile (4 mL) was sealed in a 15-mL Teflon-lined stainless container, which was heated at the same condition as those of above compounds. Dark red and block-shaped crystals of 9 were found in 15% yield and subsequently determined as K[Mn(2,2-bipy)3]2Cu6I11. The crystals were easily collected by hand and washed with 6 Environment ACS Paragon Plus


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distilled water and ethanol. Microprobe elemental analyses on clean surfaces of several single crystals of compound 9 gave average K/Mn/Cu/I molar ratio of 0.94(7) : 1.95(2) : 6.25(8) : 11.14(4), which was in good agreement with that determined by single crystal X-ray diffraction study. Elem. Anal. Calcd for C60N12H48KMn2Cu6I11: C, 25.17; H, 1.69; N, 5.87 %; found: C, 25.09; H, 1.60; N, 5.93 %. Crystallographic Studies. Single crystals of the title compounds were collected on a Bruker SMART 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 multi-scan absorption corrections were applied using the SCALE program for area detector. The structures were solved by direct method and refined on F2 by full-matrix least-squares method using the SHELXS-97 program.90 All the non-hydrogen atoms were refined with anisotropic thermal parameters, and the hydrogen atoms of 2,2-bipy molecules were generated theoretically onto the specific carbon and nitrogen atoms and isotropically refined with fixed thermal factors. Compound 6 crystallized in the orthorhombic space group Pnma (No. 62) based on systematic absence, E-value statistic and satisfactory refinement. After all the sites were anisotropically refined, the final refinement converged at reliable R1 and wR2 (I > 2σ(I)) factors but with higher displacement parameter for Cu(5) site. The result indicated that the Cu(5) site showed a slight disorder over two positions of Cu(5a) and Cu(5b) with occupancies of 0.441(5) and 0.559(5), respectively. The compounds 4 and 5 were also refined according to the same mode of 6 due to the isostructural characterizations. In compound 7, the Cu(4) atom in the structural model showed slight disorder over two positions of Cu(4a) and Cu(4b) with occupancies of 0.684(7) and 0.316(7), respectively. In compound 9, the K(1) atom also showed slight disorder over two positions with occupancies of 0.481(1) and 0.519(1), respectively. The Cu(5a), Cu(4a) and K(1a) sites of compounds 6, 7 and 9 will be used to discuss the crystal structures in the paper, respectively, due to the proper bond distances despite of the lower occupancies. The crystallographic data for all the compounds are listed in Tables 1-3 and important bond lengths are listed in Tables S1-S9. More details on the crystallographic studies are given in Supporting Information. Photocatalytic Activity Measurement. The photocatalytic activities of as-prepared samples 4, 5 and 7 Environment ACS Paragon Plus

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9 were evaluated by the degradation of Crystal Violet (CV) as model dye pollutant. In a typical process, 30 mg each sample of the compound was added to a 30 mL of 1× 10-5 mol·L-1 solution of CV. After being dispersed in an ultrasonic bath for 30 min, the mixture was then magnetically stirred in the dark for 10 hour before irradiation to ensure adsorption equilibrium between the catalyst and solution. The solution was then exposed to the visible light irradiation from a 50 W Xe lamp with distance of about 15 cm between the Xe lamp and the reaction solution. The cut-off filter was used to remove all wavelengths less than 400 nm and more than 780 nm ensuring irradiation with visible-light only. Every 10 min, 4 mL of the mixture was continually taken from the reaction cell and the catalyst was separated from the suspension by centrifugation. The degradation process was monitored through a wavelength scan on a GBC Cintra 2020 UV/Vis spectrophotometer. For collecting the adequate sample in recycling experiment, two or even more the photocatalytic processes were carried out under the same condition, and then the samples were separated through centrifugation. All the precipitates from the different processes were collected, combined and dried in an oven at 80 ºC for 12 h. After that, 30 mg of dried sample was performed for the second photocatalytic experiment according to the same method as that of first study. The third recycling experiment was also carried out with the same method.

Results and Discussion Syntheses Discussion Solvothermal reaction of cuprous salts, transition metal salts, 2,2-bipy and CuI or CuBr in different mixed solution led to a series of hybrid cuprous halides. Compounds 1-3 and 9 were prepared in mixed acetonitrile and HI solution, whereas other phases were obtained in ethanol and HI or HBr solution. Detailed experiments suggested that the reaction solution played an important role in the assembly generation of anionic framework. For example, the yields of compounds 1-3 will greatly decrease when ethanol was used instead of acetonitrile. In the reaction, the TM ions of Mn2+, Fe2+, Co2+, Ni2+ and Cu2+ were in situ coordinated to 2,2-bipy ligand into [TM(2,2-bipy)3]2+ and [TM(2,2-bipy)2I]+ complex cations. In the preparation of compound 7, the 2,2-bipy molecule was also in situ reacted with alcohol to form N-alkylated [(Me)2-2,2-bipy]2+ cation, which played a key role in the self-assembly 8 Environment ACS Paragon Plus


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reaction of anionic frameworks. Such in situ alkylation reactions under acid hydro(solvo)thermal conditions have been observed in many inorganic-organic hybrid materials, such as (MV)Bi2Cl8, [Mepy][Cu2Br3], [Mepy][Cu2I3], etc.38,48,67,69 Furthermore, the KI or KBr was added in the solution not only used as the source of I- or Br- but also effectively increase the solubility of the CuI or CuBr, respectively. Hence, moderate I- or Br- ions are able to feature relatively strong solution and coordination abilities leading to the higher yields of the title compounds. Description of Structures Structures of compounds 1-3 Single-crystal X-ray diffraction analyses revealed that compounds 1−3 belong to isostructural phases, hence 3 is taken as an example to depict the crystal structure. Compound 3 crystallizes in the orthorhombic space group P212121 (No. 19) and the asymmetric unit consists of one Ni2+, five Cu+, seven I- and three 2,2-bipy ligands. As shown in Figure 1a, all the Cu+ ions are coordinated by four I- ions with distorted tetrahedral geometries. The Cu(1) and Cu(2) ions are coordinated by one µ2-I, two µ3-I and one µ5-I atoms, and Cu(3) and Cu(4) atoms are surrounded by one µ5-I, one µ3-I and two µ2-I atoms, whereas Cu(5) atom connect with three µ3-I and one µ5-I atoms. The Cu-(µ2-I) and Cu-(µ3-I) bond lengths fall in the range of 2.569(2)-2.634(2) Å and 2.606(2)-2.751(2) Å, respectively, and the Cu-(µ5-I) distances are in the range of 2.713(2)-2.798(2) Å. These Cu-I bond distances have the approximate order of d(Cu–µ5-I) > d(Cu–µ3-I) > d(Cu–µ2-I), which is according with those of other hybrid iodocuprates, such as [Etpy][Cu3I4] and [Mepy][Cu2I3], etc.67 Each Cu(1)I4, Cu(2)I4, Cu(3)I4, Cu(4)I4 and Cu(5)I4 tetrahedra are self-condensed by edge-sharing to form a [Cu5I10] fragment (Figure 1a). The neighboring [Cu5I10] fragments are further interconnected via corner-sharing to form the 1D [Cu5I7]2- anionic chain along the a-axis (Figure 1b). In the 1D [Cu5I7]2- chain, all the iodine atoms feature different connecting modes: I(1), I(2) and I(4) connect with two Cu+ ions, and I(3), I(5) and I(6) bridge three Cu+ ions, whereas I(7) is bonded to five Cu+ ions. Although similar 1D [Ag5I7]2- chains have been reported in some iodoargentates, such as (BPO)Ag5I7, [Mn(4,4bipy)(DMF)3(H2O)]Ag5I7·4,4-bipy, (bmph)(Ag5I7), etc,91-94 the 1D [Cu5I7]2- chain has not been characterized until now. Such interconnection also leads to the abundant short Cu···Cu distances of 9 Environment ACS Paragon Plus

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2.786(2)-2.965(2) Å, which are comparable with the sum of van der Waals radii of 2.80 Å indicating the weak metal–metal interactions. The neighboring 1D [Cu5I7]2- chains feature parallel packing along the b- and c-axis. The [Ni(2,2-bipy)3]2+ complex cations as charge-balancing agents are located among the space of 1D anionic chains, forming extensive C–H···I hydrogen bonds with I atoms into a 3D Hbonding network structure (Figure 1c). The C···I separations are in the range of 3.88(1)-3.94(1) Å. Structures of compounds 4-6. The structures of 4-6 crystallize in the orthorhombic space group Pnma (No. 62) and the compound 6 is discussed as example. There are one Ru2+, five Cu+, eight I- and two 2,2-bipy ligands in the asymmetric unit of compound 6. As shown in Figure 2, all the Cu+ ions are coordinated by four I atoms with distorted tetrahedral coordination geometries except of Cu(5) atom with triangle coordination environment (µ1-I + µ2-I + µ4-I). The Cu(1) atom is surrounded by one µ2-I and three µ4-I atoms, and Cu(2) connect with one µ2-I, one µ5-I and two µ4-I atoms, whereas Cu(3) is coordinated by one µ3-I, one µ5-I and two µ4-I atoms. Each Cu(1)I4, Cu(3)I4 and two Cu(2)I4 tetrahedra are interconnected via edge-sharing into a cubane-like [Cu4I8] unit, which is similar to the [Ag4I8] cluster in [MC]Ag2I3, [EC]Ag2I3, etc.7e The [Cu4I8] unit is further attached by one [Cu(5)I3] triangle via edge-sharing to form a [Cu5I9] unit (Figure 2a). On the other hand, the Cu(4) atom contact with one µ2-I, one µ3-I, one µ4-I and one µ5-I atoms, and two Cu(4) tetrahedra are self-condensed to form a [Cu2I6] dimer (Figure 2b). The above [Cu5I9] units and [Cu2I6] dimers are alternately interconnected via edgesharing into the 1D [Cu7I9]2- anionic chain along the a-axis (Figure 2c). These 1D chains feature parallel stacking along the c-axis and are separated by [Ru(2,2-bipy)2I]+ cations along the b-axis (Figure 2d). Within the 1D [Cu7I9]2- chain, I(7) only connect one Cu+ ion as terminal, and I(4) and I(5) bridge two Cu+ ions, and I(3) connect with three Cu+ ions, and I(2) bridge four Cu+ ions, whereas I(1) is bonded to five Cu+ ions. The Cu-I bond distances fall in the range of 2.499(6)-2.759(2) Å following the approximate order of d(Cu–µ5-I) > d(Cu–µ4-I) > d(Cu–µ3-I) > d(Cu–µ2-I) > d(Cu–µ1-I). There are also abundant short Cu···Cu distances of 2.774(2)-2.962(2) Å, which are comparable with those of compound 1 indicating the weak metal–metal interactions.



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Structure of compound 7. Compound 7 crystallizes in the monoclinic space group P21/c (No. 14) and features novel 1D complex [Cu8I11]3- anionic chain directed by mixed [Cu(2,2-bipy)2I]+ complex and [(Me)2-bipy]2+ cations. In the asymmetric unit of compound 7, there are one Cu2+, eight Cu+, twelve I-, one [(Me)2-bipy]2+ and two 2,2-bipy ligands. All the Cu+ ions are coordinated by four I atoms with tetrahedral environment geometries except that the Cu(2)+ ion is surrounded by three I atoms with a planar triangle configuration (µ1-I + µ2-I + µ3-I). Each Cu(3)I4, Cu(4)I4, Cu(5)I4, Cu(7)I4 and Cu(8)I4 tetrahedra are condensed via edge-sharing to form a semi-enclosed [Cu5I10] unit with five terminal I atoms, which is similar to that of compound 3 (Figure 3a). Each Cu(1)I4 and Cu(6)I4 tetrahedron and Cu(2)I3 triangle successively attach the [Cu5I10] unit via edge-sharing to form a complex [Cu8I13] unit (Figure 3b). The neighboring [Cu8I13] units are further interconnected via edge-sharing into the novel 1D [Cu8I11]3- anionic chains along the c-axis (Figure 3c). In the 1D [Cu8I11]3- chains, all the iodine atoms feature multivariate connecting modes: I(2) connect one Cu+ ion as a terminal, I(1), I(3), I(5) and I(9) atoms bridge two Cu+ ions, and I(4), I(6), I(10) and I(11) connect with three Cu+ ions, whereas I(8) and I(7) atoms link the four and five Cu+ ions, respectively. All the Cu-I bond distances fall in the range of 2.524(1)-2.885(1) Å, which are according with those of compounds 1-6 as well as reported hybrid iodocuprates. There are also short Cu···Cu distances of 2.721(2)-2.983(1) Å in the 1D [Cu8I11]3- chains indicating the weak Cu···Cu interactions. As far as we known, such [Cu8I11]3- chain has not been reported in cuprous halides and represents a new type of 1D chain. Along the b-axis, the parallel 1D [Cu8I11]3- chains feature parallel stacking with 1D large pseudo channels. Paralleling to the a-axis, the 1D [Cu8I11]3- chains are bridged by the [Cu(2,2-bipy)2I]+ complex and [(Me)2-bipy]2+ cations via extensive C–H···I hydrogen bonds to form a 2D H-bonding network (Figure 3d). The C···I separations of 3.772(7)-3.821(7) Å are comparable with those of compounds 1-3. Structure of compound 8. Compound 8 belongs to the triclinic space group P-1 (No. 2) and features a novel 1D [Cu5Br8]3- anionic chain. In the asymmetric unit of 8, there are one Co, five Cu, eight Br and three 2,2-bipy ligands. The Cu(1)+ and Cu(4)+ ions adopt tetrahedral coordination environments and Cu(2), Cu(3) and Cu(5) atoms adopt triangle coordination geometries. Most of the Cu-Br bond distances 11 Environment ACS Paragon Plus

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in CuBr4 tetrahedra fall in the range of 2.441(1)-2.577(1) Å except of a slight longer Cu(4)-Br(4) length of 2.742(2) Å. Relatively, the Cu-Br bond distances of 2.348(1)-2.426(2) Å in the CuBr3 triangles are slightly shorter than those of CuBr4 tetrahedra. These Cu-Br bond distances are comparable with those of reported hybrid cuprous bromides, such as [dmebpp][Cu7Br9] and [Mepy][Cu2Br3], etc.67 Two Cu(4)Br4 tetrahedra are initially condensed via edge-sharing to form a [Cu2Br6] dimer, which is further attached by each Cu(2)Br3 and Cu(3)Br3 triangle on two sides via edge-sharing into a circular [Cu6Br10] unit, respectively. On the other hand, two Cu(1)Br4 tetrahedra are joined via edge-sharing to form another [Cu2Br6] dimer, the both ends of which are attached by each Cu(5)Br3 triangle via sharing Br(3) and Br(8) atoms, respectively, into a linear [Cu4Br10] tetramer. These linear [Cu4Br10] tetramers act as linkers to bridge the circular [Cu6Br10] units via sharing the Br(6) atoms to form the 1D [Cu5Br8]3anionic chain along the b-axis (Figure 4a). Within the 1D [Cu5Br8]3- chain, all the Br atoms bridge two Cu+ ions except that the Br(4) connects three Cu+ ions. The Cu···Cu distances of 2.757(2)-2.945(2) Å are comparable with those of compounds 1-7. The 1D [Cu5Br8]3- chains feature directly parallel arrangement along the b-axis without any filling. Along the a-axis, these 1D chains are bridged by [Co(2,2-bipy)3]3+ complex cations via extensive C–H···Br hydrogen bonds to form a 3D supramolecular network with C···Br distances of 3.480(7)-3.742(7) Å (Figure 4c). Structure of compound 9. Compound 9 crystallizes in the trigonal space group R-3 (No. 147) and the asymmetric unit consists of one crystallographically independent K, one Mn, one Cu, three I and three 2,2-bipy ligands. As shown in Figure 5a, the Cu(1) ion is tetrahedral surrounded by one µ3-iodine and three µ2-iodine atoms with normal Cu-I bond distances of 2.651(1)-2.742(1) Å. Three neighboring CuI4 tetrahedra are condensed via sharing I(1) and I(2) atoms to form a triangular [Cu3I7] trimer with three outside I(3) atoms. Such interconnection also leads to a [Cu3] triangle with Cu···Cu distance of 2.863(2) Å. Similar trimerical [Cu3I7] unit has also been reported in [De-DABCO]2[MeDABCO]Cu11I17.19d Each [Cu3I7] trimer as new SBU is further connected to three adjacent ones via sharing I(3) atoms to form a novel 2D [Cu6I11]5- layer along the ab-plane with a (6,3) topological network (Figure 5b). As a result, the 2D layer contains a [Cu12I12] 24-membered ring with the hexagonal 12 Environment ACS Paragon Plus


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cross-section of 12.847 ×12.847 Å2 presented along the c-axis. In the 2D [Cu6I11]5- layer, the I(1) atom connect three Cu+ ions, and I(2) and I(3) atoms bridge the two Cu+ ions. The 2D [Cu6I11]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@Cu6I11]4 – 3D framework with 1D large channel sized at 11.656 × 11.924 Å2 (Figure 5c). The K+ ion is surrounded by eight I(2) atoms in a octahedral coordination environment with the K-I bond distances of 3.8204(4)-3.8225(4) Å. All the [Mn(2,2-bipy)3]2+ complex cations as charge balance and space filling occupy the 1D channel along the c-axis, where weak C–H···I hydrogen bonds also occur. It is worth noting that the tetrahedral [CuI4] unit often undergoes a variety of self-condensation to form polyanions of cluser or oligomer as SBUs. However, most of the SBUs are self-condensed to form 1D anionic chains, such as[Cu2X3]-, [Cu2X4]2-, [Cu3X4]-, [Cu3X6]3-, [Cu4X6]2-, [Cu5X7]2-, [Cu6X7]-, etc.67-80 Occasionally, these SBUs can also be interlinked to form 2D microporous layers, for example, two isomeric 2D [Cu11I17]6- layers are composed of [Cu3I7], [Cu4I8], [Cu6I12] and [Cu12I22] units in [deDABCO]2[meDABCO]Cu11I17.74 Undoubtedly, the 2D [Cu6I11]5- layer reported here based on trimeric [Cu3I7] building blocks represents new microporous layer in hybrid iodocuprate chemistry. Furthermore, the [Cu5I7]2-, [Cu7I9]2-, [Cu8I11]3-, [Cu5Br8]3- units in compounds 1-8 have also not been characterized until now and belong to the new types of 1D chains in hybrid cuprous halides. Thermal Stabilities Thermal gravimetric behaviors of the title compounds were investigated under nitrogen atmosphere in the temperature range of 30–800 °C and the thermogravimetric analyses (TAG) curves are shown in Figure S1. The compounds 1, 2, 8 and 9 start to decompose at about 200 °C, 50°C, 220 °C and 240 °C, respectively, and do not achieve the balance to 800 ºC, which may be due to that the decomposition of complexes simultaneously lead to the complete collapse and volatilization of the anionic frameworks. Compound 3 has a one-step weight loss of 26.8% (theoretical value of 27.0%), corresponding to the loss of all 2,2-bipy ligands per formula from 230 ºC to 270 ºC. Compound 4 features two-step successive weight loss of all 2,2-bipy ligands per formula in the range of 200-350 °C and 350-410 °C, respectively. The observed weight loss of 25.5% is close to the theoretical value of 24.5%. Compound 5 starts to decompose at 200 ºC and lose all 2,2-bipy ligands and two coordinated I 13 Environment ACS Paragon Plus

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atoms per formula until 370 ºC with observed weight loss of 33.5% corresponding to the theoretical values of 33.8%. Compound 6 features successive weight loss of all 2,2-bipy molecules and two coordinated I atoms in the range of 210-470 °C, and the observed weight loss of 34.1% is comparable with the theoretical value of 32.9%. After about 500 °C, compound 6 continue to loss weight corresponding to the decomposition of inorganic network. From 210 to 370 °C, compound 7 features a one-step weight loss of 31.6% (theoretical value of 31.5%), corresponding to the loss of two 2,2-bipy ligands, one [(Me)2-2,2-bipy] molecule, one Cu atom and two I elements per formula. After the major weight loss, the compounds 3-5 and 7 continue to slowly lose weight and do not achieve the balance to 700 ºC. Optical Properties The solid-state optical diffuse reflection spectra of the title compounds were measured at room temperature and calculated from the diffuse reflectance data by using the Kubelka– Munk function (Figure S2). It can be seen that the title compounds feature two different types of optical diffuse reflection spectra. The band gaps of compounds 1-3 and 8-9 are estimated by extrapolation of the linear portion of the absorption edges as about 1.85, 1.95, 1.88, 1.69 and 1.88 eV, respectively, which are accordance with their dark red colors. The optical absorption edges of 4-7 are found to be 1.44, 1.52, 1.68 and 1.57 eV, respectively, which are slightly smaller than those of compounds 1-3 and 8-9. In addition, the peaks below the 2.0 eV in the absorption spectrum of 4-7 maybe arise from the d-d electronic transition of the TM cations. The distinction of absorption spectrum of 1-3, 8-9 and 4-7 may be caused by different coordination environments of the TM ions. In the former phases, the TM ions adopt the octahedral geometries with six nitrogen atoms of three 2,2-bipy ligands, whereas they are coordinated by four nitrogen atoms from two 2,2-bipy ligands and one I atom with distorted quadrangular pyramidal geometries in compounds 4-7. Furthermore, all the title compounds have smaller band gaps and exhibit red shifts of the absorption edges compared with the bulk CuI (2.95 eV) and CuBr (2.89 eV) as well as most of the hybrid cuprous halides directed by organic cations, which illustrate the distinct optical tunable abilities of TM complex cations comparing with organic cations.



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Photocatalytic Properties The researches on visible light responding photocatalytic properties over hybrid cuprous halides are relatively less reported. Narrow band gaps of the title compounds encourage us to investigate their visible light photocatalytic activities, which were evaluated by the photodegradation of organic contaminants, such as CV as the test pollutant. In the absence of catalysts, the CV self-photodegradation is almost negligible, and the catalytic experiment without light irradiation also shows none observable decrease in CV concentration. Figure 6 illustrates the time dependent absorption spectra of CV degraded by samples 4, 5 and 9. The degradation efficiency is defined as C/C0, where C and C0 represent the remnant and initial concentration of CV, respectively. Samples 4 and 5 feature similar photocatalytic effects, and the degradation ratio of CV reached nearly 100 % after 60 and 50 min, respectively, resulting in complete decolorization. Such phenomena is also demonstrated by the change in the color of the dispersion from an initial purple to a nearly colorless (the inset of Figure S3). Compared with 4 and 5, sample 9 shows evidently higher photocatalytic activity and it can completely decompose the CV within 10 min. At the same time, we studied the photocatalytic property of N-doped P25 as an benchmark under the completely same condition, and the result shows that more than 70% of CV is still alive after irradiation for 60 min. Obviously, both the samples have faster photodegradation speeds than N-doped P25 for CV under visible light irradiation. Furthermore, we also study their recycling performances and found only slight decay (about 3%) in the catalytic efficiencies over three cycles (Figure S3). After photocatalysis, the XRD patterns of compounds 4, 5 and 9 was still in agreement with the original values, which implies the unchanged basic structures as well as the stabilities of compounds 4, 5 and 9 as the visible light responding photocatalysts (Figure S5). We also study the photodegradation effects of the samples over a large amount of organic pollutants, such as Rhodamine B (RhB), Methyl Orange (MO) and Methylene Blue (MB), etc, but the results showed the too longer reaction time or incomplete photodegradation, which is meaningless for our study and no longer discussed.


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Conclusion In conclusion, a series of hybrid cuprous halides directed by TM complex cations have been solvothermally synthesized, structurally and optically characterized. These compounds feature novel 1D [Cu5I7]2-, [Cu7I9]2-, [Cu8I11]3-, [Cu5Br8]3- chains and 2D [Cu6I11]5- layers based on CuX3 triangles and/or CuX4 tetrahedra demonstrating the diversiform condensation modes of the building units. Meanwhile, the introduction of TM complex cations leads to red shifts of the absorption edge of hybrid materials with narrow band gaps of 1.44-1.95 eV comparing with CuI and CuBr. The photocatalytic experiments show that samples 4, 5 and 9 have the excellent photodegradative abilities for organic contaminant than N-doped P25 indicating the visible light responding photocatalytic properties. These studies further illustrate the unique tunable abilities of TM complex cations on the crystal engineering, band structures and photoelectric properties of hybrid materials. It is anticipated that more hybrid cuprous halides with novel structures and tunable photoelectric properties can be obtained by selecting suitable TM complex cations as SDAs. Further studies on the structural regulation and structure–photocatalytic property relationship are also in progress in our group.

Acknowledgments We thank the financial supports from the National Nature Science Foundation of China (Nos. 21201081 and 21571081) and Fund of state key laboratory of structural chemistry (No. 20150005).

Supplementary Information Electronic supplementary information (ESI) available: Crystallographic data in CIF format (CCDC numbers 1410565 for 1, 1410558 for 2, 1410559 for 3, 1412381 for 4, 1412384 for 5, 1412153 for 6, 1410562 for 7, 1410563 for 8 and 1410564 for 9), and tables of selected bond distances, thermogravimetric curves, optical diffuse reflectance spectra, absorption spectra of photodegradative CV and XRD powder patterns. 16 Environment ACS Paragon Plus


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References (1) Feng, P. Y.; Bu, X, H.; Zheng, N. F. Acc. Chem. Res. 2005, 38, 293–303. (2) Xiong, W. W.; Zhang, G. D.; Zhang, Q. C. Inorg. Chem. Front., 2014, 1, 292–301. (3) Zhou, J.; Dai, J.; Bian, G. Q.; Li, C. Y.; Coord. Chem. Rev. 2009, 253, 1221–1247. (4) Gong, Q. H.; Hu, Z. C.; Deibert, B. J.; Emge, T. J.; Teat, S. J.; Banerjee, D.; Mussman, B.; Rudd, N. D.; Li, J. J. Am. Chem. Soc. 2014, 136, 16724–16727. (5) Pardo, R.; Zayat, M.; Levy, D. Chem. Soc. Rev., 2011, 40, 672–687. (6) Bellitto, C.; Bauer, E. M.; Righini, G. Coord. Chem. Rev., 2015, 289–290, 123–136. (7) Wang, C.; Volotskova, O.; Lu, K. D.; Ahmad, M.; Sun, C.; Xing, L.; Lin, W. B. J. Am. Chem. Soc., 2014, 136, 6171–6174. (8) W. L. Leong, J. J. Vittal, Chem. Rev., 2011, 111, 688–764. (9) Zhao, S. P.; Ren, X. M. Dalton Trans., 2011, 40, 8261–8272. (10) Fuhr, O.; Dehnenb, S.; Fenske, D. Chem. Soc. Rev., 2013, 42, 1871–1906. (11) Lu, H. C.; Gautier, R.; Donakowski, M. D.; Tran, T. T.; Edwards, B. W.; Nino, J. C.; Halasyamani, P. S.; Liu, Z. T.; Poeppelmeier, K. R. J. Am. Chem. Soc., 2013, 135, 11942–11950. (12) Stoumpos, C. C.; Frazer, L.; Clark, D. J.; Kim, Y. S.; Rhim, S. H.; Freeman, A. J.; Ketterson, J. B.; Jang, J. I.; Kanatzidis, M. G. J. Am. Chem. Soc., 2015, 137, 6804–6819. (13) Yu, T. L.; Zhang, L.; Shen, J. J.; Fu, Y. B.; Fu, Y. L.; Dalton Trans., 2014, 43, 13115–13121. (14) Kazim, S.; Nazeeruddin, M. K.; Grätzel, M.; Ahmad, S. Angew. Chem. Int. Ed., 2014, 53, 2812– 2824. 17 Environment ACS Paragon Plus

Page 19 of 33

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


(15) Hao, F.; Stoumpos, C. C.; Chang, R. P. H.; Kanatzidis, M. G. J. Am. Chem. Soc., 2014, 136, 8094–8099. (16) Shen, Y. L.; Lu, J. L.; Tang, C. Y.; Fang, W.; Jia, D. X.; Zhang, Y. Dalton Trans., 2014, 43, 9116–9125. (17) Fang, W.; Tang, C. Y.; Chen, R. H.; Jia, D. X.; Jiang, W. Q.; Zhang, Y. Dalton Trans., 2013, 42, 15150–15158. (18) Wang, G. E.; Jiang, X. M.; Zhang, M. J.; Chen, H. F.; Liu, B. W.; Wang, M. S.; Guo, G. C. CrystEngComm, 2013, 15, 10399–10404. (19) Lemmerer, A.; Billing, D. G. CrystEngComm, 2012, 14, 1954–1966. (20) Zhao, H. R.; Li, D. P.; Ren, X. M.; Song, Y.; Jin, W. Q. J. Am. Chem. Soc. 2010, 132, 18–19. (21) Apostolico, L.; Kociok-Köhn, G.; Molloy, K. C.; Blackman, C. S.; Carmaltb, C. J.; Parkinb, I. P. Dalton Trans., 2009, 10486–10494. (22)

Knorr, M.; Khatyr, A.; Aleo, A. D.; Yaagoubi, A. E.; Strohmann, C.; Kubicki, M. M.;

Rousselin, Y.; Aly, S. M.; Fortin, D.; Lapprand, A.; Harvey, P. D. Cryst. Growth Des., 2014, 14, 53735387. (23) Gschwind, F.; Sereda, O.; Fromm, K. M. Inorg. Chem., 2009, 48, 10535-10547. (24) Knorr, M.; Bonnot, A.; Lapprand, A.; Khatyr, A.; Strohmann, C.; Kubicki, M. M.; Rousselin, Y.; Harvey, P. D. Inorg. Chem., 2015, 54, 4076-4093. (25) Knorr, M.; Guyon, F.; Khatyr, A.; Strohmann, C.; Allain, M.; Aly, S. M.; Lapprand, A.; Fortin, D.; Harvey, P. D. Inorg. Chem., 2012, 51, 9917-9934. (26) Sagué, J. L.; Fromm, K. M. Cryst. Growth Des., 2006, 6, 1566-1568.



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

Page 20 of 33

(27) Lapprand, A.; Bonnot, A.; Knorr, M.; Rousselin, Y.; Kubicki, M. M.; Fortina, D.; Harvey, P. D. Chem. Commun., 2013, 49, 8848-8850. (28) Knorr, M.; Guyon, F.; Khatyr, A.; Däschlein, C.; Strohmann, C.; Aly, S. M.; Abd-El-Aziz, A. S.; Fortinc, D.; Harvey, P. D. Dalton Trans., 2009, 948-955. (29) Mishra, S.; Jeanneau, E.; Daniele, S.; Ledoux, G.; Swamy, P. N. Inorg. Chem., 2008, 47, 9333– 9343. (30) Zhang, Z. J.; Xiang, S. C.; Guo, G. C.; Xu, G.; Wang, M. S.; Zou, J. P.; Guo, S. P.; Huang, J. S. Angew. Chem. Int. Ed., 2008, 47, 4149–4152. (31) Li, J. P.; Li, L. H.; Wu, L. M.; Chen, L. Inorg. Chem., 2009, 48, 1260–1262. (32) Mishra, S.; Jeanneau, E.; Ledouxc, G.; Daniele, S. Dalton Trans., 2009, 4954-4961. (33) Shen, J. J.; Zhang, C. F.; Yu, T. L.; An, L.; Fu, Y. L. Cryst. Growth Des., 2014, 14, 6337-6342. (34) Lin, R. G.; Xu, G.; Lu, G.; Wang, M. S.; Li, P. X.; Guo, G. C. Inorg. Chem., 2014, 53, 5538−5545. (35) Adonin, S. A.; Sokolov, M. N.; Smolentsev, A. I.; Kozlova, S. G.; Fedina, V. P. Dalton Trans., 2013, 42, 9818–9821. (36) Monakhov, K. Y.; Gourlaouen, C.; Pattacini, R.; Braunstein, P. Inorg. Chem., 2012, 51, 1562– 1568. (37) Leblanc, N.; Allain, M.; Mercier, N.; Cariati, E. Cryst. Growth Des., 2011, 11, 5200–5205. (38) Leblanc, N.; Allain, M.; Mercier, N.; Sanguinet, L. Cryst. Growth Des., 2011, 11, 2064–2069. (39) Leblanc, N.; Mercier, N.; Zorina, L.; Simonov, S.; Auban-Senzier, P.; Pasquier, C. J. Am. Chem. Soc., 2011, 133, 14924–14927. 19 Environment ACS Paragon Plus

Page 21 of 33

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


(40) Leblanc, N.; Bi, W. H.; Mercier, N.; Auban-Senzier, P.; Pasquier, C. Inorg. Chem., 2010, 49, 5824–5833. (41) Xu, G.; Guo, G. C.; Guo, J. S.; Guo, S. P.; Jiang, X. M.; Yang, C.; Wang, M. S.; Zhang, Z. J. Dalton Trans., 2010, 39, 8688–8692. (42) Goforth, A. M.; Tershansy, M. A.; Smith, M. D.; Peterson Jr. L.; Kelley, J. G.; DeBenedetti, W. J. I.; Loye, H.-C. z. J. Am. Chem. Soc., 2011, 133, 603–612. (43) Bi, W. H.; Leblanc, N.; Mercier, N.; Auban-Senzier, P.; Pasquier, C. Chem. Mater., 2009, 21, 4099–4101. (44) Mishra, S.; Jeanneau, E.; Daniele, S.; Ledoux, G. Dalton Trans., 2008, 6296–6304. (45) Mishra, S.; Jeanneau, E.; Ledoux, G.; Daniele, S. Inorg. Chem., 2014, 53, 11721–11731. (46) Yu, T. L.; An, L.; Zhang, L.; Shen, J. J.; Fu, Y. B.; Fu, Y. L. Cryst. Growth Des., 2014, 14, 3875−3879. (47) Zhang, R. C.; Zhang, Y. J.; Yuan, B. Q.; Miao, J. P.; Pei, B. H.; Liu, P. P.; Wang, J. J.; Zhang, D. J. J. Solid State Chem., 2014, 220, 185–190. (48) Chan, H.; Chen, Y.; Dai, M.; Lü, C. N.; Wang, H. F.; Ren, Z. G.; Huang, Z. J.; Nia, C. Y.; Lang, J. P. CrystEngComm, 2012, 14, 466–473. (49) Yue, J. M.; Niu, Y. Y.; Zhang, B.; Ng, S. W.; Hou, H. W. CrystEngComm, 2011, 13, 2571–2577. (50) Li, H. H.; Chen, Z. R.; Cheng, L. C.; Feng, M.; Zheng, H. D.; Li, J. Q. Dalton Trans., 2009, 4888–4895. (51) Liu, G. N.; Liu, L. L.; Chu, Y. N.; Sun, Y. Q.; Zhang, Z. W.; Li, C. C. Eur. J. Inorg. Chem., 2015, 478–487.



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

Page 22 of 33

(52) Jiang, Y. S.; Yao, H. G.; Ji, S. H.; Ji, M.; An, Y. L. Inorg. Chem., 2008, 47, 3922–3924. (53) Peng, R.; Li, M.; Li, D. Coord. Chem. Rev., 2010, 254, 1–18. (54) Hou, Y. L.; Sun, R. W. Y.; Zhou, X. P.; Wang, J. H.; Li, D. Chem. Commun., 2014, 50, 2295– 2297. (55) Healy, P. C.; Engelhardt, L. M.; Patrick, V. A.; White, A. H. J. Chem. Soc., Dalton Trans., 1985, 2541–2545. (56) Levy, A. T.; Olmstead, M. M.; Patten, T. E. Inorg. Chem., 2000, 39, 1628–1634. (57) Willett, R. D.; Pon, G.; Nagy, C. Inorg. Chem., 2001, 40, 4342–4352. (58) Liu, S. H.; Chen, J. D.; Liou, L. S.; Wang, J. C. Inorg. Chem., 2001, 40, 6499–6501. (59) Haddad, S.; Willett, R. D. Inorg. Chem., 2001, 40, 809–811. (60) Willett, R. D.; Jeitler, J. R.; Twamley, B. Inorg. Chem., 2001, 40, 6502–6505. (61) Hu, M. C.; Wang, Y.; Zhai, Q. G.; Li, S. N.; Jiang, Y. C.; Zhang, Y. Inorg. Chem., 2009, 48, 1449−1468. (62) Graham, P. M.; Pike, R. D. Inorg. Chem., 2000, 39, 5121−5132. (63) Liu, Z.-W.; Qayyum, M. F.; Wu, C.; Whited, M. T.; Djurovich, P. I.; Hodgson, K. O.; Hedman, B.; Solomon, E. I.; Thompson, M. E. J. Am. Chem. Soc., 2011, 133, 3700−3703. (64) Hartl, H.; Fuchs, J. Angew. Chem. Int. Ed., 1986, 25, 569–570. (65) Jalilian, E.; Liao, R. Z.; Himo, F.; Brismar, H.; Laurell, F.; Lidin, S. CrystEngComm, 2011, 13, 4729–4734. (66) Mahdjour-Hassan-Abadi, F.; Hartl, H.; Fuchs, J. Angew. Chem. Int. Ed., 1984, 23, 514–515.


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(67) Hou, J. J.; Li, S. L.; Li, C. R.; Zhang, X. M. Dalton Trans., 2010, 39, 2701–2707. (68) Li, S. L.; Zhang, R.; Hou, J. J.; Zhang, X. M. Inorg. Chem. Commu., 2013, 32, 12–17. (69) Hou, Q.; Xu, J. N.; Yu, J. H.; Wang, T. G.; Yang, Q. F.; Xu, J. Q. J. Solid State Chem., 2010, 183, 1561–1566. (70) Mishra, S.; Jeanneau, E.; Daniele, S.; Hubert-Pfalzgraf, L. G. CrystEngComm, 2008, 10, 814– 816. (71) Gao, X.; Zhai, Q. G.; Li, S. N.; Xia, R.; Xiang, H. J.; Jiang, Y. C.; Hu, M. C. J. Solid State Chem., 2010, 183, 1150–1158. (72) Gee, W. J.; Batten, S. R. Cryst. Growth Des., 2013, 13, 2335−2343. (73) Li, L.; Chen, H.; Qiao, Y. Z.; Niu, Y. Y. Inorg. Chem. Acta., 2014, 409, 227−232. (74) Li, S. L.; Zhang, X. M. Inorg. Chem., 2014, 53, 8376–8383. (75) (a) Jalilian, E.; Lidin, S. CrystEngComm, 2011, 13, 5730–5736. (76) Hou, J. J.; Guo, C. H.; Zhang, X. M. Inorg. Chem. Acta., 2006, 359, 3991–3995. (77) Hammond, R. P.; Chesnut, D. J.; Zubieta, J. A. J. Solid State Chem., 2001, 158, 55–60. (78) Li, G. H.; Shi, Z.; Liu, X. M.; Dai, Z. M.; Feng, S. H. Inorg. Chem., 2004, 43, 6884–6886. (79) Zhang, Y.; He, X.W.; Zhang, J.; Feng, P. Y. Cryst. Growth Des., 2011, 11, 39–32. (80) Song, J.; Hou, Y. J.; Zhang, L. F.; Fu, Y. L. CrystEngComm, 2011, 13, 3750–3755. (81) Yu, J. H.; Jia, H. B.; Pan, L. Y.; Yang, Q. X.; Wang, T. G.; Xu, J. Q.; Cui, X. B.; Liu, Y. J.; Li, Y. Z.; Lü, C. H.; Ma, T. H. J. Solid State Chem., 2003, 175, 152–158.



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(82) Tershansy, M. A.; Goforth, A. M.; Ellsworth, J. M.; Smith, M. D.; zur Loye, H.-C. CrystEngComm, 2008, 10, 833–838. (83) Li, Q. Y.; Fu, Y. L. CrystEngComm, 2009, 11, 1515–1518. (84) DeBord, J. R. D.; Lu, Y. J.; Warren, C. J.; Haushalter, R. C.; Zubieta, J. Chem. Commu., 1997, 1365–1366. (85) Mishra, S.; Jeanneau, E.; Daniele, S.; Hubert-Pfalzgraf, L. G. CrystEngComm, 2008, 10, 814– 816. (86) Mishra, S.; Jeanneau, E.; Chermette, H.; Daniele, S.; Hubert-Pfalzgraf, L. G. J. Chem. Soc. Dalton Trans., 2008, 620–630. (87) Mishra, S.; Jeanneau, E.; Ledoux, G.; Daniele, S. CrystEngComm, 2012, 14, 3894–3901. (88) Mishra, S.; Pfalzgraf, L. G. H.; Jeanneau, E.; Chermette, H. Dalton Trans., 2007, 410–413. (89) J. N. Braddock , T. J. Meyer, J. Am. Chem. Soc., 1973, 95, 3158–3162. (90) G. M. Sheldrick, SHELXTL, University of Götingen, Götingen, 2001. (91) (a) Dohner, E. R.; Hoke, E. T.; Karunadasa, H. I. J. Am. Chem. Soc., 2014, 136, 1718−1721. (92) Shen, Y. L.; Lu, J. L.; Tang, C. Y.; Fang, W.; Zhang, Y.; Jia, D. X. RSC Adv., 2014, 4, 39596– 39605. (93) Li, H. H.; Chen, Z. R.; Li, J. Q.; Huang, C. C.; Zhang, Y. F.; Jia, G. X. Eur. J. Inorg. Chem., 2006, 2447–2453. (94) Li, H. H.; Xing, Y. Y.; Lian, Z. X.; Gong, A. W.; Wu, H. Y.; Li, Y.; Chen, Z. R. CrystEngComm, 2013, 15, 1721-1728.


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Table 1. Crystal Data and Structure Refinements for compounds 1-3. Compound Chemical Formula

1 C30N6H24FeCu5I7

2 C30N6H24CoCu5I7

3 C30N6H24NiCu5I7

Formula weight

1730.40

1733.48

1733.26

Space group

P212121 (No. 19)

P212121 (No. 19)

P212121 (No. 19)

a/Å

13.4104(9)

13.5177(12)

13.4901(12)

b/Å

13.7920(10)

13.8827(13)

13.8822(12)

c/Å

23.7344(16)

23.867(2)

23.859(2)

V/Å3

4389.8(5)

4479.0(7)

4468.1(7)

Z

4

4

4

Dcalcd (g·cm-3)

2.618

2.571

2.577

Temp (K)

293(2)

293(2)

293(2)

µ (mm-1)

7.652

7.546

7.615

F(000)

3152

3156

3160

hkl range

±17, ±17, (-31,30)

±17, ±18, (-31,30)

±17, ±18, (-31,30)

Reflections collected

51394

52362

51993

Unique reflections

10097

10294

10285

Reflections (I>2σ(I))

8969

9258

9446

Completeness

99.4 %

99.7 %

99.5 %

1.037

1.138

1.116

R1,wR2 (I > 2σ(I))

0.0456/0.1318

0.0505/0.1463

0.0413/0.1150

R1,wR2 (all data)

0.0535/0.1376

0.0567/0.1502

0.0467/0.1184

GOF on F

2 a

a

R1 = ∑||Fo| -|Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 -(Fc)2]2/∑w[(Fo)2]2}1/2



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Table 2. Crystal Data and Structure Refinements for compounds 4-6. Compound

4

5

6

Chemical Formula

C40N8H32Mn2Cu7I11

C40N8H32Cu9I11

C40N8H32Ru2Cu7I11

Formula weight

2575.30

2592.50

2667.56

Space group

Pnma (No. 62)

Pnma (No. 62)

Pnma (No. 62)

a/Å

13.6964(7)

13.6990(9)

13.766(2)

b/Å

28.1015(14)

28.1382(18)

28.086(5)

15.4042(8)

15.4525(10)

15.412(3)

5928.9(5)

5956.4(7)

5958.7(19)

4

4

4

Dcalcd (g·m )

2.885

2.891

2.974

Temp (K)

293(2)

293(2)

293(2)

µ (mm )

8.633

8.884

8.673

F(000)

4656

4688

4808

hkl range

±17, (-35, 36), ±19

±17, ±36, ±19

±17, ±36, (-15, 20)


66529

66869

41228

Unique reflections

6960

6975

6932


5744

5879

6337

Completeness

99.5 %

99.4 %

99.6 %

GOF on F2

1.064

1.050

1.092

R1,wR2 (I > 2σ(I))a

0.0463/0.1271

0.0423/0.1126

0.0608/0.1804

R1,wR2 (all data)

0.0587/0.1344

0.0519/0.1198

0.0660/0.1858

c/Å 3

V(Å ) Z -3

-1

a



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Table 3. Crystal Data and Structure Refinements for compounds 7-9. Compound

7

8

9

Chemical

C32N6H30Cu9I12

C30N6H24CoCu5Br8

C60N12H48KMn2Cu6I11

Formula weight

2593.28

1484.46

2863.22

Space group

P21/c (No. 14)

P-1 (No. 2)

R-3 (No. 147)

a/Å

26.4739(12)

9.4309(6)

14.2597(7)

b/Å

14.9139(7)

10.9803(7)

14.2597(7)

c/Å

14.1172(7)

19.8098(12)

31.7534(16)

α/º

90

88.3670(10)

90

β/º

99.8200(10)

89.7470(10)

90

90

83.3930(10)

120

5492.2(5)

2036.9(2)

5591.7(5)

4

2

3

Dcalcd (g·cm )

3.136

2.420

2.551

Temp (K)

293(2)

293(2)

293(2)

µ (mm-1)

10.188

10.839

6.661

F(000)

4644

1396

3954

hkl range

±34, ±19, ±18

±12, ±14, ±25

±18, ±18, (-40, 41)


63180

23956

21749

Unique

12682

9190

2887


10381

6076

2651

Completeness

99.4 %

98.0 %

99.3 %

GOF on F2

1.004

1.046

1.079

R1,wR2 (I > 2σ(I))a

0.0320/0.0777

0.0423/0.1275

0.0371/0.0933

R1,wR2 (all data)

0.0570/0.1543

0.0438/0.0829

0.0405/0.0958

γ/º 3

V(Å ) Z -3

a




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Scheme 1. Solvothermal syntheses of the title compounds.

(a)

(b)

(c) Figure 1 View of the circular [Cu5I10] fragment (a), 1D [Cu5I7]2- chain (b) and the crystal structure of compound 3 along the a-axis (c). 27 Environment ACS Paragon Plus

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(a)

(b)

(c)

(d) Figure 2 Detailed view of the 1D [Cu5I9] unit (a) and [Cu2I6] dimer (b), 1D [Cu7I9]- chain (c) and network of the compound 6 along the a-axis (c). The green and blue modes represent the [Cu5I9] and [Cu2I6] dimer, respectively.



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(a)

Page 30 of 33

(b)

(c)

(d) Figure 3 View of the [Cu5I10] fragment (a), [Cu8I13] unit (b), 1D [Cu8I11]3- chain (b) and the packing crystal of compound 7 along the c-axis (c). The neighboring [Cu8I13] unit was shown in green and blue modes for clarity in c, respectively.


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(a)

(b) Figure 4 View of the 1D [Cu5Br8]3- chain (b) and the packing structure of compound 8 along the b-axis (b).



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(a)

(b)

(c) Figure 5 Detailed view of the [Cu3I7] SBU (a), 2D [Cu6I11]5- layer (b) and the general view of the compound 9 along the b-axis (d). The [AgI4] tetrahedra are drawn as green only for clarity.


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Figure 6 Photocatalytic decomposition of the aqueous solution of CV under irradiation of samples 4, 5, 9 and N-doped P25.


Low-Dimensional Hybrid Cuprous Halides Directed by Transition

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