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Assembly of two novel Cd3/(Cd3+Cd5)-cluster-based metal–organic frameworks: structures, luminescence and photocatalytic degradation of organic dyes Ya-Pan Wu, Xue-Qian Wu, Jian-Fang Wang, Jun Zhao, Wen-Wen Dong, Dong-Sheng Li, and Qichun Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00093 • Publication Date (Web): 14 Mar 2016 Downloaded from http://pubs.acs.org on March 14, 2016

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Crystal Growth & Design

Assembly of two novel Cd3/(Cd3+Cd5)-cluster-based metal–organic frameworks: structures, luminescence and photocatalytic degradation of organic dyes

Ya-Pan Wu†,‡, Xue-Qian Wu†, Jian-Fang Wang†, Jun Zhao†,Wen-Wen Dong†, Dong-Sheng Li†*，，Qi-Chun Zhang§*

†

College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New

Energy Microgrid, Key laboratory of inorganic nonmetallic crystalline and energy conversion materials,China ‡

Three Gorges University, Yichang, 443002, P. R. China, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, §

Xi’an 710069, P. R. China, and School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to)

* Corresponding authors

E-mail address: [email protected] (D.-S. Li), [email protected](Q.-C.Zhang).Tel./Fax: +86-717-6397516.

Cryst. Growth Des.

1

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ABSTRACT

Two new 3D multinodal Cd(II)–organic frameworks, [Cd3(dccpa)(bipy)0.5(H2O)4]·5H2O (1) and

[(CH3)2NH2]2[Cd11(dccpa)4(DMF)4(H2O)8]·4H2O

(2)

(H6dccpa=

3,4-di(3,5-dicarboxyl

phenyl) phthalic acid, bipy=4,4'-bipyridine), have been prepared and fully characterized. Compound 1 possess 3D neutral framework with a new (6, 6, 7)-connected topology based on single trinuclear

cluster, while 2 features a 3D anionic framework with a new (5, 6, 6,

10)-connected topology containing mixed trinuclear and pentanuclear clusters. Remarkably, 1 and 2 show promising photocatalytic activities toward the degradation of Rhodamine B(RhB) and methyl blue(MB), which suggests that different kinds of cluster units may exert different impact on the decomposition of organic dyes.

2


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Introduction The cluster-based metal-organic frameworks (MOFs) have emerged as an important class of crystalline materials due to their fundamental significance in crystal engineering and molecular topology as well as their promising properties including gas adsorption, luminescence, catalysis, and magnetism.1-20 It is well-known that the synthesis of cluster-based MOFs is a very intricated process and it still remains a big challenge in crystal engineering, because the cluster-based SBUs are occasionally engendered in situ in different systems.21-23 Current studies indicated that the polydentate organic ligands binding to metal centers with high coordination numbers could result in significant structural changes of the resultant clusters during the self-assembling processes.24-31 Among all polydentate organic ligands, conjugated polycarboxylic acids could be prone to ligate multiple metal ions with specific coordination geometries to produce polycarboxylato-metal clusters, such as [Cu2(OH)2(COO)4], [Co4(OH)2(COO)6], and [Zn4O(COO)6], etc.32-34 Specially, many Cd(II)-MOFs based on Cd2, Cd3, Cd4, Cd5

and Cd6 clusters can be modulated by

polycarboxylic acids and different N-donor co-ligands. In addition, these compounds possess diversified network topologies, luminescence and photocatalytic properties.35-38 However, polynuclear Cd(II) clusters with higher nuclei or mixed-clusters in the same system are still rare. In our previous work, a series of unusual 6-, 8-, and 10-connected MOFs, based on Co3, Co5, Co8, or Pb6 clusters, have been constructed from the mixed-ligand systems of different aromatic polycarboxylic and nitrogen co-ligands, which have shown interesting magnetic and luminescent properties.39-43 Continuing on this direction, we here employed a symmetric hexatopic aromatic carboxylate 3,4-di(3,5-dicarboxyl phenyl)phthalic acid(H6dccpa) (Scheme S1) as a bridging unit to build cluster complexes, which have been anticipated to possess outstanding photocatalytic activities. As to the polydentate H6dccpa ligand, the hexacarboxyl oxygen atoms could bind several metal centers with diverse chelating/bridging coordination modes, and three coplanar benzene rings may make H6dccpa become a highly conjugated organic system, which is likely to ensure the as-obtained compounds possess optical properties. In this work, we report two new 3D multinodal Cd(II)–organic frameworks, namely, [Cd3(dccpa)(bipy)0.5(H2O)4]·5H2O (1) and [(CH3)2NH2]2[Cd11(dccpa)4(DMF)4(H2O)8]·4H2O (2) based on Cd3/(Cd3+Cd5)-clusters that orginated from H6dccpa and cadmium salt in presence/absence of N-donor co-ligand. Compounds 1 and 2 not only exhibit a 3D neutral framework with a new (6, 6, 7)-connected net and a 3D 3



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anionic framework with a new (5, 6, 6, 10)-connected net respectively, but also show high photocatalytic efficiency for the degradation of organic dyes. Experimental Section Materials and General Methods. All chemicals were received as reagent grade and used directly without further purification. Elemental analysis was performed on a Perkin-Elmer 2400 Series II analyzer. FT-IR spectra were recorded as KBr pellets on a Thermo Electron NEXUS 670 FTIR spectrometer. Power X-ray diffraction (PXRD) patterns were investigated on a Rigaku Ultima IV diffractometer (Cu Kα radiation, λ = 1.5406 Å). The purity and homogeneity of the bulk products were determined by comparison of the simulated and experimental X-ray powder diffraction patterns. Thermogravimetric (TG) curves were recorded on a NETZSCH 449C thermal analyzer with a heating rate of 10oC min-1 under an air atmosphere. Photoluminescent analysis was performed on an Edinburgh FLS55 luminescence spectrometer at room temperature. The UV−vis spectra for samples were obtained on a Shimadzu UV 2550 spectrometer. Preparation of compound 1 and 2 Synthesis of [Cd3(dccpa)(bipy)0.5(H2O)4]·5H2O (1). Cd(ClO4)2·6H2O (16.8mg, 0.04mmol), H6dccpa (9.9 mg, 0.02 mmol), bipy (3.2mg, 0.02 mmol) were stirred in a mixed solvent containing 4mL DMF, 2mL H2O and one drop of concentrated HCl for about 30min. Then, the as-resulted reaction mixture was placed in a 23 mL Teflon-lined stainless steel autoclave. After sealed, the autoclave was heated at 140oC for 72h. The autoclave was allowed to cool to room temperature for 24h. Colorless block crystals of 1 were obtained in 67.0% yield. Anal. Calcd for C29H12Cd3O21N: C, 33.25; H, 1.15; N, 1.34%. Found: C, 33.45; H, 1.55; N, 1.57%. IR (KBr pellet, cm-1): 3390(s), 2358(w), 2355(w), 1604(s), 1540(s), 1436(s), 1367(s), 1260(m), 1153(w), 1108(w), 1062(w), 1008(w), 939(w), 908(w), 821(m), 780(m), 735(m), 630(m), 565(m). Synthesis of [(CH3)2NH2]2[Cd11(dccpa)4(DMF)4(H2O)8]·4H2O (2). Compound 2 was prepared in a method similar to that of 1 in the absence of bipy ligand. Colorless block crystals of 2 were obtained in 78.0% yield. 2 has a formula of [(CH3)2NH2]2[Cd11(dccpa)4(DMF)4(H2O)8]·4H2O, which was obtained based on single-crystal X-ray structural determination, elemental analysis and TGA. Anal. Calcd for C112H92Cd11O60N6: C, 36.18; H, 2.49; N, 2.26%. Found: C, 36.97; H, 2.53; N, 2.35%. IR (KBr pellet, cm-1): 3400(s), 2365(w), 2335(w), 1658(s), 1608(s), 1565(s), 1427(s), 1386(s), 1255(m), 1150(w), 1110(w), 1015(w), 917(w), 840(w), 780(m), 730(s), 680(m), 560(m). 4


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X-ray Crystallography. Single crystal X-ray diffraction analysis of 1 and 2 were tested on a Rigaku XtaLAB mini diffractometer with graphite monochromated MoKα radiation (λ = 0.71073 Ǻ) at the temperature of 296(2) K. The collected data were reduced using the program CrystalClear44 and an empirical absorption correction was applied.45 The structure was solved by direct methods and refined based on F2 by the full matrix least-squares methods using SHELXTL.46All non-H atoms were refined anisotropically. The position of hydrogen atoms attached to carbon atoms were generated geometrically. The coordinated and lattice water molecule were located at the special position and the affiliated H atoms were not determined. Additionally, in 2, the [(CH3)2NH2]+ cations were generated by the hydrolysis of DMF during the synthesis, and the charge-balancing [(CH3)2NH2]+ cations in the pores are highly disordered and cannot be identified by single-crystal X-ray diffraction. The contribution of the disordered guests was subtracted from the reflection data by the PLATON/SQUEEZE method. The resultant new files were used to further refine the structure. The crystallographic data for 1 and 2 are given in Table 1. Selected bond lengths and angles for 1 and 2 are listed in Table S1 and Table S2. (Supporting Information). Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center. CCDC reference numbers: 1412783 for 1 and 1412784 for 2. (Insert Table 1 and Scheme 1 here) Photocatalytic measurements The photocatalytic activities of both samples for the degradation of rhodamine B (RhB) and methyl blue (MB) were performed at an ambient temperature. The detailed procedure was as follows: 60mg of each sample was dispersed into 20mLof RhB aqueous solution (4.18×10-5mol·L-1) and MB aqueous solution (6.25×10-5mol·L-1), followed by the addition of a small amount of hydrogen peroxide solution (30%). In order to ensure an adsorption–desorption equilibrium of RhB/MB on the sample surface, the suspension was shaken at a constant rate in the dark overnight. A 500W xenon arc lamp was used as the visible light source to irradiate the above solution, which was continuously stirred during the degradation. At different time intervals, analytical samples were withdrawn from the reactor and the dispersed powders were removed by centrifugation. The absorbance of the as-resulted solutions was analyzed by UV-vis spectroscopy.

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Results and Discussion Description of Crystal Structures. Crystal Structures of [Cd3(dccpa)(bipy)0.5(H2O)4]·5H2O (1). Single crystal X-ray diffraction analysis reveals that 1 crystallizes in orthorhombic space group Pnna, and its asymmetric unit contains three crystallographically unique Cd(II) cations, two half of fully-deprotonated dccpa6anion with two different coordination modes, half a bpy ligand, four coordinated water and five lattice water molecules (Figure 1). Cd1 and Cd2 centers adopt a similar seven-coordinated mode with a distorted pentagonal bipyramid geometry, which are generated by six O atoms from carboxylate-(O1, O2, O5A,O8 O9A ,O10A) and one water-O (O13), six O atoms from carboxylate-(O3B, O4B, O7, O8, O5A, O12B ) and O atom from water- (O14), respectively. Cd3 center has a distorted octahedral coordination configuration occupied by three O atoms from carboxylate-(O4B, O7, O11), O atoms from water-(O15, O16) and one N atom from bpy (N1). All Cd−O bond lengths fall in the range of 2.219(5) ~2.635 (4) Å and the bond angles around Cd(II) ions are in the range of 52.83(12)~166.52(16)°, which are similar to the values found in other Cd(II)-carboxylate complexes.47 (Insert Figure 1 here) In 1, there is two half of fully-deprotonated dccpa6- anions, which adopt complicated µ10- and µ12 -bridges with the (η2-µ2)-(η2-µ2)-(η2:η1-µ2)-(η2)-(η2)-(η2:η1-µ2)-µ10 and (η1:η1-µ2)-(η1:η1-µ2)-(η2) -(η2:η1:η1-µ3)-(η2:η1:η1-µ3)-(η2)-µ12 coordination modes (Scheme 1 (I) and (II)), connecting ten and twelve Cd(II) centers, repectively. The Cd1, Cd2 and Cd3 ions are bridged by the four oxygen atoms from three carboxylate groups resulting in the trinuclear [Cd3(COO)6] unit (Figure S1). The trinuclear [Cd3(COO)6] clusters were futher linked together by dccpa6- anion and bipy ligands to form a complicated 3D framework (Figure 2).Topologically, the trinuclear [Cd3(COO)6] unit could be viewed as a 7-connected node (Figure 3b), and two dccpa6- anions with two different coordination modes could be considered as a 6-connected node (Figure 3a and 3c), and the bipy molecule can be defined as a linker. Thus, the overall structure of 1 is 3D (6, 6, 7)-connected network with the point symbol of (412·52·6)(4 9·56·66)2(49·66) (Figure 3d and Figure 3e). Although many similar trinuclear [Cd3(COO)6] units have been reported in other MOFs,48 1 is a new topological networks via searching in the latest TTO database according to the TOPOS 4.0 program.49 6


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(Insert Figure 2 and 3 here) Crystal Structures of [(CH3)2NH2]2[Cd11(dccpa)4(DMF)4(H2O)8]·4H2O (2). In the absence of bipy co-ligand, another new 3D (5, 6, 6, 10)-connected anionic framework 2 was isolated. The asymmetric unit of 2 possesses five and a half of crystallographically independent Cd (II) cations, two dccpa6- anions, two coordinated DMF molecules, four coorination water molecules and two lattice water molecules (Figure 4). The five and a half of cadmium cations including Cd1, Cd2, Cd3, Cd4, Cd5 and Cd6 (occupancy rate of 1, 1, 1, 1, 1 and 0.5) show distorted pentagonal bipyramid and octahedral coordination geometries, respectively. Cd1 and Cd3 centers are seven-coordinated by five O atoms from carboxylate-(O1, O2, O3C, O4C, O12A, O13 and O19B) and six O atoms from another carboxylate group (O3C, O14, O17G, O18G, O19B, O20B) and one O atom from DMF (O29) to give a pentagonal bipyramid coordination geometry. Cd2, Cd4 and Cd5 ions are six-coordinated by five O atoms from one carboxylate group (O5, O7D, O8D, O9F, O23E) and one O atom from water (O27), four O atoms from another carboxylate group (O10A, O11A, O15, O22H), one O atom from DMF (O25) and one O atom from water (O30), five O atoms from carboxylate groups (O6J, O10A, O16, O21H, O23I, O24I), which result in the differentlly distorted octahedral coordination geometries. However, Cd6 ions is surrounded by two six-coordinated symmetry-related carboxylate oxygen atoms (O17, O17G) and four oxygen atoms (O26, O28, O26G, O28G) to generate distorted octahedral coordination geometries. All Cd−O bond lengths fall in the range of 2.185(10) ~2.634 (9) Å and the bond angles around Cd (II) ions are in the range of 41.13(18) ~ 180.00(2) °, which is close to that of 1. (Insert Figure 4 here) The H6dccpa ligands in 2 are completely deprotonated, which adopt two different coordination modes: the first type of H6dccpa acts as a decadal-connector to link ten Cd(II) ions with the (η1:η2-µ2)-(η1:η1-µ2)-(η2)-(η1:η1-µ2)-(η2)-(η2:η1-µ2)-µ10 coordination mode (Scheme 1 III), whereas the second type of H6dccpa adopts (η1:η1-µ2)-(η1:η1-µ2)-(η2:η1-µ2)-(η2:η1-µ2)-(η1:η1-µ2)-(η2: η1-µ2)-µ12 coordination mode connecting twelve Cd(II) ions (Scheme 1 IV). Interestingly, in 2, on one hand, Cd1 and Cd3 ions are linked by two η2:η1-µ2-C8OO, -C40OO and one η1:η1-µ2 C25OO to generate a binuclear [Cd2(COO)4] SBU-a with the Cd···Cd distance about 3.682 Å (Figure S2a). Moveover, the adjacent two [Cd2(COO)4] binuclear SBU-a are further connected by single Cd6 ion, resulting in a pentanuclear [Cd5(COO)10] SBU-b (Figure S2b). On the other hand, Cd2, Cd4 7



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and Cd5 ions are also bridged by one η2:η1-µ2-C8OO and one η2:η1-µ3-C8OO to form a trinuclear [Cd3(COO)6] SBU-c (Figure S2c). Finally, the pentanuclear [Cd5(COO)10] SBU-b and trinuclear [Cd3(COO)6] SBU-c are further connected through µ10-dccpa6- and µ12-dccpa6-bridge to afford a complicated cationic 3D framework (Figure 5). Topologically, the dccpa6- anion in mode III and mode IV can be regarded as 5- and 6-connected nodes (Figure 6c and Figure 6b), separately. As for SBU-b and SBU-c, they link ten dccpa6- and six dccpa6- anions, thus, they could be simplified as 10- and 6-connected nodes (Figure 6a and Figure 6d). Hence, the resulting structure of 2 features a 3D 4-nodal (5, 6, 6, 10)-connected (411·64)4(4

26

·618·8)(49·6)2 point symbol calculated

by the TOPOS program (Figure 6e). To our knowledge, 2 is a new, 4-nodal (5, 6, 6, 10)-connected network and also represents the first multinodal cationic framework constructed from trinuclear and pentanuclear cadmium clusters. (Insert Figure 5 and 6 here) PXRD and Thermal Analysis. To confirm the phase purity of bulk materials 1 and 2, both samples were measured by powder X-ray diffraction (PXRD) at room temperature. The peak positions at the experimental patterns are in good agreement with the simulated patterns resulted from single-crystal diffraction data, indicating that both 1 and 2 have high purity (Figure S3 and Figure S4). Additionally, the thermogravimetric analysis was carried out under an air atmosphere (Figure S5). The TGA curves of 1 and 2 are similar and exhibit two main step of weight loss corresponding to the loss of cordinated or lattice solvent and the combustion of the organic groups. 1 shows the first mass loss of 13.73% below 200oC due to the release of the coordinated and lattice water molecules (calcd: 13.45 %), and the second step is from 220 to 450 oC, where the organic ligands began to decompose with the residual weight of 32.51% (calcd: 31.80%). For 2, the weight loss between 80 and 200 oC corresponds to the release of coordinated water molecules, lattice water molecules, and coordinated DMF molecules (obsd: 13.87% and calcd: 13.50%). The removal of organic components occurred at 220oC. Luminescent properties. The solid-state luminescent emission spectra of 1, 2 and the free H6dccpa ligand were investigated at ambient temperature. For compound 1, excited at 330 nm, it gives rise to an emission band at 425 nm. While the emission spectrum of 2 displays an emission band centered at 8


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413 nm with excitation maximum at 320 nm (Figure S6). The free H6dccpa ligand displays a relatively strong emission band at 387 nm (λex = 300 nm) (Figure S7). Meanwhile, according to the literature, the emission peak of bipy molecule is about 428 nm (λex=350 nm).47 Compared with that of the H6dccpa ligand, the emission bands present larger red-shifts, which should be ascribed to the metal–ligand coordinative interactions. The emissions of 1 and 2 can probably be assigned to the intraligand (π–π*) transfer. Accordingly, the spectral differences between 1 and 2 are intrinsic and could plausibly be due to the aforementioned structural variation.48 The smaller hypsochromic shifts of emission in 2 can be tentatively rationalized by its more complicated 3D skeletons comparing with 1. Photocatalysis activities. Previous studies have already reported that many transition metal coordination polymers could exhibit promising photocatalytic behaviors to degrade different organic dye pollutants.50-52 The band gaps of 1 and 2 were investigated by UV- diffuse reflection method at room temperature. The results give Eg (band gap energy) values of 2.87eV for 1, and 2.79 eV for 2 (Figure S9), which are suitable for the photocatalytic measurement. To study the photocatalytic activities of 1 and 2, rhodamine B (RhB) and methyl blue (MB) were used as model pollutants in aqueous media under xenon arc lamp illumination. The experiments were carried out in subjacent three parallel processes: (a) without catalyst under visible light irradiation; (b) with compounds 1 and 2 under visible light irradiation; and (c) with compounds 1 and 2 and H2O2 under visible light irradiation. The characteristic absorption of RhB (approximately 554 nm) and MB (approximately 664 nm) were selected to monitor photocatalytic degradation process. As illustrated in Figure 7 and Figure 8, the absorption peaks of RhB/MB decreased obviously under visible light in the presence of 1 and 2. In addition, the changes of the concentration of RhB and MB solution under visible-light irradiation were plotted versus irradiation time. The control experiments show that the photocatalytic decomposition rates of RhB/MB were approximately 88.6% for 1, 91.5% for 2, and 86.5% for 1 and 92.3% for 2, repectively (Figure 9). The distinctly shortened degradation times compared with the control experiments indicate that 1 and 2 are superior activity for the decomposition of RhB and MB under visible-light irradiation. The proposed photocatalytic degradation mechanism was very similar to those previously reported.53, 54 The PXRD pattern after the photocatalytic experiment is almost the same as that of the as-prepared samples (Figure S3 and 9



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Figure S4). (Insert Figure 7, 8 and 9 here) As reported in the literature, multinuclear Cd(II) clusters are possibly in favor of the degradation process of dyes.50 Herein, 1 only contains trinuclear [Cd3(COO)6] culster unit, while 2 is made up of the two kinds of different nuclei: trinuclear [Cd3(COO)6] and pentanuclear [Cd5(COO)10] cluster units. The cooperation of trinuclear Cd(II) cluster and pentanuclear Cd(II) clusters in 2 perhaps play a key role in the degradation process of RhB/MB. Conclusions In summary, we have successfully synthesized and characterized two new Cd (II)-MOFs. Compounds 1 and 2 exhibit new 3D 3-nodal (6, 6, 7)-connected network and 4-nodal (5, 6, 6, 10)-connected network with different Cd(II)-clusters as building units. Compounds 1 and 2 display high photocatalytic activities for the decomposition of RhB/MB under visible light irradiation. Our results indicate that cluster-based MOFs containing different carboxyl-metal units could show different impact on the decomposition of organic dyes. Clearly, this work provides not only new examples of cluster-based MOFs with aromatic ploycarboxylate tectonic as ligands, but also new insights into the design of Cd(II)-based photocatalytic materials. Acknowledgments This work was financially supported by the NSF of China (Nos: 21373122, 21301106, 51572152), the NSF of Hubei Province of China (No. 2014CFB277), and the Open Foundation of Ministry of Education Key Laboratory of Synthetic and Natural Functional Molecular Chemistry (No.338080057). Supporting Information Available: X-ray crystallographic files in CIF format, selected bond lengths and bond angles, TGA curves, PXRD curves and other valuable figures for 1, and 2 are available free of charge via the Internet at http://pubs.acs.org. References: (1) Zhang, Y. B.; Furukawa, H.; Ko, N.; Nie,W.; Park, H. J.; Okajima,S.; K. Cordova, E.; Deng, H.; Kim, J.; Yaghi, O. M. J. Am. Chem. Soc., 2015, 137, 2641−2650. (2) O’Keeffe, M.; Yaghi, O. M. Chem. Rev. 2012, 112, 675−702. (3) Jiang, J. C.; Yaghi, O. M. Chem. Rev. 2015, 115, 6966−6997.

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Table 1 Crystal data and structure refinement parameters of 1 and 2. Compound

1

2

Empirical formula

C29H12Cd3NO21

C108H76Cd11N4O60

Formula weight

1047.63

3626.13

Crystal system

Orthorhombic

Triclinic

Space group

Pnna

P-1

a (Ǻ)

18.845(6)

10.143(3)

b (Ǻ)

29.996(8)

16.127(5)

c (Ǻ)

12.410(4)

22.937(7)

α (°)

90

79.015(7)

β (°)

90

84.963(9)

γ (°)

90

77.484(9)

Volume (Ǻ 3)

7015(3)

3591.3(19)

Z

8

1

T(K)

296(2)

296(2)

Dc (g·cm-3)

2.291

1.677

F(000)

4760

1760

Data collected

70429

31595

Independent data

8044

12667

Rint

0.0926

0.0605

Goodness-of-fit

1.083

1.064

R1 [I > 2σ(I)]a

0.0473

0.0569

wR2 [I > 2σ(I)]b

0.1254

0.1606

R1 (all data)

0.0592

0.0730

wR2 (all data)

0.1418

0.1741

a

R = Σ‫|׀‬F0|−|FC|‫׀‬/Σ|F0|; bwR2 = [Σ[w(F02−FC2)2]/Σ[(F02)2]]1/2

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Scheme 1 View of the three coordination modes: (η2-µ2)-(η2-µ2)-(η2:η1-µ2)-(η2)-(η2)-(η2: η1-µ2)-µ10 (I), (η1:η1-µ2)-(η1:η1-µ2)-(η2)-(η2:η1:η1-µ3)(η2:η1:η1-µ3)-(η2)-µ12 (II), (η1:η2-µ2)-(η1: η1-µ2)-(η2)-(η1:η1-µ2)-(η2)-(η2:η1-µ2)-µ10 (III) and (η1:η1-µ2)-(η1:η1-µ2)-(η2:η1-µ2)-(η2:η1-µ2)(η1:η1-µ2)-( η2:η1-µ2)-µ12 (IV) of H6dccpa ligand in 1 and 2.

(I)

(II)

(III)

(IV)

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Figure 1 The coordination environment of CdII ions in 1. The hydrogen atoms and water molecules are omitted for clarity. Symmetry codes: A, x-1/2, y, -z+1; B, x, y, z+1.

Figure 2 View of the complicated 3D framework of 1 along the c axis.

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Figure

3 Crystal structures of 1: (a), (c) Define a two 6-connected node based on dccpa linkers; (b) Define a

7-connected node based on trinuclear Cd(II) clusters; (d) Define a (6,6,7)-connected node; (e) Schematic description of new 3-nodal net (6,6,7)-connected (412·52·6) (49·56·66)2(49·66) point symbol discriminated by colors, constructed from the 6-connected dccpa linkers and 7-connected Cd3 nodes.

Figure 4. The coordination environment of CdII ions in 2. The hydrogen atoms and the water molecules are omitted for clarity. Symmetry codes: A, -x, -y+2, -z; B, -x, -y+2, -z+1; C, x+1, y, z; D, x-1, y, z; E, -x-1, -y+2, -z+1; F, –x-1, -y+3, -z; G, –x+1, -y+2, -z+1; H, –x+1, -y+1,-z+1; I, -x, -y+1, -z+1; J, x+1, y-1, z.

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Figure 5 View of the complicated 3D framework of 2 along the c axis.

Figure 6 Crystal structures of 2: (a) Define a 6-connected node based on trinuclear Cd(II) clusters; (b) Define a

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10-connected node based on pentanuclear Cd(II) clusters; (c), (d) Define 5-, 6-connected node based on dccpa linkers; (e) Schematic description of new 4-nodal (5, 6, 6,10)-connected (411·64)4(426·618·8)(49·6)2 point symbol discriminated by colors, constructed from the 5-, 6-connected dccpa linkers, 6-connected Cd5 nodes and 10-connected Cd6 nodes.

(b)

(a)

Figure 7 The UV–vis absorption spectra of the RhB solution during the decomposition reaction in the presence of 1 (a) and 2 (b).

(b)

(a)

Figure 8 The UV–vis absorption spectra of the MB solution during the decomposition reaction in the presence of 1 (a) and 2 (b).

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(a)

(b)

Figure 9 Photocatalytic degradation of RhB (a) and MB (b) solution under visible-light irradiation with the use of 1 and 2, the black curve is the control experiment without any catalyst.

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For Table of Contents Use Only

Assembly of two novel Cd3/(Cd3+Cd5)-cluster-based metal–organic frameworks: structures, luminescence and photocatalytic degradation of organic dyes

Ya-Pan Wu, Xue-Qian Wu, Jian-Fang Wang, Jun Zhao, Wen-Wen Dong, Dong-Sheng Li, Qi-Chun Zhang Two novel 3D multinodal Cd(II)-cluster-based–organic frameworks not only represent a new 3D 3-nodal (6, 6, 7)-connected network and a new 3D 4-nodal (5, 6, 6, 10)-connected network, respectively, but also show a high photocatalytic activities toward the degradation of Rhodamine B(RhB) and methyl blue(MB).

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(Cd

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