CoII MOFs modulated by dicarboxylate and bis(imidazole) mixed ligands: Syntheses, topology structure, photodegradation properties

Accepted Manuscript 5- and 7-fold interpenetrating 3D NiII/CoII MOFs modulated by dicarboxylate and bis(imidazole) mixed ligands: Syntheses, topology structure, photodegradation properties

Qing-Dan Luo, Chuan-Bin Fan, Xia Zhang, Xiang-Min Meng, Zheng Zhu, Fan Jin, Yu-Hua Fan PII: DOI: Reference:

S1387-7003(16)30553-6 doi: 10.1016/j.inoche.2017.01.003 INOCHE 6517

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

27 November 2016 22 December 2016 2 January 2017

Please cite this article as: Qing-Dan Luo, Chuan-Bin Fan, Xia Zhang, Xiang-Min Meng, Zheng Zhu, Fan Jin, Yu-Hua Fan , 5- and 7-fold interpenetrating 3D NiII/CoII MOFs modulated by dicarboxylate and bis(imidazole) mixed ligands: Syntheses, topology structure, photodegradation properties. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Inoche(2017), doi: 10.1016/j.inoche.2017.01.003

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ACCEPTED MANUSCRIPT 5- and 7-fold interpenetrating 3D NiII/CoII MOFs modulated by dicarboxylate and bis(imidazole) mixed ligands: syntheses, topology structure, photodegradation properties Qing-Dan Luo1a, Chuan-Bin Fan1a, Xia Zhanga, Xiang-Min Menga, Zheng Zhua, Fan Jinb,*, Yu-Hua Fan a,*

a

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Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of

Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100,

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PR China b

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Max Planck Institute for Terrestrial Microbiology & LOEWE Center for Synthetic

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Microbiology(SYNMIKRO), Marburg, Germany

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Abstract Two novel metal-organic frameworks (MOFs) based on transition metals, namely [Ni(sbdc)(4,4′-bbibp)(H2O)2]n (1) and [Co(sbdc)(4,4′-bbibp)]n (2) (H2sbdc = 4,4′-stilbenedicarboxylic, 4,4′-bbibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl), have been designed and successfully synthesized under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 5-fold classical Ia interpenetrated dia framework with 4-connected (66) sqc6 topology and complex 2 displays a 7-fold classical Ia interpenetrated dia network. Further, the photocatalytic properties of complexes 1-2 have been investigated. Significantly, the complexes 1-2 are good photo-catalysts for the degradation of organic dyes (MB/MV/RhB).

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Keywords: MOFs; 5-fold and 7-fold interpenetrated frameworks; photo-catalysts.

ACCEPTED MANUSCRIPT Over the past few decades, design and synthesis of diverse coordination polymers (CPs) as well as metal-organic frameworks (MOFs), have caught enormous attention of chemical researchers, not only because of their charming constructions and topologies [1], but also for they have shown a variety of potential applications in the fields of gas storage/separation [2], heterogeneous

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catalysis [3], electro-chemistry [4], magnetism [5], ion exchange [6], luminescence [7], drug

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delivery [8], and so on. Fascinating interpenetrating networks in mounting numbers have been

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investigated and comprehensively discussed [9–12]. Organic linkers and metal clusters containing secondary building units (SBUs) are very important to acquire interpenetrating topologies with

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self-interpenetration or multi-fold interpenetrated CPs. Generally, the metal ions used are confined

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to transition metals for their kinetic stability and higher coordination numbers [13–14]. In addition, the mixed organic linkers constructed by rigid N-donor ligands and semi-flexible O-donor ligands

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also play significant role in the construction of CPs with interpenetrating structures [15–16]. For

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example, the 18-fold interpenetration of diamondoid frames has been reported for the hydrogen-bonded complex of methanetetrabenzoic acid and 4,4'-bipyridine [17]. The complex

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CdCu2(pybz)4 (Hpybz = 4-(pyridin-4-yl)benzoic acid) shows the highest 25-fold interpenetrating

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diamondoid network exclusively based on coordination bonds [18]. However, it has been still difficult to estimate the final structure of CPs because various factors, such as organic linkers, coordination geometry of metal centers, pH, temperature, and solvents, have great influence in the self-assembly process of CPs [19–20]. Semiconductor MOFs have received great research interests. One of the important applications is photocatalysis. A variety of MOFs from the mixed-ligand systems have been adopted to photodegrade organic dyes [21], but systematic investigations on the influence of the final MOFs structures on their photocatalytic properties have

ACCEPTED MANUSCRIPT been astricted. With this background information, we designed and selected the semi-flexible H2sbdc and rigid 4,4′-bbibp (H2sbdc = 4,4′-stilbenedicarboxylic, 4,4′-bbibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl) (Scheme 1) as the building unit to construct interpenetrated CPs, which features two special

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characteristics: (1) the long size makes it a reasonable candidate to generate CPs of entangled

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topology and (2) the –CH=CH– group makes a semi-flexible ligand meet the requirement of

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coordination geometries of metal ion for tuning the fine structure. Successfully, we reported two novel CPs, [Ni(sbdc)(4,4′-bbibp)(H2O)2]n (1) and [Co(sbdc)(4,4′-bbibp)]n (2), which display

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unusual interpenetrating diamondoid networks. Furthermore, complexes 1-2 exhibit good

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photocatalytic activity for the degradation of organic dyes (MB/MV/RhB). Complex 1 is synthesized by Ni(NO3)2·6H2O, H2sbdc and 4,4′-bbibp ligands under

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solvothermal conditions at 130 °C [22]. Single crystal X-ray diffraction analysis [23] reveals that

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complex 1 crystallizes in the monoclinic space group C2/c. In the asymmetric unit, there exists one crystallographically unique Ni(II) ion, one sbdc2- anion, one 4,4′-bbibp ligand and two

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coordinated water. As shown in Fig. 1a, the Ni(II) atom is six-coordinated by two nitrogen atoms

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(N2 and N2a) from two individual 4,4′-bbibp bridging linkers (Ni–N 2.076(3) Å) and four oxygen atoms (O1, O1a, O3, O3a.) from two sbdc2- anions (O1, O1a.), two coordinated water molecules (O3, O3a.) (Ni–O 2.035(2)–2.125(2) Å), displaying a distorted octahedral geometry. Ni(II) to O/N distances and bond angles are within the normal range (Table S2). The sbdc2- anion connects two Ni(II) atoms with two monodentate carboxylates (µ2–κ1:κ0) (Scheme 2, Mode I). The 4,4′-bbibp ligand acts as a linker to join two adjacent Ni(II) atoms. The carboxylate groups of the H2sbdc ligands link the Ni(II) cation centers into an infinite 1D

ACCEPTED MANUSCRIPT waved chain ([Ni–sbdc]n), which contains a Ni···Ni separation of 17.857 Å, however the neighbouring Ni(II) ions are bridged by 4,4′-bbibp N-donor ligands showing a straight spin chains ([Ni–4,4′-bbibp]n), which contains a Ni···Ni separation of 17.657 Å. The two types of 1D chains ([Ni–sbdc]n and [Ni–4,4′-bbibp]n) are alternatively connected with each other, constructing a 1D

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→ 3D network (Fig. 1b). A better insight into the nature of this 3D framework can be provided by

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a topology analysis. By considering Ni(II) ions as the 4-connected nodes and all ligands as the

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2-connected spacers (Fig. 1c), the 3D structure of complex 1 can be interpreted as a classical 4-connected diamond (dia) lattice. Notably, the cages in a single framework exhibit maximum

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dimensions with an approximate pore size (corresponding to the longest intracage Ni···Ni

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distances) of 17.857 Å × 17.657 Å × 17.857 Å × 17.657 Å. This large superadamantane gives the single diamond framework a huge chamber which allows the other four identical 3D single

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networks to penetrate, leading to a 5-fold interpenetrated dia net without available void space (Fig.

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1d and e). An analysis of the topology of interpenetration according to a recent classification reveals that complex 1 belongs to class Ia [28]. Complex 1 displays a 4-connected sqc6 topology

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with the point symbol of (66).

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The synthetic procedure for complex 2 is the same as for complex 1 except that Co(NO3)2·6H2O was used instead of Ni(NO3)2·6H2O. In order to obtain higher fold interpenetration CPs, the Co(NO3)2·6H2O is employed in the same reaction system [29]. Single crystal X-ray diffraction analysis reveals that complex 1 is a 3D framework. It crystallizes in the monoclinic crystal system with a space group of C2/c and features a 7-fold interpenetrated diamond topological framework. As shown in Fig. 2a, the asymmetric unit consists of one crystallographically unique Co(II) ion, one sbdc2- anion and one 4,4′-bbibp ligand. The coordination geometry of the Co(II) ion can be

ACCEPTED MANUSCRIPT described as a distorted octahedral {CoN2O4} geometry defined by six atoms, including four carboxylate oxygen atoms (O1, O1a, O2 and O2a.) from two different H 2sbdc ligands (Co–O 2.040(4) Å) and two nitrogen atoms (N2 and N2a) from two 4,4′-bbibp ligands (Co–N 2.079(4) Å). Co(II) to O/N distances and bond angles are within the normal range (Table S2). The sbdc2- anion

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4,4′-bbibp ligand acts as a linker to join two adjacent Co(II) atoms.

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connects two Co(II) atoms with two bidentate carboxylates (µ2–κ1:κ1) (Scheme 2, Mode II). The

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In the structure, each Co(II) center is connected to four other metal centers by the organic spacers to construct a 3D open framework. The adjacent Co(II) ions are linked to each other by

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sbdc2- carboxylate ligands forming a waved chains ([Co–sbdc]n), but the neighbouring Co(II) ions

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are bridged by 4,4′-bbibp N–donor ligands showing a chair arrangement chains ([Co–4,4′-bbibp]n). The two types of 1D chains ([Co–sbdc]n and [Co–4,4′-bbibp]n) are alternatively connected with

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each other, constructing a 1D → 3D network (Fig. 2b). The adjoining metal centers are separated

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by distances of 17.428 Å (through 4,4′-bbibp) and 17.509 Å (through sbdc2-). If the 4,4′-bbibp ligands and sbdc2- anions are considered as linkers, and metal centers are considered as

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4-connected nodes, the architecture can be regarded as a typical 3D diamond framework. A single

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adamantanoid cage is illustrated in Fig. 2c, which exhibits maximum dimensions of 32.662 Å × 24.517 Å × 24.517 Å × 32.662 Å (corresponding to the longest intracage Co···Co distances). Because of the spacious nature of the single network, the potential voids are filled via mutual interpenetration of the other six independent equivalent frameworks, generating a 7-fold interpenetrating architecture (Fig. 2d and e). An analysis of the topology of interpenetration according to a recent classification reveals that complex 1 belongs to class Ia [28]. From a topology view, the framework of 1 can be rationalized to a 4-connected dia net with the Point

ACCEPTED MANUSCRIPT Schläfli symbol of (66), in which {CoN2O4} SBUs act as 4-connected nodes, and all organic ligands as linkers. All above, the center metal cation of 1-2 is different. The difference of Ni(II) ion on Co(II) ion is that it has two coordinated water. The numbers of the coordinated water molecules could affect

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the semiconductor properties [29]. The size, angle, steric hindrance of O-donor and N-donor

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ligands have significant effects on final interpenetrated networks. The influence of the coordinated

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angle and water on complexes 1-2 makes 1 and 2 display 5-fold and 7-fold interpenetrated networks, respectively. The H2sbdc ligand is completely deprotonated in complexes 1-2, but 1

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exhibits a µ2-(κ1-κ0)-(κ1-κ0) coordination mode and 2 displays a µ2-(κ1-κ1)-(κ1-κ1) coordination

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mode.

For exploring the conductivity of the complexes 1-2, the measurement of diffuse reflectivity for

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a powder sample is used to obtain the band gap Eg [31–32]. The band gap Eg is determined as the

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intersection point between the energy axis and the line extrapolated from the linear portion of the absorption edge in a plot of Kubelka–Munk function F against energy E. The Kubelka–Munk

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function, F = (1 – R)2 /2R, is obtained from the UV–Vis DRS data, where R is the reflectance of an

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infinitely thick layer at a given wavelength. Plots of F versus E for complexes 1-2 are shown in Fig. 3, where steep absorption edges are displayed, and the Eg values of complexes 1-2 are acquired as 3.0 and 3.1 eV, respectively, which indicate that complexes 1-2 are potential wide gap semi-conductive materials [33–35]. Photo-catalysts have attracted much attention due to their potential applications in purifying water and air by decomposing organic pollutants [36–40]. In recent years, CPs as photo-catalysts have attracted much attention due to their potential applications in purifying waste streams under

ACCEPTED MANUSCRIPT UV irradiation by decomposing organic dyes [41–43]. The optical band gaps of complexes 1-2 are found to be 3.0 eV and 3.1 eV, respectively, indicating that the complexes 1-2 may be used as a photo-catalyst using the UV irradiation. In order to study the photocatalytic activity of the complexes 1-2, the common organic dyes (MB, MV, RhB) are selected to evaluate the

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photocatalytic effectiveness in the purification of waste water.

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The details of photocatalytic reaction experiment are given [44]. The degradation experiment of

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MB is tracked by spectroscopy and the results are depicted in Fig. 4 (1) a–c. It is found that the degradation rates of MB are 94.0% for 1, 94.7% for 2 after 120 min, and the photo-degradation

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capability is that 2 > 1. The photo-degradation capability of complexes 1-2 in MV solution is

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shown in Fig. 4 (2) a–c. The degradation ratios of MV are 95.9% for 1, and 97.4% for 2 after 120 min, and the order of the photo-degradation capability is 2 > 1. As shown in Fig. 4 (3) a–c, the

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degradation ratios of RhB are 77.0% for 1, and 87.5% for 2 after 120 min, and the order of

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photo-degradation capability is 2 > 1. Meanwhile, all the MB/MV/RhB degradation ratios of control experiments don’t surpass 20% and nearly cease after 120 min under UV irradiation. The

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better photo-degradation performance of 2 may be due to electronic charges on its solid surface.

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As we all know, cheng’s group also reported the degradation of MB, the degradation ratios are 82.0% and 69.2% for the title complexes [21]. In comparison with the previous reports, these experimental results reveal that complexes 1-2 possess more photocatalytic activities for the degradation of MB/MV/RhB under UV irradiation (Fig. 5), which could be used as potential candidates as photocatalysts for the reduction of some organic dyes. In order to understand the photocatalytic degradation of MB/MV/RhB with the complexes 1-2, a simple mechanism bases on highest occupied molecular orbital (HOMO) and lowest unoccupied

ACCEPTED MANUSCRIPT molecular orbital (LUMO) considerations is proposed [45]. Complexes 1-2 involve both N and O coordinating atoms. It is known that when the complex is exposed in UV light (photo-excitation), there is an electron transfer from the HOMO contributed by the oxygen or nitrogen 2p bonding orbital (valence band) to the LUMO contributed by an empty metal orbital (conduction band). The

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HOMO strongly demands one electron to return to its stable state. Therefore, one electron is

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captured from the water molecule, which is oxygenated to the ·OH radical. Meanwhile, the ·OH

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groups allow the adsorption of O2 from water, and the photo-formed electrons reduce O2 to O2species, which in turn can interact with water to form further oxygenated radicals (mainly

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hydroxyl radicals ·OH). The ·OH active species could decompose MB/MV/RhB effectively to

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complete the photo-degradation process [46–51].

The measured and simulated PXRDs conform the purity of complexes 1-2 (Fig. S1–2†). To

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characterize the thermal stabilities of complexes 1-2, their thermal behaviors are investigated by

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TGA (Fig. S3†). The experiments are performed on samples consisting of numerous single crystals of complexes 1-2 under nitrogen atmosphere with a heating rate of 10 °C·min-1. All of the

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TG curves exhibit obvious weight loss steps in the region of 300–800 °C. The coordinated water

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molecules of complex 1 are completely lost at 156 °C (obsd: 4.81% and calcd: 4.80%), and the remaining substance is stable up to 390 °C. The residue of complex 1 at 800 °C should be NiO (obsd: 10.66% and calcd: 9.99%). For complex 2, the overall structure is stable up to 430 °C, and then the decomposition of the organic ligands begins, finally giving the residual weight at 800 °C (obsd: 13.57% and calcd: 10.53%). In summary, we have successfully designed and synthesized two new Ni(II)/Co(II) CPs which are 3D frameworks. Although both complex 1 and complex 2 feature class Ia interpenetrated dia

ACCEPTED MANUSCRIPT network with 4-connected (66) sqc6 topology, 1 shows a five-fold interpenetrated framework and 2 displays a seven-fold interpenetrated network. The photocatalytic properties of complexes 1-2 are examined. Furthermore, the complexes 1-2 could be good candidates for the photocatalytic

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degradation of organic dyes (MB/MV/RhB).

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Acknowledgements

This research was supported by the National Natural Science Foundation of China to C. F. Bi (No.

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21371161), the Specialized Research Fund for the Doctoral Program of Higher Education of

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China (No. 20120132110015).

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22. Complex 1 was prepared by mixing H2sbdc (0.20 mmol, 0.054 g), 4,4′-bbibp (0.20 mmol,

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0.077 g), Ni(NO3)2·6H2O (0.20 mmol, 0.059 g) and 8 mL of DMF-H2O (v/v = 1:1) were

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placed in a Teflon-lined stainless-steel vessel, heated to 130 °C for 72 h under autogenous pressure, and then cooled to room temperature at a descent rate of 5 °C h-1. Blue block crystals of 1 were obtained in 58 % yield based on Ni. Calcd. for C42H32N4O6Ni: C, 67.43; H, 4.28; N, 7.49. Found: C, 67.40; H, 4.26; N, 7.45. IR (KBr pellet, cm-1): 3443 (w), 3111 (w), 1593 (s), 1542 (s), 1512 (vs) 1459 (s), 1391 (vs), 1297 (m), 1233 (w), 1182 (m), 1165 (m), 988 (s), 950 (s), 891 (m), 832 (s), 785 (s), 756 (vs), 709 (w). 23. Suitable single crystals of the complexes 1-2 were picked under an optical microscope and

ACCEPTED MANUSCRIPT glued to thin glass fibers. X-ray crystallography data for complexes 1-2 was collected on a Bruker Apex Smart CCD diffractometer at 293(2) K with graphite-monochromatized Mo-Kα radiation (λ = 0.71073 Å) by using the ω-2θ scan mode. The structures were solved by direct methods and refined with the full-matrix least-squares technique (SHELXTL package) [24–

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25]. The non-hydrogen atoms were defined by the Fourier synthesis method. Thermal and

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positional parameters were refined by the full matrix least-squares method (on F2) to

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convergence [26]. Hydrogen atoms were placed at calculated positions and included as riding atoms with isotropic displacement parameters 1.2–1.5 times Ueq of the attached C atoms. All

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structures were investigated by the Addsym subroutine of PLATON [27] to assure that no

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additional symmetry could be applied to the models. Crystallographic data for complexes 1-2 is provided in Table S1. Selected bond lengths and angles for complexes 1-2 are listed in

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Table S2. CCDC numbers for complexes 1-2 are 1448437 for complex 1, and 1457729 for

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complex 2.

24. G. M. Sheldrick, Acta Crystallogr. Sect. A: Fundam.Crystallogr. 64 (2008) 112–122.

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25. G. M. Sheldrick, Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 71 (2015) 3–8.

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26. Bruker 2000, SMART, version 5.0, SAINT-plus version 6, SHELXTL, version 6.1, and SADABS version 2.03, Bruker AXS Inc., Madison, WI. 27. A. L. Spek, Implemented as the PLATON Procedure, a Multipurpose Crystal lographic Tool, Utrecht University, Utrecht, The Netherlands 1998. 28. V. A. Blatov, L. Carlucci, G. Ciani and D. M. Proserpio, CrystEngComm 6 (2004) 377–395. 29. A. K. Paul, R. Karthik and S. Natarajan. Cryst. Growth Des. 11(2011), 5741–5749. 30. Complex 2 was prepared by mixing H2sbdc (0.20 mmol, 0.054 g), 4,4′-bbibp (0.20 mmol,

ACCEPTED MANUSCRIPT 0.077 g), Co(NO3)2·6H2O (0.20 mmol, 0.058 g) and 8 mL of DMF-H2O (v/v = 1:1) were placed in a Teflon-lined stainless-steel vessel, heated to 130 °C for 72 h under autogenous pressure, and then cooled to room temperature at a descent rate of 5 °C h-1. Pink block crystals of 1 were obtained in 56 % yield based on Co. Calcd. for C42H28N4O4Co: C, 70.83; H, 3.93; N,

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7.87. Found: C, 70.80; H, 3.91; N, 7.85. IR (KBr pellet, cm-1): 1604 (vs), 1539 (s), 1513 (vs)

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1459 (s), 1392 (s), 1301 (s), 1239 (s), 1012 (m), 963 (m), 860 (s), 821 (s), 790 (s), 748 (vs),

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710 (s), 668 (s), 637 (m).

31. W. J. Ji, Q. G. Zhai, S. N. Li, Y. C. Jiang, M. C. Hu, Inorg. Chem. Commun. 24 (2012) 209–

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211.

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32. P. Du, Y. Yang, J. Yang, B. K. Liu, J. F. Ma, Dalton Trans. 42(5) (2013) 1567–1580. 33. C. C. Wang, Y. X. Song, Y. L. Wang, P. Wang, Chin. J. Inorg. Chem. 27 (2011) 361–366.

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34. J. L. Wang, C. Wang, W. Lin, ACS Catal. 2 (2012) 2630–2640.

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35. C. G. Silva, A. Corma, H. García, J. Mater. Chem. 20 (2010) 3141–3156. 36. X. L. Wang, F. F. Sui, H. Y. Lin, J. W. Zhang and G. C. Liu, Cryst. Growth Des. 14 (2014)

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3438–3452.

37.

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37. K. Li, L. Liu, S. Zhao, Y. F. Peng, B. L. Li and B. Wu, Inorg. Chem. Commun. 52 (2015) 34–

38. M. Li, L. Liu, L. Zhang, X. F. Lv, J. Ding, H. W. Hou and Y. T. Fan, CrystEngComm 16 (2014) 6408–6416. 39. L. M. Fan, W. L. Fan, B. Li, X. Zhao and X. T. Zhang, CrystEngComm 17 (2015) 9413–9422. 40. H. X. Yang, T. F. Liu, M. N. Cao, H. F. Li, S. Y. Gao and R. Cao, Chem. Commun. 46 (2010) 2429–2431.

ACCEPTED MANUSCRIPT 41. B. Liu, Z. T. Yu, J. Yang, H. Wu, Y. Y. Liu and J. F. Ma, Inorg. Chem. 50 (2011) 8967–8972. 42. Y. Q. Chen, G. R.Li, Y. K. Qu, Y. H.Zhang, K. H.He, Q. Gao and X. H. Bu, Cryst. Growth Des. 13 (2013) 901–907. 43. C. Y. Sun, X. L. Wang, C. Qin, J. L. Jin, Z. M. Su, P. Huang and K. Z. Shao, Chem. Eur. J. 11

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(2013) 3639–3645.

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44. The potential of the complexes 1-2 as photocatalysts was evaluated via degradation of

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methylene Blue (MB), methylene violet (MV), and Rhodamine B (RhB) dyes at room temperature and under 125–W Hg lamp irradiation in a photocatalytic assessment system.

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Complex 1 (0.020 g) or Complex 2 (0.020 g) was added to a solution of MB (100mL, mg·L-1),

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MV (100mL, mg·L-1) or RhB (100mL, mg·L-1). After stirring in the dark for 30 min to ensure the establishment of an adsorption/desorption equilibrium, and then the solution was stirred

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continuously under UV irradiation. The absorbance of the solution was measured by using a

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UV–Vis spectrophotometer every 15 min at the maximum absorption wavelength of 664 nm for MB, 583 nm for MV, 554 nm for RhB. The control experiment was carried out by the

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same way without these MOFs.

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45. C. C. Wang, H. P. Jing, P. Wang, J. Mol. Struct. 1074 (2014) 92–99. 46. Y. Li, J. Niu, L. Yin, W. Wang, Y. Bao, J. Chen, Y, Duan, J. Environ. Sci. 23 (2011) 1911– 1918.

47. J. X. Meng, Y. Lu, Y. G. Li, H. Fu, E. B. Wang, CrystEngComm 13 (2011) 2479–2486. 48. J. Guo, J. Yang, Y. Y. Liu, J. F. Ma, CrystEngComm 14 (2012) 6609–6617. 49. Y. Q. Chen, S. J. Liu, Y. W. Li, G. R. Li, K. H. He, Y. K. Qu, T. L. Hu and X. H. Bu, Cryst. Growth Des. 12 (2012) 5426–5431.

ACCEPTED MANUSCRIPT 50. G. H. Cui, C. H. He, C. H. Jiao, J. C. Geng and V. A. Blatov, CrystEngComm 14 (2012) 4210– 4216. 51. L. L. Wen, J. B. Zhao, K. L. Lv, Y. H. Wu, K. J. Deng, X. K. Leng and D. F. Li, Cryst. Growth

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Des. 12 (2012) 1603–1612.

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Scheme 1. Structures of H2sbdc and auxiliary N-donor bridging linkers.

Scheme 2. Two different coordination modes of H2sbdc in complexes 1-2.

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Fig. 1. (a) Coordination environment of the Ni(II) ion in complex 1 (Symmetry codes: A -x, y, -z+3/2; B -x+1, -y, -z+2; C -x-1/2, -y+1/2, -z.); (b) View of the single 3D framework of complex 1 along the b axis; (c) View of the 3D framework of complex 1 along the b axis; (d) schematic representation of the 5-fold interpenetrating 3D framework viewed along the b axis; (e) Schematic representation of the 5-fold interpenetrating dia networks.

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Fig. 2. (a) Coordination environment of the Co(II) ion in complex 2 (Symmetry codes: A -x+1, y, -z+1/2; B -x+3/2, -y+5/2, -z+1; C -x+1,-y-1,-z.); (b) View of the single 3D framework of complex 2 along the b axis; (c) The perspective view of the diamondoid network; (d) and (e) Schematic representation of the 7-fold interpenetrating

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Fig. 3. Kubelka–Munk–transformed diffuse reflectance spectra of complexes 1-2.

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Fig. 4. (1) (a) Absorption spectra of the MB solution in the presence of complex 1; (b) Absorption spectra of the MB solution in the presence of complex 2. (c) Plots of concentration ratios of MB (CT /C0) against irradiation time (min) in the presence of complexes 1-2, ligands, and without any catalyst during the decomposition reaction under UV irradiation. (2) (a) Absorption spectra of the MV solution in the presence of complex 1; (b) Absorption spectra of the MV solution in the presence of complex 2. (c) Plots of concentration ratios of MV (CT /C0) against irradiation time (min) in the presence of complexes 1-2, ligands, and without any catalyst during the decomposition reaction under UV irradiation. (3) (a) Absorption spectra of the RhB solution in the presence of complex 1; (b) Absorption spectra of the RhB solution in the presence of complex 2. (c) Plots of concentration ratios of RhB (CT /C0) against irradiation time (min) in the presence of complexes 1-2, ligands, and without any catalyst during the decomposition reaction under UV irradiation.

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Fig. 5. Degradation rates of the MB/MV/RhB solutions in the presence of complexes 1-2 under UV light.

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Graphical Abstract

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Two novel Ni(II)/Co(II) CPs have been successfully synthesized, which could be good candidates for the photocatalytic degradation of organic dyes.

ACCEPTED MANUSCRIPT Highlights 5– and 7–fold classical Ia interpenetrated frameworks have been acquired.

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Topology structure and photodegradation properties of the two complexes have been discussed.

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The photo-degradation performance may be due to electronic charges on its solid surface.

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