(a) The different coordination geometries of the Cu(II) ions in 1. Symmetry code: #1 −x, −y + 1, −z + 1. (b) A view of the 2D [Cu 3 (1,3,5-BTC) 2 ] layer in complex 1. (c) The 2D layer with " U-shaped " 4-bpah ligands. (d) The simplified representation of the 2D layer in complex 1.  

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... Cu1 ion adopts a distorted tetrahedron coordi- nation environment, which is completed by two nitrogen atoms from two different 4-bpah ligands and two oxygen atoms afforded by two different 1,3,5-BTC anions. While Cu2 is five- coordinated by three oxygen atoms of three bridging 1,3,5-BTC ligands and two pyridyl nitrogen atoms from 4-bpah ligands (Fig. 1a). The Cu-N distances range from 2.019 (4) ...

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... network along the ac plane (Fig. 1b). There exists three types of rings with sizes of 15.27 Å × 14.28 Å for A, 8.47 Å × 7.33 Å for B and 4.61 Å × 4.38 Å for C in the 2D ...

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... 4-bpah ligands exhibit two kinds of coordination modes: one is a μ 2 -bridging mode with a "U-shaped" confor- mation, consolidating the 2D [Cu 3 (1,3,5-BTC) 2 ] layer, the other is a monodentate coordination mode with only one pyridyl nitrogen atom coordinating to the Cu(II) ion (Fig. 1c). On the basis of the topological approach, the 2D network can be simplified by considering the 1,3,5-BTC anion and Cu(II) center as 4-connected nodes, while the μ 2 -bridging 4-bpah serves as a 2-connect node, so the topological structure of 1 is a (4 2 ·8 3 ·10)(4 3 ·6 2 ·8) 4 (4) 2 network (Fig. 1d). The 2D layers are further ...

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... nitrogen atom coordinating to the Cu(II) ion (Fig. 1c). On the basis of the topological approach, the 2D network can be simplified by considering the 1,3,5-BTC anion and Cu(II) center as 4-connected nodes, while the μ 2 -bridging 4-bpah serves as a 2-connect node, so the topological structure of 1 is a (4 2 ·8 3 ·10)(4 3 ·6 2 ·8) 4 (4) 2 network (Fig. 1d). The 2D layers are further extended to a 3D supramolecular framework by a hydrogen bonding interaction between the uncoordinated carbonyl oxygen atoms from the 4-bpah ligands and the uncoordinated amino groups of the 4-bpah (Fig. S1 †). Fur- thermore, due to padding the water molecules in the large ...

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... serves as a 2-connect node, so the topological structure of 1 is a (4 2 ·8 3 ·10)(4 3 ·6 2 ·8) 4 (4) 2 network (Fig. 1d). The 2D layers are further extended to a 3D supramolecular framework by a hydrogen bonding interaction between the uncoordinated carbonyl oxygen atoms from the 4-bpah ligands and the uncoordinated amino groups of the 4-bpah (Fig. S1 †). Fur- thermore, due to padding the water molecules in the large ...

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... IR spectra of complexes 1-9 are determined in the fre- quency range of 500-4000 cm −1 , as shown in Fig. S10. † The strong peaks at 1635 and 1440 cm −1 for 1, 1637 and 1425 cm −1 for 2, 1608 and 1427 cm −1 for 3, 1609 and 1419 cm −1 for 4, 1610 and 1449 cm −1 for 5, 1610 and 1438 cm −1 for 6, 1605 and 1446 cm −1 for 7, 1601 and 1439 cm −1 for 8, 1608 and 1454 cm −1 for 9, may be attributed to the asymmetric and symmetric vibrations of the ...

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... cm −1 for 8, and 1657 cm −1 for 9, are characteristic of the carbonyl groups. 15a,15b The presence of the characteris- tic bands at 1361 and 1097 cm −1 for 1, 1380 and 1097 cm −1 for 2, 1367 and 1074 cm −1 for 3, 1382 and 1072 cm −1 for 4, 1383 and 1069 cm −1 for 5, 1373 and 1074 cm −1 for 6, 1382 and 1095 cm −1 for 7, 1382 and 1102 cm −1 for 8, 1396 and 1063 cm −1 for 9, suggest the ν C-N stretching vibrations of the pyridyl ring of the 4-bpah or 3-bpah ligands. 15a,15b For complexes 1-6 and 8- 9, the strong absorption peaks observed at 3292, 3388, 3402, 3294, 3316, 3268, 3330 and 3330 cm −1 indicate the presence of the -OH groups of the water molecules, respectively. ...

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... powder X-ray diffraction (PXRD) patterns for complexes 1-9 are presented in Fig. S11. † The as-synthesized patterns are in good agreement with the corresponding simulated ones, indicating the phase purities of the samples. In order to characterize the complexes more fully in terms of thermal stability, the thermal behaviors of 1-9 were examined by thermogravimetric analyses (TGA). The experiments were performed on ...

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... indicating the phase purities of the samples. In order to characterize the complexes more fully in terms of thermal stability, the thermal behaviors of 1-9 were examined by thermogravimetric analyses (TGA). The experiments were performed on samples consisting of numerous single crystals under an N 2 atmosphere with a heating rate of 10 °C min −1 (Fig. S12 ...

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... dispersed in the MB solu- tion (10.0 mg·L −1 ). Then, the mixture was stirred and continu- ously exposed to UV irradiation from a 15 W high pressure mercury vapor lamp. A sample was taken every 30 min from the vessel, and subsequently analyzed by UV-visible spectros- copy. The photocatalytic properties of title complexes are shown in Fig. 8 and Fig. S13. † In addition, control experiments on the photodegradation of MB were carried out. No signifi- cant change in the degradation of MB was observed in the following reaction conditions: (1) in the dark; (2) without cata- lyst; (3) only CuCl 2 ·2H 2 O/CoCl 2 ·6H 2 O/NiCl 2 ·6H 2 O/Zn(NO) 3 ·6H 2 O/ CdCl 2 ·2.5H 2 O; (4) only 4-bpah/3-bpah ...

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... stable state. Therefore, one electron was cap- tured from water molecules, which was oxygenated into the ·OH active species. Then the ·OH radicals could cleave MB effectively to complete the photocatalytic process. 23 In addition, the stability of complexes 1-9 was monitored using IR spectra and PXRD patterns after the photocatalytic reactions ( Fig. S10 and Fig. S11 †). The IR spectra and PXRD patterns of complexes 1-9 after photocatalysis are nearly identical to those of the original complexes, which indicate their good stability toward the photocatalysis of MB. In order to evaluate the reproducible ability of the title complexes, the repeated photocatalysis experiment was also performed with a ...

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... filtered, washed with distilled water under stirring for 120 min, then filtered again. After drying in air, the recyclable samples were obtained. As shown in Fig. S14, † there is no significant reduction of decolorization rate when the photocatalyst is used five times in the same photodegradation process. The result indicated that the photocatalysis of 9 has a good reproducibility. After being used as a photocatalysis five times, the IR spectra and PXRD patterns of photocatalyst 9 was nearly ...

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... reduction of decolorization rate when the photocatalyst is used five times in the same photodegradation process. The result indicated that the photocatalysis of 9 has a good reproducibility. After being used as a photocatalysis five times, the IR spectra and PXRD patterns of photocatalyst 9 was nearly identical to that of the original complex ( Fig. S10 and Fig. S11 †), implying that complex 9 is a stable and reproducible ...

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... decolorization rate when the photocatalyst is used five times in the same photodegradation process. The result indicated that the photocatalysis of 9 has a good reproducibility. After being used as a photocatalysis five times, the IR spectra and PXRD patterns of photocatalyst 9 was nearly identical to that of the original complex ( Fig. S10 and Fig. S11 †), implying that complex 9 is a stable and reproducible ...

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... addition, similar procedures were performed to check the photocatalytic activities of 9 for the degradation of methyl orange (MO) and rhodamine B (RhB). The degradations of MO and RhB after 240 min only reaches 18% and 12%, respectively ( Fig. 10 and Fig. S15, S16 †). The results indicate that complex 9 is a good selective photocatalyst for MB. The IR patterns and PXRD patterns at the end of each repeated bleaching experiment are almost the same as that of the as- prepared sample (Fig. S10 and Fig. S11 ...

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... B (RhB). The degradations of MO and RhB after 240 min only reaches 18% and 12%, respectively ( Fig. 10 and Fig. S15, S16 †). The results indicate that complex 9 is a good selective photocatalyst for MB. The IR patterns and PXRD patterns at the end of each repeated bleaching experiment are almost the same as that of the as- prepared sample (Fig. S10 and Fig. S11 ...