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A Series of Lanthanide Coordination Polymers Based on Designed Bifunctional 1,4-Bis(imidazol-1-yl)terephthalic Acid Ligand: Structural Diversites, Luminescence, and Magnetic Properties Xiu-tang Zhang, Liming Fan, Weiliu Fan, Bin Li, Guagzeng Liu, Xinzheng Liu, and Xian Zhao Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00540 • Publication Date (Web): 07 Jun 2016 Downloaded from http://pubs.acs.org on June 8, 2016

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Crystal Growth & Design

A Series of Lanthanide Coordination Polymers Based on Designed Bifunctional 1,4-Bis(imidazol-1-yl)terephthalic Acid Ligand: Structural Diversities, Luminescence, and Magnetic Properties Xiu-Tang Zhang,*

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Li-Ming Fan,

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Wei-Liu Fan, Bin Li, Guang-Zeng Liu, Xin-Zheng Liu, and Xian Zhao*

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Advanced Material Institute of Research, College of Chemistry and Chemical Engineering, Qilu Normal University, Jinan, 250013, P. R. China. ‡ State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, P. R. China. Supporting Information Placeholder 10

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ABSTRACT: Based on the designed bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA) ligand, a series of 3D lanthanide coordination polymers, namely, [La2(BTA)1.5(ox)1.5(H2O)3]n (1), [Nd(BTA)(ox)0.5(H2O)]n (2), {[Ln(HBTA)(ox)(H2O)]·xH2O} n (Ln = Pr for 3 (x=0), Sm for 4 (x=0), Dy for 5 (x=1.5), and Eu for 6 (x=1)), and [Ln(BTA)(SO4)0.5(H2O)]n (Ln = Eu for 7, and Tb for 8) were obtained with the help of oxalate or sulfate ions. Based on the binuclear La2 SBUs, the framework of 1 displays an unprecedented (3,3,4,9)-connected net with the point symbol of 11 5 14 5 2 3 4 2 2(4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ). While in complex 2, the binuclear Nd2 SBUs are connected by the BTA ligands to generate an 12 16 12 5 6 interestingly (4,10)-connected (4 .5 .6 .7 )(4 )2 net. Complexes 3-6 are isomorphism and show 2-fold interpenetrated 6 4 2 4 6 4-connected (6 )-dia net. Complexes 7 and 8 are isomorphism and show novel (4,5)-connected (4 .6 ) (4 .6 ) net. Photoluminescence investigations show that 2 is a good near-infrared luminescent material, and 4 is a rarely reported single component white light emitting material. Complexes 6 and 7 show typically red emission, while complex 8 shows typically green emission, which can be used as red or green emitting phosphor. Moreover, the luminescent lifetimes and quantum yields of the titled complexes were investigated. And the magnetic susceptibility data of 2 indicated there are III antiferromagnetic interactions between the Nd ions. INTRODUCTION

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The lanthanide coordination polymers (LnCPs), have attracted upsurging research interest for their attractive structures as well as gigantic prospective applications in the field of gas storage, electronic device, molecular switch, 1-13 catalysis, nonlinear optics, and biological activity. Such materials are generally constructed from the organic linkers and Ln ions, which are often affected by a myriad of 14-18 influence factors. The design and selection of organic linkers proved to be an efficiently routine in the assembly of functional 19-29 Notably, the polycarboxylates and nitrogen LnCPs. heterocyclic compounds are two most selective candidates in building high-dimensional architectures for their strong 30-53 coordination abilities and versatile bridging fashions. However, the bifuctional organic ligands, which contain both polycarboxylate and imidazole ring, were rarely 54-56 reported, comparatively. As we all known, applications are determined by properties, which are essentially derived from their III microstructure. The 4f electron configurations of the Ln ions endow the LnCPs unique luminescence with high luminescence quantum yield, sharp, narrow, and 57-64 well-separated emission bands. Thus, the lanthanide coordination polymers can generate high purity visible and near-infrared light-emitting emission, which make it possible to act as luminescent materials, highlighted by

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some articles recently. The introduction of organic linkers makes the LnCPs tunable platforms to generate luminescence with the model of the metal-ligand or ligand-metal charge transfers. Thus, these considerations inspired us to explore novel LnCPs by using the designed bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA) with the help of oxalate or sulfate ions. Herein, a series of 3D LnCPs, with the structures ranging from binuclear La2 SBUs based 11 5 14 5 2 3 4 2 (3,3,4,9)-connected (4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ) net, 12 16 12 5 6 binuclear Nd2 SBUs based (4,10)-connected (4 .5 .6 .7 )(4 )2 6 net, 2-fold interpenetrated 4-connected (6 )-dia net, to 4 2 4 6 (4,5)-connected (4 .6 ) (4 .6 ) net. The photoluminescence investigations shows the 2 is a good near-infrared luminescent material, 4 is a rarely reported single component white light emitting material. Complexes 6 and 7 show typically red emission, while complex 8 shows typically green emission, which can be used as red or green emitting phosphor.

Experimental Section 70

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Materials and General Methods. The ligand of 1,4-bis(imidazol-1-yl)terephthalic acid was synthesized with the help of Jinan Henghua Sci. & Tec. Co. Ltd.. All other starting reagents were commercially obtained without further purification. IR spectra were collected on a Nicolet 740 FTIR Spectrometer from KBr pellets. Elemental

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analyses (EA) of C, N and H were conducted on the CE instruments EA 1110 elemental analyzer. TG curves were carried out on a SDT Q600 instrument from room o o temperature to 800 C with the heating rate of 10 C/min under a N2 flow. Powder X-ray diffraction (PXRD) analyses for titled complexes were obtained on a Panalytical X-Pert pro diffractometer (Cu-Kα, λ = 1.5418 Å). Solid state emission spectra were detected on an F-4600 FL spectrophotometer. And the temperature dependence of magnetic susceptibility data was measured on a Quantum Design SQUID MPMS XL-7 instruments. The design of 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA) (Scheme 1). Synthesis of 2,5-dibromo-p-xylene (II). p-xylene (10.6 g, 0.1 mol), I2 (0.1 g), and 30% H2O2 (10 ml) was dissolved in 1000 ml CH2Cl2 and was cooled below 5 °C in icewater bath. Br2 (11.3 ml, 0.22 mol) was dropped the cooled solution and stirred for 24 h. And then saturated sodium hyposulfite solution was added to remove redundant Br2 and I2. The separated organic solution was reduced to 200 ml by evaporation. Colourless crystalline 2,5-dibromo-p-xylene (II) was obtained with the yield of 95 %. Anal. (%) calcd. for C8H8Br2: C, 36.40; H, 3.05. Found: C, 36.34; H, 2.99. Synthesis of 2,5-dibromoterephthalic acid (III). The mixture of 2,5-dibromo-p-xylene (II) (0.1 mol, 26.2 g) and 100 mL tert-Butanol in 1000 mL H2O was refluxed and then potassium permanganate (76 g, 0.48 mol) was slowly added in participle. Refluxed for further 4 h and ethanol was added to remove redundant potassium permanganate. Filtrated solution was acidified with the concentrated HCl and then the white predicate was obtained, which was recrystallized with DMF. The yield is 65 %. Anal. (%) calcd. for C8H4Br2O4: C, 29.66; H, 1.24. Found: C, 29.47; H, 1.11. Synthesis of ethyl 2,5-dibromoterephthalate (IV). 2,5-dibromoterephthalic acid (0.05 mol, 16.0 g) was suspended in 500 mL ethanol with 20 mL H2SO4 was refluxed overnight, and then was poured into 1000 mL icewater. The solution was neutralized with ammonium water and extracted with CH2Cl2 three times. Obtained organic solution was concentrated and colourless crystalline product was collected with 90 % yield. Anal. (%) calcd. for C12H12Br2O4: C, 37.93; H, 3.18. Found: C, 37.72; H, 3.08. Synthesis of diethyl 1,4-bis(imidazol-1-yl)terephthalate (V). The mixture of IV (0.01 mol, 3.8 g), imidazole (0.1 mol, 6.8 g), CuSO4 (0.5 g), and K2CO3 (0.1 mol, 13.8 g) was refluxed for 4h and was dissolved in 500 ml EtOH. The solution was decoloured with activated carbon and concentrated to 100 ml. Crude product was obtained and recrystallized with mixed solvent of ethyl acetate and DMF. Anal. (%) calcd. for C18H18N4O4: C, 61.01; H, 5.12; N, 15.81. Found: C, 60.85; H, 5.03; N, 15.65. Synthesis of 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA) (VI). The mixture of V (0.01 mol, 3.5 g) and 20 ml concentrated HCl in 100 mL H2O was refluxed for overnight and filtrated. The obtained precipitate was recrystallized – DMF to obtain white powder. EI-MS: m/z [M-H] , 297.07 (calcd for C14H10N4O4, 298.07). Anal. (%) calcd. for C14H10N4O4: C, 56.38; H, 3.38; N, 18.78. Found: C, 56.22; H, 3.16; N, 18.60.

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Scheme 1. The synthesis of 1,4-bis(imidazol-1-yl)terephthalic acid.

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The syntheses of H2BTA based LnCPs. Synthesis of [La2(BTA)1.5(ox)1.5(H2O)3]n (1). A mixture of H2BTA (0.15 mmol, 0.045 g), La(NO3)3·6H2O (0.20 mmol, 0.087 g), K2(C2O4)·H2O (0.20 mmol, 0.037 g), NaOH (0.30 mmol, 0.012 g), and 8 mL H2O in a 25mL Teflon-lined stainless steel vessel was put into an oven at 150 °C for 3 days, and then was slow cooled to room temperature with a o descent rate of 10 C/h. Colorless block crystals of 1 were obtained with the yield of ca. 67% (based on H2BTA). Anal. Calcd for C24H18La2N6O15: C, 31.74; H, 2.00; N, 9.25 (%). -1 Found: C, 32.03; H, 2.21; N, 9.16 (%). IR (cm , KBr): 3128 (m), 1603 (vs), 1511 (vs), 1429 (vs), 1379 (s), 1310 (s), 1244 (m), 1068 (m), 977 (m), 926 (m), 833 (m), 786 (m), 735 (m), 657 (m). Synthesis of [Nd(BTA)(ox)0.5(H2O)]n (2). H2BTA (0.15 mmol, 0.045 g), Nd(NO3)3·6H2O (0.20 mmol, 0.089 g), K2(C2O4)·H2O (0.20 mmol, 0.037 g), NaOH (0.30 mmol, 0.012 g), 8 mL H2O and 4 mL CH3OH was successively placed into a 25 mL Teflon-lined stainless steel vessel. And then the mixture was kept to 150 °C for 3 days, and then slowly cooled o to ambient temperature with a descent rate of 10 C/h. Violet block crystals of 2 were obtained with the yield of 71% (based on H2BTA). Anal. Calcd for C15H10N4NdO7: C, 35.85; H, 2.01; -1 N, 11.15 (%). Found: C, 35.63; H, 2.19; N, 10.96 (%). IR (cm , KBr): 3485 (m), 1668 (m),1598 (s),1431 (m), 1376 (s), 1312 (m), 1155 (vs), 1065 (vs), 991 (s), 844 (m), 742 (m), 644 (m). Synthesis of {[Ln(HBTA)(ox)(H2O)]·xH2O}n (Ln = Pr for 3 (x=0), Sm for 4 (x=0), Dy for 5 (x=1.5), and Eu for 6 (x=1)). The synthesis processes of 3-6 were similar with that of complex 1, except that the La(NO3)3·6H2O (0.20 mmol, 0.087 g) was insteaded by Pr(NO3)3·6H2O (0.20 mmol, 0.087 g) for 3, Sm(NO3)3·6H2O (0.20 mmol, 0.089 g) for 4, Dy(NO3)3·6H2O (0.20 mmol, 0.091 g) for 5, and Eu(NO3)3·6H2O (0.20 mmol, 0.089 g) for 6. Yield of 73 % for 3 (based on H2BTA). Anal. Calcd for C16H11N4O9Pr: C, 35.31; H, 2.04; N, 10.30 (%). Found: C, 35.67; H, 2.13; N, 10.73 -1 (%). IR (cm , KBr): 3122 (s), 1664 (m), 1567 (s), 1505 (m), 1415 (s), 1371 (s), 1313 (m), 1240 (m), 1110 (m), 1066 (s), 976 (m), 925 (m), 838 (m), 793 (m), 746 (m), 659 (m). For 4, the Yield is 74 % (based on H2BTA). Anal. Calcd for C16H12N4O9Sm: C, 34.65; H, 2.18; N, 10.10 (%). Found: C, 34.91; H, 2.29; N, 10.18 -1 (%). IR (cm , KBr): 3120 (m), 1671 (m), 1576 (s), 1434 (m), 1381 (vs), 1313 (s), 1128 (m), 1066 (s), 911 (w), 845 (s), 797 (s), 741 (s), 646 (m). For 5, the yield is 51 % (based on H2BTA). Anal. Calcd for C16H14DyN4O10.5: C, 32.42; H, 2.38; N, 9.45 (%). -1 Found: C, 32.66; H, 2.71; N, 9.71 (%). IR (cm , KBr): 3117 (s), 1673 (m), 1574 (s), 1437 (m), 1384 (s), 1313 (s), 1066 (s), 848


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(m), 797 (s), 741 (m), 646 (m). For 6, the yield is 68 % (based on H2BTA). Anal. Calcd for C16H14EuN4O10: C, 33.46; H, 2.46; -1 N, 9.76 (%). Found: C, 33.73; H, 2.72; N, 9.63 (%). IR (cm , KBr): 3120 (s), 1671 (m), 1580 (s), 1434 (s), 1381 (s), 1314 (s), 1066 (s), 845 (m), 797 (s), 742 (m), 647 (w). Synthesis of [Ln(BTA)(SO4)0.5(H2O)]n (Ln = Eu for 7, and Tb for 8). A mixture of H2BTA (0.15 mmol, 0.066 g) and Ln(NO3)3·6H2O (0.20 mmol, 0.092 g) were added in 8 mL H2O, and then were adjust the pH value to about 5.5 by using the NaOH and H2SO4. After stirred for half hours, the mixture was transferred into the 25 mL Teflon-lined stainless steel vessel and heated to 150 °C for 5 days, and then slowly cooled to ambient temperature with a descent rate of 10 o C/h. Colorless block crystals of 7 were obtained with the yield of ca. 67% (based on H2BTA). Anal. Calcd for C28H20Eu2N8O14S: C, 32.70; H, 1.96; N, 10.89 (%). Found: C, -1 32.82; H, 2.01; N, 10.94 (%). IR (cm , KBr): 3196 (m), 1694 (vs), 1603 (m), 1529 (vs), 1420 (s), 1357 (vs), 1210 (s), 1120 (m), 892 (m), 765 (m), 680 (m). For complex 8, the yield is 73 % (based on H2BTA). Anal. Calcd for C28H20N8O14STb2: C, 32.26; H, 1.93; N, 10.75 (%). Found: C, 32.41; H, 2.07; N, 10.94 -1 (%).IR (cm , KBr): 3453 (m), 3134 (m), 1621 (s), 1530 (vs), 1393 (s), 1311 (s), 1266 (m), 1129 (w), 1065 (s), 956 (m),774 (w), 728 (w). X-ray crystallography. The single-crystal data of titled LnCPs of 1-8 were collected on a Siemens SMART diffractometer with graphite-monochromatized Mo-Kα radiation (λ = 0.71073 Å). Empirical absorption corrections and Lorentz polarization were applied. Those structures were resolved by direct methods with SHELXS-97 and refined by 2 full-matrix least-squares methods on F by using the package 69,70 of SHELXTL-97. Detailed crystallographic data and structural refinements of those complexes were gathered in Table S1. And the Ln-N/O bond distances and selected angles around the Ln ions were given in Table S2. Further informations of the data can be obtained by visiting the website of http://www.ccdc.cam.ac.uk/ on quoting the depository number CCDC-1471606 for 1, 1471607 for 2, 1471608 for 3, 1471609 for 4, 1471610 for 5, 1471611 for 6, 1471612 for 7, and 1471613 for 8, respectively.

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RESULT AND DISCUSSION

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General Synthesis and Characterization. Complexes 1-8 were obtained from the reaction of designed H2BTA and related lanthanide salts in the help of the oxalate or sulfate ions under the solvothermal reactions. The titled complexes can be stable in the air and hold very poor solubility in the common solvents. The X-ray Powder diffraction (PXRD) analyses proved the titled complexes have good phase purity (Fig. S1). And the main vibrations in the IR spectra around -1 1510/1620 cm of the carboxyl groups’ asymmetric/symmetric stretching vibrations are also in aggrement with the crystal 71-73 strctures (Fig. S2). Structural Description of [La2(BTA)1.5(ox)1.5(H2O)3]n (1). Complex 1 crystallized in triclinic space group P-1, with III 2two La ions, one and a half of BTA ligands, one and a half of oxalate ions, and three coordinated water molecules in the asymmetric unit (Fig. 1a). La1 located in a distorted [LaNO8] tricapped trigonal prismatic coordination geometry with the O2, O5, O3B, O4B, O10C and N5D form a trigonal

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prism, and O6A, O7C, and O10E as capping atoms (Fig. 1b). La2 is nonacoordinated with one imidazole N atom (N4) 2from one BTA ligand, two carboxyl O atoms (O12, and O1E) 2from two other BTA ligands, three O atoms (O8, O9, and 2O8E) from two different ox ligands, and three coordinated water molecules, displaying the similar distorted [LaNO8] tricapped trigonal prismatic coordination geometry with the O9, O14, O15, O1E, O8E and N4 form a trigonal prism, and O8, O11 and O12 act as capping atoms (Fig. 1c). Besides, the La-O bond distances span ranged from 2.432(1) Å to 2.736(8) Å, and the La-N bond lengths are 2.667(2) Å and 2.728(7) Å, respectively. In the assembly of LnCPs, the oxalate was often selected as the secondary linker to construct high-connected architectures, which can be attributed to the strong coordination ability as well as various coordination modes. Besides, the oxalate and its related salt can be used as a buffer system to offer a stable reaction environment. It is interestingly to note that oxalate adopted two distinct III modes when coordinating the La ions in complex 1, one is 1 1 1 1 the normal μ2-κ :κ :κ :κ type (Type I) and the other is the 1 2 1 2 first reported μ4-κ :κ :κ :κ type (Type II), proved by the CSD survey by using the ConQuest version 1.3. The Type II typed oxalate linked with two La1 ions and two La2 ions alternately, leaving 1D [La2(ox)]n chains, which were further expanded into a 2D [La2(ox)3]n sheet by the Type I typed oxalate bridged the neighbouring La2 ions (Fig. 1d). In the formation of complex 1, the bifunctional H2BTA ligand completely deprotonated and adopted two different III coordination modes when interacted with the La ions. One 22 1 1 1 kind of BTA ligand adopted μ4-(η )-κ N-(η :η ) mode (Mode III I, in Scheme 2, linked with four La ions through the one 1 1 2 imidazole N atom and the bridging μ2-η :η , and chelating η 2carboxyl groups. At the same times, the other BTA ligand 1 1 1 1 adopted μ4-(η )-κ N-(η )-κ N mode (Mode II), connected with III four La ions with two imidazole N atoms and two 1 monodentate η carboxyl groups. Notably, the bridging 1 1 μ2-η :η carboxyl group bridged adjacent La1 and La2 ions, giving a binuclear La2 secondary building unit (SBU), with the La1···La2 distance is 5.194(3) Å. And in the assembly of complex 1, the imidazole rings can be rotated through the III C-C bonds to satisfy the coordination preference of La ion, with the dihedral angles for δ, ε, and ζ are 52.22(6)°, 41.15(6)°, 2and 11.43(0)° for Mode I typed BTA ligand (Table 2), and 35.88(8)°, 35.88(8)°, and 0.00(0)° for Mode II, in which the δ, ε, and ζ corresponding to the dihedral angles between aromatic rings of A/B, B/C, and A/C, respectively. Two kinds 2of BTA linkers coordinated with the La2 SBUs, successfully constructed a 3D [La2(BTA)2]n network (Fig. 1e), which can be simplified to be a 3,4,5-connected 2 2 4 3 6 (4 .6)2(4 .8 )(4 .6.8 )2-3,4,5T3 net (Fig. 1f and Fig. 2a). By sharing the La2 SBUs, the 3D [La2(BTA)2]n network incorporated with the 2D [La2(ox)3]n sheets, finally given a 3D architecture (Fig. 1g). 74-76 At the slight of topology, the final 3D framewrok of complex 1 is an unprecedented (3,3,4,9)-connected 11 5 14 5 2 3 4 2 (4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ) net by denoting the La2 22SBUs to 9-connected nodes, and type II ox , mode I BTA 2ligand, and mode II BTA ligand to 3-, 3-, and 4-connected nodes, respectively (Fig. 1h). To better understand the



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modular assembly of the 3D architectures, the tiling featured

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nets were given in the Fig. 2b.

Figure 1. (a) The asymmetric unit of 1 (Symmetry codes: A: –x, –y, –z; B: x, –1+y, z; C: x, y, –1+z; E: 1–x, –y, 1–z; H: 2–x, –1–y, 1–z.). Coordination geometry of La1 (b) and La2 (c) in 1. (d) The 2D [La2(ox)3]n sheet in 1 view along b axis. (e) The 3D [La2(BTA)2]n network in 1. (f) The 3,4,5-connected (42.6)2(42.84)(43.6.86)2-3,4,5T3 net of the [La2(BTA)2]n network. (g) Schematic view of the 3D framework of 1. (h) The unprecedented 3D (3,3,4,9)-connected (411.55.614.75.8)2(42.5)2(43)2(44.62) net of 1 (dark red spheres: Type II ox2- ligands, dark spheres: Mode I BTA 2ligands, dark green spheres: Mode II BTA 2- ligands, green spheres: binuclear La2 SBUs.).

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Figure 2. The tiling featured 3D [La2(BTA)3]n net (a) and the framework of complex 1 (b).

Structural Description of [Nd(BTA)(ox)0.5(H2O)]n (2). Although under the similar reaction condition, when the La(NO3)3 was replaced by the Nd(NO3)3, a distinct 3D

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(4,10)-connected net was generated. 2 crystallized in monoclinic space group P21 /n with the asymmetric unit III 2comprising one Nd ion, one BTA ligand, a half of oxalate


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III

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ions, one coordinated water molecule (Fig. 3a). Each Nd centre is surrounded by two N atoms (N4F, N1G) from two 22BTA ligands, six O atoms from three other BTA ligands (O4, O5D, and O6E), one oxalate (O1, and O2A), and one water molecule (O3), leaving a [NdN2O6] bicapped trigonal prismatic geometry with the O2A, O4, O5D, O6E, N1G and N4F form a trigonal prism, and O1 and O3 act as capping atoms (Fig. 3b). Besides, the Nd-O bond distances ranged from 2.427(2) Å to 2.576(4) Å, and the Nd-N bond lengths are 2.684(5) Å and 2.693(1) Å, respectively. 21 1 1 1 1 The BTA ligand adopted μ5-(η )-κ N-(η :η )-κ N coordination mode (Mode III) in complex 2, with the dihedral angles of δ, ε, and ζ are 29.76(7)°, 49.90(2)°, and 1 1 78.45(2)°, respectively. Notably, the bridging μ2-η :η carboxyl group bridged adjacent Nd ions, giving a binuclear Nd2 SBU, with the Nd···Nd distance is 5.746(9) Å. The oxalate ions bridged the neighbouring Nd2 SBUs, successfully created an interestingly 1D chain with the oxalate separated adjacent Nd2 SBUs distance being 6.644(5) Å (Fig. 3c). And along the

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expanded direction of terephthalic acid, the Nd2 SBUs were bridged with the terephthalic acid units, forming a 1D ladder 2III chain (Fig. 3d). Each μ5-BTA linker connected five Nd 1 1 ions by using two imidazole N atoms, one bridging μ2-η :η , 1 and one monodentate η carboxyl groups, successfully constructed a 3D [Nd(BTA)]n network (Fig. 3e), which can 12 12 4 6 be defined as a 4,8-connected (4 .6 .8 )(4 )2-flu net (Fig. 3f). Incorporating with the oxalate ions, the final 3D framework was constructed (Fig. 3g). 2Topologically, each Nd2 SBU surrounded by eight BTA 22ligands and two ox ligands, and each BTA ligand linked 2with four Nd2 SBUs. Thus, the BTA ligands and the Nd2 SBUs can be simplified into the 4-connected, and 10-connected nodes. On the basis of this simplification, the whole structure of 2 can be regarded as a novel binodal 12 16 12 5 6 (4,10)-connected (4 .5 .6 .7 )(4 )2 net (Fig. 3h). And the tiling featured nets were given in the Fig. 4 for the 3D [Nd(BTA)]n net (Fig. 4a) and the framework of complex 2 (Fig. 4b).

Figure 3. (a) The asymmetric unit of 2 (Symmetry codes: A: 2–x, 2–y,–z; D: 2–x, 1–y,–z; E: 1+x, y, z; F: 1/2+x, 3/2–y, 1/2+z; G: 1/2+x, 3/2–y, –1/2+z.). (b) Coordination geometry of Nd1 in 2. (c) The oxalate bridged Nd2 SBUs formed 1D chain. (d) The 1D ladder chain of [Nd(terephthalic acid)]n. (e) The 3D [Nd(BTA)]n network in 2. (f) The 3D (4,8)-connected (412.612.84)(46)2-flu net for the 3D [Nd(BTA)]n network in 2. (g) Schematic view of 3D architecture of 2. (d) The novel binodal (4,10)-connected 3D net with the Point Symbol of (412.516.612.75)(46)2 for 2 (blue spheres: BTA 2- ligands, green spheres: binuclear Nd2 SBUs.).



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Figure 4. The tiling featured 3D [Nd(BTA)]n net (a) and the framework of complex 2 (b).

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Figure 5. (a) The asymmetric unit of 3 (Symmetry codes: B: 1–x, 2–y, 1-z; D: 2–x, 1/2+y, 1/2-z.). (b) Coordination geometry of Pr1 in 3. (c) 2D The [Pr(ox)]n chain in 3. (d) Schematic view of the 3D architecture of 3. (e) The 4-connected 66-dia network for 3. (f) Tiling featured dia net for 3. (g) The 2-fold interpenetrated dia net for the final structure of 3.

Structural Description of [Ln(HBTA)(ox)(H2O)]n (Ln = Pr for 3, Sm for 4, Dy for 5, and Eu for 6). Under same condition, 2-fold interpenetrated 3D dia architectures were obtained when the Ln(NO3)3 (Ln=Pr, Eu, Dy, and Sm) were introduced into the reaction. X-ray single-crystal analyses of complexes 3-6 show that they are isostructural and the structure of complex 3 was selected as a representative herein. Complex 3 crystallized in monoclinic space group III P21 /c, and the asymmetric unit contains one Pr ion, one HBTA ligand, one oxalate ion, and one coordinated water III molecule (Fig. 5a). Each Pr ion is coordinated with nine 2 oxygen atoms from two HBTA ligands through chelating η carboxyl groups (O1, O2, O3D, and O4D), two oxalate ions

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(O5, O6, O8, and O9), and one water molecule (O7), to form a distorted [PrO9] tricapped trigonal prismatic coordination polyhedron with the O2, O3D, O5, O6, O8 and O9 form a trigonal prism, and O1, O7, and O4D act as capping atoms (Fig. 5b). And the Pr-O bond distances spanned from 2.467(6) Å to 2.623(5) Å. Different form it does in the former complexes, the HBTA 2 2 ligand adopted μ2-(η )-(η ) mode (Mode IV) in complex 3, III 2 linked two Pr ions only through the chelating η carboxyl groups, successfully generated a 1D zigzag [Pr(HBTA)]n chain with the neighbouring Pr···Pr distance is 11.597(6) Å. The dihedral angles of δ, ε, and ζ for HBTA ligand are 48.74(7)°, 42.33(2)°, and 6.70(7)°, respectively, which


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indicating that imidazole ring rotated through the C-C bonds when the carboxyl oxygen atoms coordinated with the metal centres to reduce the steric effect. Besides, the III oxalate ions bridged the adjacent Pr ions, emerged a 1D 2[Pr(ox)]n polymeric chain, with the ox separated Pr···Pr distances are 6.388(7) Å (Pr1···Pr1B), and 6.450(1) Å (Pr1···Pr1C), respectively (Fig. 5c). III Sharing the Pr ions, those 1D chains of [Pr(ox)]n and [Pr(HBTA)]n chain finally constructed a 3D framework with 2 the opening area about 15.011(5) × 10.692(0) Å along ab plane (Fig. 5d). And the 3D architecture can be viewed as the 6 normal 4-connected 6 -dia net (Fig.5e and Fig.5f). The larger channels of the 3D structure make the interpenetration appeared. Two adjacent 3D nets interspersed with each other, given a 3D 2-fold 6 interpenetrated 6 -dia frameworks ultimately by treating III the Pr ions as 4-connected nodes (Fig. 5g). Structure of [Ln(BTA)(SO4)0.5(H2O)]n (Ln = Eu for 7, and Tb for 8). Complexes 7 and 8 are isostructural and the structure of complex 7 was selected as a representative herein. Complex 7 crystallized in the monoclinic C2/c. There III 2are one Eu ion, one BTA ligand, a half of sulfate ions, and one coordinated water molecule in the asymmetric unit (Fig. III 6a). Each Eu ion is coordinated two nitrogen atoms (N2, and N3), three carboxyl oxygen atoms of O1, O3, and O4, two sulfate oxygen atoms (O5, O6F), and the O7 from coordinated H2O, displaying a distorted [EuN2O6] bicapped trigonal prismatic geometry with the O3, O5, O7, O6F, N2

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and N3 form a bigonal prism, and O1, and O4 act as capping atoms (Fig. 6b). Besides, the Eu-O band distances in the scope of 1.936(4) –2.670(2) Å, and the Eu-N bond distances are 1.936(4), 2.670(2) Å, respectively. In complex 7, H2BTA ligand adopted two different 1 1 1 1 coordination modes, μ4-(η )-κ N-(η )-κ N mode (Mode II), 2 1 2 1 and μ4-(η )-κ N-(η )-κ N mode (Mode V). Although the 2Mode II BTA ligand adopted the same mode like that in 1, the dihedral angles for δ, ε, and ζ are 62.30(1)°, 62.30(1)°, and 20.00(0)°, indicating the BTA ligand holding different 2rotation between the aromatic rings. Mode II BTA ligand III linked with four Eu ions through the two imidazole N 1 atoms and the monodentate η carboxyl groups. And the 2III Mode V BTA ligand connected with four Eu ions with two 2 imidazole N atoms and two chelating η carboxyl groups, with the δ, ε, and ζ are 41.31(3)°, 41.31(3)°, and 0.00(0)°, 2respectively. Two kinds of BTA ligands coordinated with III Eu ions, finally emerged a 2D [Eu(BTA)]n sheet (Fig.6c), with the adjacent Eu···Eu distances are 10.985(1) Å 2(Eu1···Eu1B), and 11.437(71) Å (Eu1···Eu1A). The SO4 anion bridged the neighbouring [Eu(BTA)]n sheets, successfully 2constructed a 3D framework (Fig. 6d), in which the SO4 anion separated Eu···Eu distance being 5.967(0) Å (Eu1···Eu1F). From the point of topology, the final 3D architecture can be simplified to be a (4,5)–connected 4 2 4 6 III (4 ·6 )(4 ·6 ) net, in which the Eu ions as 4-connected 2nodes, and the BTA ligands as 5-connected nodes, respectively (Fig.6e and Fig.6f).

Figure 6. (a) The asymmetric unit of 7 (Symmetry codes: A: –x, y, –1/2–z; B: –x, y, 1/2–z; C: 1/2–x, 1/2–y, –z; D: 1/2–x, –1/2+y, 1/2–z. (b) Coordination geometry of Eu1 in 7. (c) The 2D [Eu2(BTA)3]n sheet. (d) 3D framework of 7 along b axis. (e) 3D (4,5)–connected (44·62)(44·66) topology of 7 (green spheres: Eu(III) ions, blue spheres: BAT2- ligands, green bonds: sulfate ions). (f) Tiling featured net of the 3D architecture of 7.



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Scheme 2 Coordination modes of H2BTA in complex 1-8. 2-

Table 1. The dihedral angles of BTA /HBTA- in complexes 1, 2, 3 (representative of 3-6), and 7 (representative of 7 and 8). Complex Mode I in 1 Mode II in 1 Mode II in 7 Mode III in 2 Mode IV in 3 δ (°) 52.22(6) 35.88(8) 62.30(1) 29.76(7) 48.74(7) ε (°) 41.15(6) 35.88(8) 62.30(1) 49.90(2) 42.33(2) ζ (°) 11.43(0) 0 0 78.45(2) 6.70(7) δ, ε, and ζ corresponding to the dihedral angles between rings of A/B, B/C, and A/C, respectively. 5

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Mode V in 7 42.31(3) 42.31(3) 0

Table 2. The comparisons of the coordination modes, Ln-ox/SO4 motifs, Ln-(H)BTA motifs, and the final 3D nets for complexes 1-8. Complex Coordination modes Ln-ox/SO4 motifs Ln-(H)BTA motifs 3D architectures 1 μ4-(η2)-κ1N-(η1:η1) Mode I 2D [La2(ox)3]n sheet 3D (42.6)2(42.84)(43.6.86)2 net (411.55.614.75.8)2(42.5)2(43)2(44.62) net 1 1 1 1 2 2 4 3 6 1 μ4-(η )-κ N-(η )-κ N Mode II 2D [La2(ox)3]n sheet 3D (4 .6)2(4 .8 )(4 .6.8 )2 net (411.55.614.75.8)2(42.5)2(43)2(44.62) net 2 μ5-(η1)-κ1N-(η1:η1)-κ1N Mode III 0D [Nd2(ox)] linker 3D (412.612.84)(46)2 net (412.516.612.75)(46)2 net 2 2 3-6 μ2-(η )-(η ) Mode IV 1D [Ln(ox)]n chain 1D zigzag [Ln(HBTA)]n chain 2-fold interpenetrated 66-dia net 7 and 8 μ4-(η1)-κ1N-(η1)-κ1N Mode II 0D [Ln2(SO4)] linker 2D (44.62)-sql sheet (44·62)(44·66) net 2 1 2 1 4 2 7 and 8 μ4-(η )-κ N-(η )-κ N Mode V 0D [Ln2(SO4)] linker 2D (4 .6 )-sql sheet (44·62)(44·66) net

Structural Comparison. It is interestingly to note that although all the eight LnCPs were constructed from the H2BTA ligand, Ln(NO3)3·6H2O with the help of oxalate or sulfate ions under similar reaction conditions, they exhibited entirely different 3D architectures, which mainly attributed to lanthanide contraction as well as the influences of anions. H2BTA ligand adopted five coordination modes in the assembly of 1-8 (Scheme 2), with two carboxyl groups completely deprotonated and participated in coordination 2for all modes. Whereas, two imidazole N atoms of the BTA III ligand linked with one Ln ion in Mode I, two Ln ions in Mode II, Mode III, and Mode V, no ion in Mode IV, 2respectively. And the dihedral angles of BTA /HBTA ligands indicated that the ligand twisted when coordinating III 2with the Ln ions (Table 1). In 1, the BTA ligands adopted 2 1 1 1 1 1 1 1 μ4-(η )-κ N-(η :η ) (Mode I) and μ4-(η )-κ N-(η )-κ N (Mode II) III coordination modes, linking with La ions, successfully constructed a 3D [La2(BTA)2]n network with 3D 2 2 4 3 6 (4 .6)2(4 .8 )(4 .6.8 )2 topology. For complex 2, each 1 1 1 1 1 2μ5-(η )-κ N-(η :η )-κ N (Mode III) BTA ligand contacted with III five Nd ions, giving a 3D [Nd(BTA)]n network, which can 12 12 4 6 be simiplified to be a 3D (4 .6 .8 )(4 )2 net. While in the isostructural of complexes 3-6, one imidazole N attached the III hydrogen atom, and each HBTA ligand connected two Ln 2 ions through two chelating η carboxyl groups, leaving a 1D zigzag [Ln(HBTA)]n chains. In complex 7 and 8, two kinds 2III completely deprotonated BTA ligands attached the Ln 1 1 1 1 ions by adopting μ4-(η )-κ N-(η )-κ N (Mode II) and 2 1 2 1 μ4-(η )-κ N-(η )-κ N (Mode V) coordination modes, finally 4 2 building a 2D (4 .6 )-sql [Ln2(BTA)3]n sheet. On the other hand, the oxalate and sulfate ions play crucial roles in the assembly of titled LnCPs. As can be seen 2in Table 2, the ox apply two different coordination types 1 1 1 1 1 2 1 2 (μ2-κ :κ :κ :κ type (Type I) and μ4-κ :κ :κ :κ type (Type II)) in III the formation of complex 1, joined with La ions, granting

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an unprecedented 2D [La2(ox)3]n sheet. While in complex 2, 2III the ox just bridged two neighbouring Nd ions, leaving a 2[Nd2(ox)] linker. For complexes 3-6, the ox connected with III adjacent La ions, providing the 1D [Ln(ox)]n chains. When the sulfate ions were introduced to replace the oxalate ions 2in the formation of complex 7 and 8, the SO4 act as the III bridger linked two La ions, giving [La2(SO4)] linkers. The Ln-(H)BTA motifs and Ln-ox/SO4 motifs work III together by sharing the Ln ions, finally constructed series LnCPs with structures ranged from binuclear La2 SBUs 11 5 14 5 2 3 4 2 based (3,3,4,9)-connected (4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ) net (1), binuclear Nd2 SBUs based (4,10)-connected 12 16 12 5 6 (4 .5 .6 .7 )(4 )2 net (2), 2-fold interpenetrated 4-connected 6 4 2 4 6 (6 )-dia net (3-6), to (4,5)-connected (4 .6 ) (4 .6 ) net (7, 8). In summary, the versatility of the bifunctional H2BTA and the bridged oxalate/sulfate ions make contribution to the structure diversity of obtained LnCPs. Thermogravimetric Analyses. Thermogravimetric analyses measurements of complexes 1–8 were performed and given in the Fig. S3. For complex 1, the first weight loss below 140 °C can be attributed to the coordinated water lost (obsd: 5.67 %; calcd: 5.95 %), above this temperature, the whole structure began to collapse with the residual weight is ca. 54.3 % at 800 °C. For complex 2, the release of water molecules (free and coordinated) took placed below 190 °C (obsd: 3.92 %; calcd: 3.58 %), and then the framework broke down at around 380 °C, finally leaving a residual weight is ca. 43.8 % at 800 °C. The curve of 3 was selected as a respective of isomorphism 3-6 to discussed here, the initial weight loss of 3.4 % in 80-185 °C implying the loss of lattice water (calcd: 3.3 %). The second weight loss entailes the pyrolysis behaviors of organic ligands with the residual weight is ca. 36.0 % at 800 °C. Complex 7 and 8 show similar thermal degradation curves, with the first weight loss of 3.7 % (calcd: 3.5 %) for 7, and 3.6 % (calcd:


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3.5 %) for 8, can be ascribed to the remove of coordinated water molecules. And then the frameworks can be stable existed until the temperature up to about 380 °C, finally given the residual weight at 800 °C. Magnetic Properties. Variable-temperature magnetic susceptibility of complex 2 was examined with the temperature ranged from 1.8K to 300 K at 1000 Oe. As can be 3 -1 seen in the Fig. 7, the χmT value at 300 K is 1.55 cm K mol , 3 -1 closed with the expected value of 1.64 cm K mol for III 77 noninteracting Nd ion in it ground state with g = 8/11. 3 -1 The χmT product declines continuously to 0.78 cm K mol at 1.8 K as the temperature decreases. The temperature dependence χM followed the Curie-Weiss law χM= C/(T–θ) 3 -1 -1 with C= 1.62 cm K mol , θ= –15.64 K (Fig. 7). And the χm -T curve was given in the Fig. S4. The thermal depopulation of the crystal-field energy levels of the multiplet make contribution to the magnetic behavior of 2. And the negative value of θ also indicates the antiferromagnetic interactions III of the nearest Nd ions.

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above mentioned peaks are closed to the theoretical values III of the Nd ion, according to the historical work of W. T. 82, 83 Carnall and the review of E. G. Moore. And the main energy level assignments of the titled complexes were listed in the Table 3. III The Pr ion based luminescent coordination polymers 84 have been rarely reported. As claimed by Decadt, there are III two emissive electronic states for the Pr ion, and the emission can be occurred form both of them. We tested the emission spectra of 3 (PrCP) under excitation at 400 nm, and the bands at 458 and 499 nm derived from the π*-π transition of the p electrons, and the other bands can be III 3 assigned to the energy transitions of Pr ion at 481 ( P0 → 3 3 3 3 3 1 3 3 H4), 524 ( P0 → H5), 614 ( P0 → H6 & D2 → H4), 646 ( P0 3 1 3 → F2), and 682 nm ( D2 → H5) (Table 3 and Fig. 10). As shown in the Fig. S6, the decay curve indicating that the average luminescent lifetime of luminescent of 3 is 0.94 ms, with τ1=0.19 ms (f1=42.486), τ2=1.5 ms (f2=57.514), and χ²=1.181, fitted well the biexponential function. And the quantum yield Φf is 5.36 %.

Figure 8. The solid state emission spectrum of H2BTA and 1 (LaCP) with the λex = 350 nm at room temperature. 20

Figure 7. The variable-temperature magnetic susceptibility of 2.

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Luminescent Properties. Then the solid state ﬂuorescence spectrum of 1-8 and the free H2BTA ligand were examined at room temperature. As shown in the Fig. 8, the H2BTA displays emission peak at 438 nm upon excitation at −1 350 nm, with the calculated triplet level is 22826 cm (Table 3), which can be attributed to the π*-π transition of the p 78-80 electrons of the aromatic rings. And when the H2BTA III ligand coordinated with the La ion, the complex of 1 (LaCP) exhibits green-blue emission centred at 428 nm (λex = 350 nm), have a blue shift of 10 nm, which can be assigned to the ligand-to-metal charge transfer (LMCT). The luminescent lifetime of 1 (LaCP) was measured from the decay profile (Fig. S5), and is well fitted with the double exponential function with average luminescent lifetime τ= 2.35 ms, with the τ1=0.39 ms (f1=15.187), τ2=2.7 ms (f2=84.813), and χ²=1.247. Besides, the quantum yield Φf of 1 is 2.40 %. III The Nd based materials are the most promising near-infrared luminescent materials, which can be widely used in the field of optical telecommunication as well as 81 laser systems. Upon excitation at 315 nm, the emission spectra of 2 (NdCP) exhibits three strong bands at 896, 1064 and 1337 nm in the NIR region, which are attributed to the 4 4 transitions of F3/2 → IJ with J = 9/2, 11/2 and 13/2, respectively (Fig. 9). The calculated triplet energy of the

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Figure 9. The NIR emission spectra of 2 (NdCP) under 315 nm light in the solid state at room temperature.

Figure 10. Solid-state emission spectra of 3 (PrCP) under 400 nm light.

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Table 3. Assignment of the energy transitions of the LnCPs. Complex Wavelength (nm) Energy (cm-1) transition H2BTA 438.1 22826 π*-π LaCP 1 427.3 23402 π*-π 4 896.3 11157 F3/2 → 4I9/2 4 NdCP 2 1063.8 9400 F3/2 → 4I11/2 4 1336.5 7482 F3/2 → 4I13/2 3 481.3 20777 P0 → 3H4 3 524.1 19080 P0 → 3H5 3 P0 → 3H6 PrCP 3 613.7 16295 1 D2 → 3H4 3 645.2 15499 P0 → 3F2 1 682.4 14654 D2 → 3H5 4 562.1 17790 G5/2 → 6H5/2 4 SmCP 4 601.4 16628 G5/2 → 6H7/2 4 642.2 16020 G5/2 → 6H9/2 4 481.2 20781 F9/2 → 6H15/2 DyCP 5 4 570.8 17519 F9/2 → 6H13/2 5 591.2 16915 D0 → 7F1 5 614.2 16281 D0 → 7F2 EuCP-1 6 5 649.0 15408 D0 → 7F3 5 691.3 14465 D0 → 7F4 5 590.7 16929 D0 → 7F1 5 613.4 16302 D0 → 7F2 EuCP-2 7 5 651.1 15359 D0 → 7F3 5 698.7 14312 D0 → 7F4 5 487.4 20517 D4 → 7F6 5 544.2 18376 D4 → 7F5 TbCP 8 5 582.9 17155 D4 → 7F4 5 620.3 16121 D4 → 7F3

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The doping Ln ions strategy has been widely considered for white-light emitting, but only several single component 85-90 white light emitting have been reported up to date. For 4 (SmCP), under the excitation of 400 nm, a broad band of 375-475 nm centred at 450 nm deriving from the π*-π transition of organic ligands, and three sharp bands at 562 nm, 601 nm, and 642 nm originating from the transitions of 4 6 G5/2 → HJ (J = 5/2, 7/2, and 9/2) (Table 3) have been occurred, with the characteristic colours of those peaks are green, orange, and red, respectively (Fig. 11). Considering the remaining ligand fluorescence as well as the characteristic III luminescence of the Sm ions, the SmCP can generated single-component white-light material, with the CIE colour coordinates is (0.33, 0.30), according to the 1931 CIE chromaticity diagram, closely with the standard white light of (0.33, 0.33). The average luminescent lifetime of the white light SmCP is 0.35 ms, with τ1=0.19 ms (f1=70.888), τ2=0.75 ms (f2=29.112), and χ²=1.091, fitted well the biexponential function (Fig. S7). And the quantum yield Φf is 8.27 %.

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Figure 12. Solid-state emission spectra of 5 (DyCP) under 350 nm light at room temperature.

Figure 13. Red emission spectrum of 6 (EuCP-1) and 7 (EuCP-2) under 395 nm light. Inset: CIE chromaticity diagram (0.58, 0.32) for 6 (EuCP-1) and (0.62, 0.34) for 7 (EuCP-2).

Figure 14. Emission spectrum of 8 (TbCP). Inset: CIE chromaticity diagram (right) of 8 (TbCP) under 315 nm light. Inset: CIE chromaticity diagram (0.29, 0.56) for 8 (TbCP) 35

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Figure 11. White light emission spectrum of 4 (SmCP) under 400 nm light. Inset: CIE chromaticity diagram (0.33, 0.30) of 4 (SmCP).

When excited at 400 nm, complex 5 (DyCP) emitted one remaining ligand fluorescence of 417 nm with a shoulder of III 436 nm, and two typical bands of Dy ion at 481 nm and 572 4 6 nm, which are assigned to F9/2 → HJ (J = 15/2 and 13/2) transitions (Fig. 12 and Table 3). And the CIE colour coordinates is (0.18, 0.15) for 5 (DyCP), indicating it is a blue fluorescent material. The decay curve of the luminescent showing the average lifetime is 1.59 ms, with τ1=0.34 ms (f1=39.403), τ2=2.4 ms (f2=60.597), and χ²=1.181, fitted well the double exponential function (Fig. S8). And the quantum yield Φf is 25.50 %. III As the most promising red emitting phosphor, the Eu complexes have been fully investigated for the sharp emission at about 615 nm. For 6 (EuCP-1), under excitation at 395 nm, the emission spectra shows intense bands at 591, 614, and 691 nm, refering to the energy level diagrams 91 proved by W. T. Carnall, those bands can be attributed to 5 7 the D0 → FJ transitions with J = 1, 2, and 4, respectively, 5 7 while the intensity of D0 → F3 transition at 649 nm is too


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weak to be observed (Fig. 13). In addition, the intensity of 5 7 5 7 D0 → F2 transition is much stronger than that of D0 → F1 92-94 transition. The complex 7 (EuCP-2) displays a similar emission spectra with 6, the intense bands appeared at about 590, 613, 651 and 699 nm, which are attributed to the 5 7 transitions of D0 → FJ with J = 1, 2, 3, and 4, respectively. And the CIE colour coordinates is (0.58, 0.32) for 6 (EuCP-1), and (0.62, 0.34) for 7 (EuCP-2), indicating that they are good candidates as the red light emitter. As shown in the Fig. S9 and Fig. S10, two EuCPs displaying similar decay curves, both fitted well with the double exponential function, with the average photoluminescent lifetimes being 0.34 ms (τ1=0.30 ms, f1=70.750, τ2=0.42 ms, f2=29.250, and χ²=1.286) for 6 (EuCP-1), and 0.48 ms (τ1=0.47 ms, f1=95.243, τ2=0.60 ms, f2=4.757, and χ²=1.121) for 7 (EuCP-2), respectively. Besides, the quantum yields Φf for 6 and 7 are 7.89%, and 3.33%, respectively. And under excitation at 315 nm, the emission spectrum of 8 (TbCP) exhibits sharp bands at 487, 544, 583, and 620 nm, 5 which correspond to the characteristic transitions of D4 → 7 III FJ of the Tb ion with J = 6, 5, 4, and 3, respectively (Fig. 95-97 14). The most intense emission at 544 nm corresponds to 5 7 the D4 → F5. And the CIE colour coordinates is (0.29, 0.56) for 8 (TbCP). As can be seen in the Fig. S11, the decay curve of 8 (TbCP) fitted well with the double exponential function, with the average photoluminescent lifetime being 0.36 ms (τ1=0.31 ms, f1=81.732, τ2=0.57 ms, f2=18.268, and χ²=1.137). Besides, the quantum yields Φf for 8 is 6.74%.

CONCLUSION 30

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ACKNOWLEDGEMENT

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Supporting Information: X-ray crystallographic data in CIF format, IR spectra, TG curves, PXRD patterns, and decay profiles for 1 – 8. This material is available free of charge via the Internet of http://pubs.acs.org.

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AUTHOR INFORMATION

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Corresponding Author *[email protected] “Xiu-Tang Zhang” *[email protected] “Xian Zhao” Notes

This work was supported by financial support from the National Natural Science Foundation of China (Grant No. 21451001) and the Key Discipline, Innovation Team, and Key Lab. of Qilu Normal University.

References

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In generally, based on the designed bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid and oxalate/sulfate ions, a series 3D lanthanide coordination polymers have been designed with the structure ranged from 11 5 14 5 2 3 4 2 (3,3,4,9)-connected (4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ) net, 12 16 12 5 6 (4,10)-connected (4 .5 .6 .7 )(4 )2 net, (4,5)–connected 4 2 4 6 (4 ·6 )(4 ·6 ) net, to 2-fold interpenetrated 4-connected 6 (6 )-dia net. Photoluminscence inverstigation shows the 2 (NdCP) is a good near-infrared luminescent material, 4 (SmCP) is a reraly reported single component white light emitting material, 6 (EuCP-1) and 7 (EuCP-2) show typically red emission, which can be used as red emitting phosphor, while 8 (TbCP) shows typically green emission, which can be used as green emitting phosphor as well as fluorescent labeling. Further work of the LnCPs are underway in our lab.

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The authors declare no competing financial interest.

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Table of Contents Graphic and Synopsis

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A Series of Lanthanide Coordination Polymers Based on Designed Bifunctional 1,4-Bis(imidazol-1-yl)terephthalic Acid Ligand: Structural Diversites, Luminescence, and Magnetic Properties Xiu-Tang Zhang,* Li-Ming Fan, Wei-Liu Fan, Bin Li, Guang-Zeng Liu, Xin-Zheng Liu, and Xian Zhao*

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Based on the designed bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid, series 3D LnCPs have been designed with the 11 5 14 5 2 3 4 2 12 16 12 5 6 structure ranged from (3,3,4,9)-connected (4 .5 .6 .7 .8)2(4 .5)2(4 )2(4 .6 ) net, (4,10)-connected (4 .5 .6 .7 )(4 )2 net, 2-fold 6 4 2 4 6 interpenetrated 4-connected (6 )-dia net, to (4,5)-connected (4 .6 )(4 .6 ) net. Photoluminscence inverstigation shows the 2 (NdCP) is a good near-infrared optical telecommunication luminescent material, 4 (SmCP) is a rarely reported single component white light emitting material, 6 (EuCP-1) and 7 (EuCP-2) show typically red emission, and 8 (TbCP) shows typically green emission, which can be used as red or green emitting phosphor.


terephthalic Acid Ligand - ACS Publications - American Chemical

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