Syntheses, Structures, and Properties of a Series of Multidimensional

Article pubs.acs.org/crystal

Syntheses, Structures, and Properties of a Series of Multidimensional Metal−Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N‑Donor Ancillary Ligands Xiutang Zhang,*,†,‡ Liming Fan,†,‡ Zhong Sun,† Wei Zhang,† Dacheng Li,‡ Jianmin Dou,*,‡ and Lei Han*,§ †

Advanced Material Institute of Research, College of Chemistry and Chemical Engineering, Qilu Normal University, Jinan 250013, China ‡ College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, China § State Key Laboratory Base of Novel Functional Materials & Preparation Science, Faculty of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China S Supporting Information *

ABSTRACT: Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H4bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M(H2bpt)(Hpptp)]n (M = Mn (1), Fe (2), Co (3), and Zn (4)), [Mn2(bpt)(Hpptp)2]n (5), {[Zn3(Hbpt)(bpt)(H2O)2][(4,4′-H2bmib)0.5]·H2O}n (6), {[Cu(bpt)0.5(4,4′-bimbp)]· H2O}n (7), {[Co(H2bpt)(2,7-dfo)]·H2O}n (8), and {[Ni2(bpt)(4,4′bibp)2.5(H2O)]·3(H2O)}n (9) (Hpptp = 2-(3-(4-(pyridin-4-yl)phenyl)1H-1,2,4-triazol-5-yl)pyridine; 4,4′-bmib = 4,4′-bis(2-methylimidazol1-yl)benzene; 4,4′-bimbp = 4,4′-bis(imidazol-1-ylmethyl)biphenyl; 2,7-dfo = 2,7-di(imidazo-1-ly)-9H-fluoren-9-one; 4,4′-bibp = 4,4′-bis(imidazol)biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1−4 are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex 5 displays a pillared-layer 3D porous network with a (62.8)2(62.82.102) topology. Compound 6 shows an unprecedented 3D host-framework consisting of Zn6 clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (410.65)(419.616.8)(46.64)(47.63)2. The topology of 7 is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (62.84)(42.82)2. Complex 8 exhibits a 3D (66) structure with left- and right-handed helical chains arranged alternately. Complex 9 is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (64.82)(65.8)(68.82). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for 6, binodal (4,4)-connected for 7, and trinodal (4,4,5)connected for 9 have never been documented to date. Moreover, the luminescent properties of 4 and 6 have been investigated.

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INTRODUCTION The design and synthesis of metal−organic frameworks (MOFs) have attracted upsurging research interest not only because of their appealing structural and topological novelty but also owing to their tremendous potential applications in gas storage, microelectronics, ion exchange, chemical separations, nonlinear optics, and heterogeneous catalysis.1−3 In the assembly process of MOFs, the rational selection of the characteristic polycarboxylate ligands is one key factor in the construction of the desired MOFs.4,5 However, relatively less attention was given to the supramolecular architectures based on the rigid tetracarboxylate ligand of 3,3′,5,5′-biphenyltetracarboxylic acid (H4bpt), which may be a good candidate for the construction of coordination complexes with new topologies and potential useful properties.6 Apart from the carboxylate linkers, N-donor polyamine ligands are frequently used as ancillary © 2012 American Chemical Society

ligand to give multipodal anions acting as bridging, chelating, and charge balance ligands for synthesizing polynuclear species.7−9 The particular behaviors allow them to be promising candidates for designing beautiful metal building blocks. In the selfassembly process, the aromatic carboxylate and amine ligands can easily form π···π interactions due to the existence of a conjugated biphenyl system.10 Whereas, the combination of 3,3′,5,5′biphenyltetracarboxylic acid and N-donor polyamine in the metal−organic frameworks (MOFs) is rarely documented to date. Thus, these considerations inspired us to explore new coordination frameworks with 3,3′,5,5′-biphenyltetracarboxylic acid (H4bpt) and different N-donor ancillary ligands. Compared Received: October 14, 2012 Revised: December 9, 2012 Published: December 19, 2012 792

dx.doi.org/10.1021/cg301502u | Cryst. Growth Des. 2013, 13, 792−803

Crystal Growth & Design

Article

Table 1. Crystallographic Data and Details of Diffraction Experiments for Complexes 1−9 formula Mr crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρ (g cm−3) μ (mm−1) T (K) Rint R [I > 2σ(I)] R (all data) Gof formula Mr crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρ (g cm−3) μ (mm−1) T (K) Rint R [I > 2σ(I)] R (all data) Gof

1

2

3

4

5

C34H21N5O8Mn 682.50 monoclinic P2/c 19.31(2) 8.558(11) 27.25(4) 90.00 108.28(3) 90.00 4276(9) 4 1.060 0.354 293(2) 0.1104 R1 = 0.0677 wR2 = 0.1289 R1 = 0.1286 wR2 = 0.1455 1.001 6

C34H21N5O8Fe 683.41 monoclinic P2/c 19.282(9) 8.542(4) 27.116(13) 90.00 108.450(10) 90.00 4237(3) 4 1.071 0.401 293(2) 0.0749 R1 = 0.0445 wR2 = 0.1091 R1 = 0.0650 wR2 = 0.1198 0.999

C34H21N5O8Co 686.49 monoclinic P2/c 19.002(3) 8.390(5) 26.833(1) 90.00 108.73(2) 90.00 4051(5) 4 1.125 0.471 293(2) 0.0645 R1 = 0.0673 wR2 = 0.0940 R1 = 0.0624 wR2 = 0.1043 0.895

C34H21N5O8Zn 692.93 monoclinic P2/c 19.392(9) 8.516(4) 27.144(12) 90.00 109.504(10) 90.00 4226(3) 4 1.089 0.627 293(2) 0.0631 R1 = 0.0955 wR2 = 0.1872 R1 = 0.1887 wR2 = 0.2255 0.998 8

C52H32N10O8Mn2 1034.76 triclinic P̅1 14.723(8) 15.872(8) 16.294(8) 93.029(6) 109.689(5) 110.236(5) 3301(3) 2 1.041 0.431 293(2) 0.0393 R1 = 0.0445 wR2 = 0.1091 R1 = 0.0650 wR2 = 0.1198 0.998 9

C40H29N2O19Zn3 1037.76 triclinic P1̅ 11.360(3) 11.799(4) 16.350(5) 74.017(6) 82.914(6) 63.634(6) 1887(7) 2 1.826 1.983 296(2) 0.0574 R1 = 0.0673 wR2 = 0.1307 R1 = 0.1037 wR2 = 0.1523 0.999

7 C28H23N4O5Cu 559.04 monoclinic P2/c 9.354(4) 14.614(7) 19.726(9) 90.00 94.889(8) 90.00 2687(2) 4 1.382 0.857 273(2) 0.0489 R1 = 0.0682 wR2 = 0.1520 R1 = 0.1001 wR2 = 0.1635 1.001

to rigid 1,2,4,5-benzenetetracarboxylic acid, H4bpt is a more flexible and longer ligand, which possesses several interesting characters: (i) It has four carboxyl groups that may be completely or partially deprotonated, inducing rich coordination modes and allowing interesting structures with higher dimensionalities. (ii) It can act as hydrogen-bond acceptor as well as donor, depending upon the degree of deprotonation. (iii) Two sets of carboxyl groups separated can form different dihedral angles through the rotation of C−C single bonds; thus, it may ligate metal centers in different orientations. These characters may lead to cavities, interpenetration, helical structures, and other novel motifs with unique topologies. Taking account of these, recently we began to assemble H4bpt and different transitional metal ions into polymeric complexes in the presence of rigid or flexible N-donor ancillary ligands under solvothermal conditions and anticipated that the rich structural features stored in H4bpt will induce novel polymeric structures. In this article, we

C35H22N4O10Co 717.50 monoclinic C2/c 37.92(3) 7.642(5) 23.501(2) 90.00 117.73(5) 90.00 6028(7) 8 1.581 0.641 273(2) 0.0439 R1 = 0.0649 wR2 = 0.1848 R1 = 0.0812 wR2 = 0.2055 1.004

C61H49N10O12Ni2 1231.52 monoclinic P2/n 19.308(4) 14.196(3) 20.379(4) 90.00 103.150(4) 90.00 5439(4) 4 1.504 0.769 293(2) 0.0563 R1 = 0.0553 wR2 = 0.1372 R1 = 0.0888 wR2 = 0.1574 1.001

reported the syntheses and characterizations of nine new coordination polymers, [M(H2bpt)(Hpptp)]n (M = Mn (1), Fe (2), Co (3), and Zn (4)), [Mn2(bpt)(Hpptp)2]n (5), {[Zn3(Hbpt)(bpt)2(H2O)][(4,4′-H2bmib)0.5]·H2O}n (6), {[Cu(bpt)0.5(4,4′-bimbp)]· H2O}n (7), {[Co(H2bpt)(2,7-dfo)]·H2O}n (8), and {[Ni2(bpt)(4,4′-bibp)2.5(H2O)]·3(H2O)}n (9), which exhibit a systematic variation of architectures from 2D layers to 3D frameworks by the employment of H4bpt and five different N-donor ancillary ligands (Hpptp, 4,4′-bmib, 4,4′-bimbp, 2,7-dfo, and 4,4′-bibp).

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EXPERIMENTAL SECTION

Materials and Physical Measurements. The organic chemicals of H4bpt, Hpptp, 4,4′-bmib, 4,4′-bimbp, 2,7-dfo, and 4,4′-bibp were purchased from Jinan Henghua Sci. & Tec. Co. Ltd. without further purification. Elemental analyses of C, N, and H were performed on an EA1110 CHNS-0 CE elemental analyzer. IR (KBr pellet) spectra were recorded on a Nicolet Magna 750FT-IR spectrometer. Fluorescent 793



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Table 2. Selected Bond Lengths (Å) and Angles (deg) for 1−9 complex 1 Mn(1)−N(1) Mn(1)−O(4)#1 O(8)−Mn(1)−N(5)#2 O(4)#1−Mn(1)−N(1) symmetry code: #1 x, −y

2.263(4) Mn(1)−N(2) 2.257(4) Mn(1)−O(7) 2.155(3) Mn(1)−N(5)#2 2.238(4) O(4)#1−Mn(1)−O(8) #1 96.95(14) O(4) −Mn(1)−N(2) 131.79(12) O(8)−Mn(1)−N(2) 88.97(14) O(8)−Mn(1)−N(1) 89.76(14) N(5)#2−Mn(1)−N(1) + 1, z + 1/2. #2 −x, −y, −z + 1. #3 x, −y + 1, z − 1/2. complex 2

Fe(1)−N(1) 2.182(6) Fe(1)−O(6)#3 2.078(5) N(5)#1−Fe(1)−O(1) 94.5(2) O(6)#3−Fe(1)−N(2) 131.34(2) symmetry code: #1 −x, −y, −z + 1. #2 Co(1)−O(6)#1 Co(1)−N(1) N(5)#2−Co(1)−O(2) N(5)#2−Co(1)−N(2) symmetry code: #1 x, −y

Fe(1)−N(2) Fe(1)−N(5)#1 O(6)#3−Fe(1)−N(1) N(5)#1−Fe(1)−N(2) x, −y + 1, z − 1/2. #3 x,

2.041(3) Co(1)−N(5)#2 2.093(5) Co(1)−O(1) 94.18(2) O(6)#1−Co(1)−N(2) 98.65(2) O(2)−Co(1)−N(2) + 1, z + 1/2. #2 −x, −y + 2, −z + 1.

2.394(4) 81.70(14) 141.12(13) 173.29(14)

2.200(5) Fe(1)−O(1) 2.161(6) O(6)#3−Fe(1)−N(5)#1 89.3(2) N(5)#1−Fe(1)−N(1) 99.1(2) O(1)−Fe(1)−N(2) −y + 1, z + 1/2. complex 3

2.084(5) 2.294(3) 129.45(14) 144.12(16)

Mn(1)−O(8) O(4)#1−Mn(1)−N(5)#2 N(5)#2−Mn(1)−N(2) N(2)−Mn(1)−N(1)

2.208(3) 92.09(14) 100.18(13) 74.29(12)

2.168(4) 92.3(2) 175.0(2) 143.16(18)

Fe(1)−O(2) O(6)#3−Fe(1)−O(1) O(1)−Fe(1)−N(1) N(1)−Fe(1)−N(2)

2.330(5) 81.70(18) 90.4(2) 76.4(2)

2.105(3) 92.34(18) 98.65(18) 88.53(15)

Co(1)−N(2) O(6)#1−Co(1)−O(2) O(2)−Co(1)−N(2) N(5)#2−Co(1)−N(1)

2.097(4) 82.96(14) 144.12(2) 176.31(2)

2.114(4) 85.73(17) 90.7(2) 96.7(2)

Zn(1)−O(2) O(6)#3−Zn(1)−N(5)#1 N(5)#1−Zn(1)−N(1) N(1)−Zn(1)−N(2)

2.414(5) 93.8(2) 173.6(2) 76.9(2)

2.273(9) 2.043(9) 2.276(8) 155.8(4) 98.8(4)

Mn(1)−O(8A)#1 Mn(2)−O(3) Mn(2)−N(6) O(1)−Mn(1)−O(8A)#1 O(3)−Mn(2)−N(6)

2.271(8) 2.212(7) 2.235(11) 159.7(3) 90.8(3)

Co(1)−O(2) (O6)#1−Co(1)−N(5)#2 N(5)#2−Co(1)−N(2) O(6)#1−Co(1)−N(1)

complex 4 Zn(1)−N(1) 2.162(7) Zn(1)−O(6)#3 2.045(4) O(1)−Zn(1)−N(5)#1 94.8(2) O(6)#3−Zn(1)−N(2) 128.53(2) symmetry code: #1 −x, −y, −z + 1. #2

Zn(1)−N(2) Zn(1)−N(5)#1 O(6)#3−Zn(1)−N(1) O(1)−Zn(1)−N(2) x, −y + 1, z − 1/2. #3 x,

Mn(1)−O(1) Mn(1)−N(10)#2 Mn(2)−N(7) O(1)−Mn(1)−O(7A)#1 N(7)−Mn(2)−O(4) symmetry code: #1 x − 1,

Mn(1)−O(7A)#1 2.202(7) Mn(1)−N(2) Mn(1)−N(1) 2.263(11) Mn(2)−O(5) Mn(2)−N(5)#2 2.217(11) Mn(2)−O(4) O(1)−Mn(1)−N(2) 99.4(4) O(7A)#1−Mn(1)−N(2) N(5)#4−Mn(2)−O(4) 84.3(4) O(5)−Mn(2)−N(6) 1, −y + 1, −z. #3 −x + 1, −y + 1, −z + 1. #4 −x + 2, −y + 2, −z. complex 6

2.038(9) 2.242(11) 2.259(9) 101.6(3) 101.0(3) y, z. #2 −x +

2.175(5) Zn(1)−O(1) 2.122(7) O(6)#3−Zn(1)−O(1) 90.0(2) O(1)−Zn(1)−N(1 142.72(18) N(5)#1−Zn(1)−N(2) −y + 1, z + 1/2. complex 5

Zn(1)−O(4)#3 2.123(7) Zn(1)−O(8)#4 2.132(7) Zn(1)−O(10) 2.146(8) Zn(1)−O(12) 2.192(8) #5 Zn(1)−O(9) 2.224(7) Zn(1)−O(8)#5 2.503(7) Zn(2)−O(6)#1 2.086(8) Zn(2)−O(13) 2.108(7) Zn(2)−O(15)#6 2.145(7) Zn(2)−O(5)#3 2.143(7) Zn(2)−O(14) 2.189(8) Zn(3)−O(18)#7 2.132(8) Zn(3)−O(16)#8 2.133(8) Zn(3)−O(7)#9 2.132(7) Zn(3)−O(2) 2.150(9) Zn(3)−O(1) 2.216(7) Zn(3)−O(3) 2.246(10) O(4)−Zn(1)#3 2.123(7) O(5)−Zn(2)#3 2.143(7) O(6)−Zn(2)#1 2.086(8) O(7)−Zn(3)#10 2.132(7) O(8)−Zn(1)#4 2.132(7) O(8)−Zn(1)#11 2.503(7) O(9)−Zn(1)#11 2.224(7) O(15)−Zn(2)#6 2.145(7) O(16)−Zn(3)#12 2.133(8) O(18)−Zn(3)#7 2.132(8) O(8)#4−Zn(1)−O(12) 81.8(3) O(4)#3−Zn(1)−O(8)#4 107.5(3) O(4)#3−Zn(1)−O(10) 87.3(3) O(8)#4−Zn(1)−O(10) 91.8(3) O(4)#3−Zn(1)−O(12) 102.1(3) O(10)−Zn(1)−O(12) 169.8(3) O(4)#3−Zn(1)−O(9)#5 115.9(3) O(8)#4−Zn(1)−O(9)#5 136.6(3) O(10)−Zn(1)−O(9)#5 90.3(3) O(12)−Zn(1)−O(9)#5 88.9(3) O(4)#3−Zn(1)−O(8)#5 168.7(3) O(8)#4−Zn(1)−O(8)#5 82.1(3) O(10)−Zn(1)−O(8)#5 86.3(2) O(12)−Zn(1)−O(8)#5 85.0(3) O(9)#5−Zn(1)−O(8)#5 54.8(2) O(6)#1−Zn(2)−O(13) 88.3(3) O(6)#1−Zn(2)−O(15)#6 98.1(3) O(13)−Zn(2)−O(15)#6 82.9(3) O(6)#1−Zn(2)−O(5)#3 169.2(3) O(13)−Zn(2)−O(5)#3 92.1(3) O(15)#6−Zn(2)−O(5)#3 92.7(3) #1 #6 O(6) −Zn(2)−O(14) 89.8(3) O(13)−Zn(2)−O(14) 178.1(3) O(15) −Zn(2)−O(14) 97.4(3) O(5)#3−Zn(2)−O(14) 89.8(3) O(18)#7−Zn(3)−O(16)#8 91.0(3) O(18)#7−Zn(3)−O(7)#9 89.7(3) O(16)#8−Zn(3)−O(7)#9 100.4(3) O(18)#7−Zn(3)−O(2) 93.5(3) O(16)#8−Zn(3)−O(2) 91.0(3) O(7)#9−Zn(3)−O(2) 168.2(3) O(18)#7−Zn(3)−O(1) 172.5(3) O(16)#8−Zn(3)−O(1) 81.9(3) O(7)#9−Zn(3)−O(1) 89.2(3) O(2)−Zn(3)−O(1) 89.0(3) O(18)#7−Zn(3)−O(3) 82.2(4) O(16)#8−Zn(3)−O(3) 172.8(3) O(7)#9−Zn(3)−O(3) 81.9(4) O(2)−Zn(3)−O(3) 87.2(4) O(1)−Zn(3)−O(3) 105.0(3) symmetry code: #1 −x, −y + 2, −z + 1. #2 −x + 1, −y + 2, −z + 2. #3 −x, −y + 1, −z + 1. #4 −x − 1, −y + 2, −z + 1. #5 x + 1, y, z. #6 −x + 1, −y + 1, −z + 2. #7 −x + 1, −y + 1, −z + 1. #8 x, y, z − 1. #9 x + 1, y − 1, z. #10 x − 1, y + 1, z. #11 x − 1, y, z. #12 x, y, z + 1. complex 7 Cu(1)−O(1)#1 N(3)−Cu(1)#4 N(1)−Cu(1)−N(3)#3 symmetry code: #1 −x +

1.941(6) 1.979(8) 164.2(4) 1, −y + 1, −z

Cu(1)−N(1) O(1)−Cu(1)#5 O(1)#2−Cu(1)−O(4) + 2. #2 x, −y + 1/2, z −

Co(1)−O(3)#1 2.008(3) Co(1)−N(1) Co(1)−O(8) 2.394(3) N(4)−Co(1)#3 #1 #2 O(3) −Co(1)−N(4) 92.60(15) N(1)−Co(1)−N(4)#2 N(4)#2−Co(1)−O(7) 108.20(15) O(3)#1−Co(1)−O(8) O(7)−Co(1)−O(8) 56.78(11) symmetry code: #1 x,−y, z + 1/2. #2 x − 1/2, −y + 3/2, z − 1/2.

1.967(9) Cu(1)−N(3) 1.979(9) 1.941(6) O(1)#2−Cu(1)−N(1) 91.8(3) 159.6(3) N(1)−Cu(1)−O(4) 90.1(3) 1/2. #3 x + 1, y + 1, z. #4 x − 1, y − 1, z. #5 x, −y complex 8 2.058(4) 2.071(4) 106.39(16) 91.98(13)

Co(1)−N(4)#2 O(3)−Co(1)#4 O(3)#1−Co(1)−O(7) N(1)−Co(1)−O(8)

2.071(4) 2.008(3) 140.85(14) 147.22(13)

Cu(1)−O(4) O(1)#2−Cu(1)−N(3)#3 N(3)#3−Cu(1)−O(4) + 1/2, z + 1/2.

1.995(6) 94.1(3) 89.4(3)

Co(1)−O(7) O(3)#1−Co(1)−N(1) N(1)−Co(1)−O(7) N(4)#2−Co(1)−O(8)

2.115(3) 115.38(2) 90.64(14) 89.02(15)

#3 x + 1/2, −y + 3/2, z + 1/2. #4 x, −y, z − 1/2. 794



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Table 2. continued complex 9 2.062(4) N(5)−Ni(1) 2.050(4) N(1)−Ni(2) 2.076(4) N(4)−Ni(1)#2 #3 N(10)−Ni(2) 2.052(4) Ni(1)−O(4)#4 1.993(3) Ni(1)−N(4)#2 2.062(4) Ni(1)−O(6) 2.314(3) Ni(2)−O(8)#5 2.014(3) Ni(2)−N(10)#3 2.052(4) Ni(2)−O(2) 2.117(3) Ni(2)−O(1) 2.180(3) O(4)−Ni(1)#6 1.993(3) O(4)#4−Ni(1)−N(5) 109.22(14) O(4)#4−Ni(1)−N(4)#2 88.13(13) N(5)−Ni(1)−N(4)#2 99.40(14) N(5)−Ni(1)−N(7) 89.44(14) N(4)#2−Ni(1)−N(7) 170.52(14) O(4)#4−Ni(1)−O(5) 157.73(12) N(4)#2−Ni(1)−O(5) 92.73(12) N(7)−Ni(1)−O(5) 90.27(13) O(4)#4−Ni(1)−O(6) 98.94(11) #2 N(4) −Ni(1)−O(6) 91.85(12) N(7)−Ni(1)−O(6) 82.01(13) O(5)−Ni(1)−O(6) 58.79(10) O(8)#5−Ni(2)−O(9) 95.77(12) N(10)#3−Ni(2)−O(9) 91.47(14) O(8)#5−Ni(2)−N(1) 91.38(14) #5 O(9)−Ni(2)−N(1) 86.35(14) O(8) −Ni(2)−O(2) 92.62(11) N(10)#3−Ni(2)−O(2) 90.08(13) N(1)−Ni(2)−O(2) 91.52(13) O(8)#5−Ni(2)−O(1) 153.79(11) N(10)#3−Ni(2)−O(1) 85.37(13) N(1)−Ni(2)−O(1) 91.82(13) O(2)−Ni(2)−O(1) 61.30(11) symmetry code: #1 −x + 1, −y + 1, −z. #2 −x + 2, −y + 1, −z + 1. #3 −x + 2, −y + 3, −z. #4 −x + 3/2, y + 1/2, −z #6 −x + 3/2, y − 1/2, −z + 1/2. #7 −x + 5/2, y + 1/2, −z + 1/2.

Table 3. Coordination Types of H4bpt Ligand and the Roles of Ancillary Ligands in Complexes 1−9 and Previously Reported Polymersa compound

H4bpt coordination mode

1

μ2/Type I

2

μ2/Type I

3

μ2/Type I

4

μ2/Type I

5

μ4/Type II

6

μ6, μ9/Type III, IV

7 8 9

μ4/Type III μ2/Type I μ4/Type II

Co2(bpt)4a Co2(bpt)4a Ni2(bpt)(bme)4c Ni2(bpt)(bmb)4c Sc2(bpt)4d Mg2(bpt)4e Zn(bpt)4e Cu2(bpt)4g Zn(bpt)0.5(phen)4f

μ8/Type μ7/Type μ4/Type μ4/Type μ8/Type μ8/Type μ4/Type μ8/Type μ6/Type

VI V II II VI VI II VI III

ancillary ligands/role Hpptp/μ3-bridging chelating Hpptp/μ3-bridging chelating Hpptp/μ3-bridging chelating Hpptp/μ3-bridging chelating Hpptp/μ3-bridging chelating

N(7)−Ni(1) Ni(1)−O(5) Ni(2)−O(9) O(8)−Ni(2)#7 O(4)#4−Ni(1)−N(7) N(5)−Ni(1)−O(5) N(5)−Ni(1)−O(6) O(8)#5−Ni(2)−N(10)#3 N(10)#3−Ni(2)−N(1) O(9)−Ni(2)−O(2) O(9)−Ni(2)−O(1)

2.089(4) 2.125(3) 2.053(3) 2.014(3) 85.71(13) 92.60(13) 149.86(13) 92.63(14) 175.62(15) 171.39(12) 110.39(12)

+ 1/2. #5 −x + 5/2, y − 1/2, −z + 1/2.

Scheme 1. Diverse Coordination Modes of H4bpt in Complexes 1−9 and Previously Reported Polymers

dimension/topology +

2D/63

+

2D/63

+

2D/63

+

2D/63

+

3D/ (62.8)2(62.82.102) 3D/(410.65) (419.616.8)(46.64) (47.63)2 4,4′-bimbp/μ2-bridging 3D/(62.84)(42.82)2 2,7-dfo/μ2-bridging 3D/66 4,4′-bibp/μ2-bridging 3D/(64.82)(65.8) (68.82) 3D 3D Bme/μ2-bridging 3D Bmb/μ2-bridging 3D 3D 3D 3D 3D Phen/cheating 2D

Synthesis of {[Mn(H2bpt)(Hpptp)]}n (1). A mixture of H4bpt (0.15 mmol, 0.050 g), Hpptp (0.20 mmol, 0.060 g), manganese(II) sulfate monohydrate (0.20 mmol, 0.034 g), oxalic acid (0.40 mmol, 0.036 g), NaOH (0.10 mmol, 0.004g), and 14 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature. Orange block crystals were obtained. Yield of 57% (based on Mn). Anal. (%) calcd. for C34H21N5O8Mn: C, 59.83; H, 3.10; N, 10.26. Found: C, 59.78; H, 3.06; N, 10.13. IR (KBr pellet, cm−1): 3435 (vs), 3069 (s), 1712 (s), 1678 (s), 1550 (s), 1415 (s), 1241 (s), 1142 (w), 777 (m), 725 (m), 673 (w). Synthesis of {[Fe(H2bpt)(Hpptp)]}n (2). The same synthetic procedure as for 1 was used except that manganese(II) sulfate monohydrate was replaced by iron(II) sulfate heptahydrate, giving red block crystals. Yield of 87% (based on Fe). Anal. (%) calcd. for C34H21N5O8Fe: C, 59.75; H, 3.10; N, 10.25. Found: C, 59.68; H, 3.05; N, 10.14. IR (KBr pellet, cm−1): 3409 (vs), 3050 (s), 1712 (vs), 1548 (vs), 1412 (vs), 1295 (m), 1227 (m), 849 (m), 773 (m), 604 (w). Synthesis of {[Co(H2bpt)(Hpptp)]}n (3). The same synthetic procedure as for 1 was used except that manganese(II) sulfate monohydrate was replaced by cobalt(II) sulfate heptahydrate, giving red block crystals. Yield of 69% (based on Co). Anal. (%) calcd. for C34H21N5O8Co: C, 59.49; H, 3.08; N, 10.20. Found: C, 59.37; H, 2.92; N, 10.16. IR (KBr pellet, cm−1): 3438 (vs), 3065 (m), 1708 (vs), 1573 (vs), 1412 (vs), 1225 (s), 1143 (s), 850 (m), 792 (m), 514 (w). Synthesis of {[Zn(H2bpt)(Hpptp)]}n (4). The same synthetic procedure as for 1 was used except that manganese(II) sulfate monohydrate was replaced by zinc(II) acetate dihydrate, giving colorless block crystals.

a

Note: bme = 1,2-bis(1,3,5,8,12-pentaazacyclotetradecan-3-yl)ethane; phen = 1,10-phenanthroline; bmb = 1,4-bis(1,3,5,8,12-pentaazacyclotetradecan-3- yl)butane.

data were collected on an Edinburgh FLS920 TCSPC system. Thermogravimetric measurements were carried out in a nitrogen stream using a Netzsch STA449C apparatus with a heating rate of 10 °C min−1. X-ray powder diffraction (XRPD) was carried out on a RIGAKU DMAX2500 apparatus. Synthesis of Complexes 1−9. The syntheses for the target nine complexes were all performed in 25 mL Teflon-lined stainless steel vessels by utilizing the hydrothermal method. During the synthetic process, oxalic acid and sodium hydroxide were used as a buffer to deprotonate the carboxylate groups of H4bpt and promote the selfassembly.10d The carboxylate groups of H4bpt in complexes 1−4 and 8 are partially deprotonated. With the pH rising by adding more NaOH and removing oxalic acid, the four carboxyl groups of H4bpt in 5−7 and 9 are completely deprotonated. 795



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Figure 1. (a) Coordination environment of MnII atom in 1 (symmetry codes: A, x, 1 − y, 0.5 + z; B, −x, −y, 1 − z). (b) The 2D sheet of 1 consisting of 1D zigzag [Mn(H2bpt)]n chain and binuclear [Mn2(Hpptp)2] subunit. (c) Two-fold parallel interpenetrating network of 1 based on intertwined helices consisting of channels. (d) The 3D porous network of 1 formed via the interlayer π···π stacking. sulfate pentahydrate (0.20 mmol, 0.050 g), oxalic acid (0.50 mmol, 0.045 g), NaOH (0.20 mmol, 0.008 g), and 13 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature, giving blue block crystals. Yield of 53% (based on Cu). Anal. (%) calcd. for C28H23N4O5Cu: C, 60.16; H, 4.15; N, 10.02. Found: C, 59.96; H, 4.07; N, 10.18. IR (KBr pellet, cm−1): 3443 (vs), 3052 (vs), 1691 (vs), 1542 (vs), 1397 (vs), 1323 (vs), 1153 (s), 856 (s), 734 (s), 645 (w). Synthesis of {[Co(H2bpt)(2,7-dfo)]·H2O}n (8). A mixture of H4bpt (0.10 mmol, 0.033 g), 2,7-dfo (0.20 mmol, 0.062 g), cobalt(II) nitrate hexahydrate (0.20 mmol, 0.058 g), oxalic acid (0.50 mmol, 0.045 g), and 13 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature, giving red block crystals. Yield of 47% (based on Co). Anal. (%) calcd. for C35H22N4O10Co: C, 58.59; H, 3.09; N, 7.81. Found: C, 58.12; H, 2.98; N, 7.43. IR (KBr pellet, cm−1): 3469 (vs), 3072 (vs), 1769 (vs), 1546 (vs), 1422 (vs), 1267 (vs), 1147 (s), 862 (s), 719 (s), 662(w). Synthesis of {[Ni2(bpt)(4,4′-bibp)2.5(H2O)]·3(H2O)}n (9). A mixture of H4bpt (0.10 mmol, 0.033 g), 4,4′-bibp (0.20 mmol, 0.059 g), nickel(II) dichloride hexahydrate (0.20 mmol, 0.047 g), NaOH (0.30 mmol, 0.012 g), and 12 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature, giving red block crystals. Yield of 47% (based on Co). Anal. (%) calcd. for C61H49N10O12Ni2: C, 59.49; H, 4.01; N, 11.38. Found: C, 59.12; H,

Yield of 74% (based on Zn). Anal. (%) calcd. for C34H21N5O8Zn: C, 58.93; H, 3.05; N, 10.10. Found: C, 58.88; H, 2.85; N, 9.92. IR (KBr pellet, cm−1): 3426 (vs), 3066 (s), 1713 (m), 1587 (vs), 1415 (s), 1373 (s), 777 (m), 727 (m), 535 (w). Synthesis of {[Mn2(bpt)(Hpptp)2]}n (5). A mixture of H4bpt (0.10 mmol, 0.033 g), Hpptp (0.20 mmol, 0.060 g), manganese(II) sulfate monohydrate (0.20 mmol, 0.034 g), 4,5-di(4′-carboxylphenyl)phthalic acid (0.08 mmol, 0.030 g), NaOH (0.20 mmol, 0.008 g), and 12 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature, giving orange block crystals. Yield of 64% (based on Mn). Anal. (%) calcd. for C52H32N10O8Mn2: C, 60.30; H, 3.12; N, 13.54. Found: C, 59.98; H, 3.02; N, 13.47. IR (KBr pellet, cm−1): 3473 (vs), 3069 (vs), 1703 (vs), 1577 (vs), 1416 (vs), 1388 (vs), 1230 (vs), 1140 (s), 852 (s), 726 (s), 653 (w). Synthesis of {[Zn3(Hbpt)(bpt)(H2O)2][(4,4′-H2bmib)0.5]·H2O}n (6). A mixture of H4bpt (0.10 mmol, 0.033 g), 4,4′-bmib (0.18 mmol, 0.060 g), zinc(II) acetate dihydrate (0.20 mmol, 0.044 g), NaOH (0.20 mmol, 0.008 g), and 10 mL of H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 °C/h) to room temperature, giving colorless block crystals. Yield of 34% (based on Zn). Anal. (%) calcd. for C40H29N2O19Zn3: C, 46.29; H, 2.82; N, 2.67. Found: C, 45.98; H, 3.04; N, 2.59. IR (KBr pellet, cm−1): 3428 (vs), 3073 (vs), 1693 (vs), 1589 (vs), 1438 (vs), 1362 (vs), 1147 (s), 792 (s), 723 (s), 560 (w). Synthesis of {[Cu(bpt)0.5(4,4′-bimbp)]·H2O}n (7). A mixture of H4bpt (0.10 mmol, 0.033 g), 4,4′-bimbp (0.20 mmol, 0.057 g), copper(II) 796



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Figure 2. (a) Coordination environment of MnII atom in 5 (symmetry codes: A, −x, −y, 1− z; B, x, 1 − y, −0.5 + z). (b) The 2D sheet of 5 in ac plane. (c) The pillared-layer 3D porous network of 5. (d) Schematic view of the (3,4)-connected network of 5 (green spheres, MnII atoms; purple spheres, bpt4− ligands). 4.02; N, 11.29. IR (KBr pellet, cm−1): 3458 (vs), 3072 (vs), 1708(vs), 1569 (vs), 1412 (vs), 1264 (vs), 1147 (s), 879 (s), 713 (s), 629 (w). Single Crystal Structure Determination. Intensity data collection was carried out on a Siemens SMART diffractometer equipped with a CCD detector using Mo-Kα monochromatized radiation (λ = 0.71073 Å) at 293(2) K. The absorption correction was based on multiple and symmetry-equivalent reflections in the data set using the SADABS program based on the method of Blessing. The structures were solved by direct methods and refined by full-matrix least-squares using the SHELXTL package.11 Crystallographic data for complexes 1−9 are given in Table 1. Selected bond lengths and angles for 1−9 are listed in Table 2. For complexes of 1−9, further details on the crystal structure investigations may be obtained from the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, CAMBRIDGE CB2 1EZ, UK, [Telephone: +44-(0)1223−762−910, Fax: +44-(0)1223− 336−033; Email: [email protected]; http://www.ccdc.cam.ac.uk/ deposit], on quoting the depository number CCDC-903965 for 1, 903966 for 2, 903967 for 3, 903968 for 4, 903969 for 5, 903970 for 6, 903971 for 7, 903972 for 8, and 903973 for 9.

show the coordination modes μ1-η1:η0, μ1-η1:η1, μ1-η1:η0, and μ1-η1:η1 in a clockwise direction (Type II). Such coordination mode also exists in the previously reported complexes of Ni2(bpt)(bme),4c Ni2(bpt)(bmb),4c and Zn(bpt).4e In 6, bpt4− exhibits the coordination modes syn-syn μ2-η1:η1, μ3-η2:η2, syn-syn μ2-η1:η1, and syn-anti μ2-η1:η1 (Type III); Hbpt3‑, μ1-η1:η0, synsyn μ2-η1:η1, μ1-η1:η0, and syn-anti μ2-η1:η1 (Type IV). The coordination mode of Type V (μ1-η1:η0, μ2-η2:η1, syn-syn μ2-η1:η1, and syn-anti μ2-η1:η1 in a clockwise direction) also exists in the complex of Co2(bpt).4a The previously reported complexes of Sc2(bpt),4d Mg2(bpt),4e and Cu2(bpt)4g adopt the single synsyn μ2-η1:η1 coordination mode (Type VI). Judging by Table 3 and Scheme 1, although the carboxylate groups of H4bpt in complexes 1−4 and 8 are partially deprotonated and H2bpt2− acts as a Z-shaped bridge to link metal cations of M2+ into a 1D zigzag polymeric [M(H2bpt)]n chain, complexes 1−4 own a 2D network via the bond linkage, different from the 3D one for complex 8 due to that more coordination sites around M2+ are occupied by two μ3-bridging + chelating ligands of Hpptp. In 7 and 9, the four carboxyl groups of H4bpt are completely deprotonated and bpt4− acts as an H-shaped bridge, linking four neighboring MII ions into 2D layers, which are further linked by bidenate ancillary ligands to form the anticipated 3D frameworks. Thus, the crystal architectures are attributed to the complicated factors, such as the versatility of metal cations and ligands, the subtle influences of weak interactions, and other factors including synthetic conditions.12 Structure of {[M(H2bpt)(Hpptp)]}n (M = Mn (1), Fe (2), Co (3), and Zn (4)). The single-crystal X-ray diffraction analysis

■

RESULTS AND DISCUSSION Diverse Coordination Modes of H4bpt and Structural Comparison. As shown in the Table 3 and Scheme 1, H4bpt exhibits versatile coordination modes in complexes 1−9 and the previously reported ones.4a,c−f In complexes 1−4 and 8, four carboxyl groups of H4bpt are partially deprotonated, and the two deprotonated ones adopt μ1-η1:η1 coordination mode (named as Type I), linking the metal ions into a 1D [M(H2bpt)]n. By adding more NaOH and removing oxalic acid, the four carboxyl groups of H4bpt in 5−7 and 9 are completely deprotonated and 797



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Figure 3. (a) Coordination environment of ZnII atoms in 6 (symmetry codes: A, −x, 2 − y, 1 − z; B, 1 − x, 2 − y, −z + 2; C, −x, 1 − y, 1 − z; D, −1 − x, 2 − y, 1 − z; E, 1 + x, y, z; F, 1 − x, 1 − y, 2 − z; G, 1 − x, 1 − y, 1 − z). (b) The view of 1D unusual Zn6-based chain of 6. (c) The 3D honeycomb porous network consisting of 1D channels. (d) Schematic view of the (5,5,5,6,9)-connected network of 6 (blue spheres, ZnII atoms; pink spheres, bpt4− ligands).

Furthermore, the adjacent layers are linked to generate a 3D porous network (Figure 1d) via the interlayer π···π stacking between Hpptp ligands with the centroid−centroid separation of 3.834 Å. The void volume of 1 is 39.4% of the crystal volume (1685.9 out of the 4276.0 Å3 unit cell volume), calculated by PLATON.13 To better understand the structure of 1, the topological analysis approach is employed. In the 2D sheet, all Mn(II) ions are 3-connecting, and the shortest circuit is a six-membered ring. So the 2D sheet can be simplified to a 2-fold parallel interpenetrating binodal 3-connected 63-hcb net. Structure of {[Mn2(bpt)(Hpptp)2]}n (5). Single-crystal X-ray diffraction analysis reveals that complex 5 crystallizes in the triclinic system, space group P̅1, showing a pillared-layer 3D porous network. The asymmetric unit of 5 consists of two MnII atoms, one bpt4−, and two Hpptp ligands. Both of Mn(1) and Mn(2) own a distorted octahedral coordination geometry, completed by three O atoms from two bpt4− ligands and three N atoms from two Hpptp ligands (Figure 2a). The Mn−O/N bond lengths and the bond angles around each MnII center are 2.038(9)−2.276(8)/2.217(11)−2.273(9) Å and 58.5(3)− 164.6(4)°, respectively. The four carboxyl groups of H4bpt in 5, different from the ones in compounds 1−4 due to the higher pH by adding more NaOH and removing oxalic acid in the reaction environment, are completely deprotonated and adopt the coordination modes of μ1-η1:η0, μ1-η1:η1, μ1-η1:η0, and μ1-η1:η1 in a clockwise direction (Type II). The ligand of bpt4− acts as an H-shape ligand to connect the MnII centers, generating a 2D grid

reveals that complexes 1−4 are isomorphism and crystallize in the monoclinic system, P2/c space group; herein, only the structure of 1 will be discussed as a representation. The asymmetric unit of 1 consists of one crystallographically independent MnII atom, one H2bpt2−, and one Hpptp ligand. Each MnII center is hepta-coordinated by three N atoms from two Hpptp ligands [Mn(1)−N(1) = 2.263(4), Mn(1)−N(2) = 2.257(4), and Mn(1)−N(5) = 2.238(4) Å] and four O atoms from two H2bpt2− ligands [Mn(1)−O(3) = 2.761(9), Mn(1)−O(4) = 2.155(3), Mn(1)−O(7) = 2.394(4), and Mn(1)−O(8) = 2.208(3) Å], showing a distorted pentagonal bipyramid coordination geometry. Two Hpptp ligands adopt the μ3-bridging + chelating modes to bind two Mn(II) centers forming a rodlike binuclear [Mn2(Hpptp)2] subunit (Figure S3, Supporting Information). The two deprotonated carboxyl groups of H2bpt2− show μ1-η1:η1 coordination mode, and H2bpt2− acts as a Z-shaped ligand (Scheme 1, Type I) linking the MnII centers to a 1D zigzag polymeric [Mn(H2bpt)]n chain along the c axis with the adjacent Mn···Mn separation of 14.097 Å. The neighboring chains are further connected by Hpptp ligands to form the resulting 2D network (Figure 1b). Two such 2D networks are mutually interpenetrated with each other to form a 2-fold parallel interpenetrating network consisting of channels, shown in Figure 1c. Interestingly, each channel is enclosed by two intertwined helices with the same handedness. These double-stranded helices in the 2D double layer are built up from two identical right-handed single-helical chains with a pitch of 17.12 Å and alternately arrange in a right- and left-handed sequence, so that the whole sheet does not show chirality. 798



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Figure 4. (a) Coordination environment of CuII atom in 7 (symmetry codes: A, 1 − x, 1 − y, 2 − z). (b) The 4-connected 2-D layer of 7 along the bc plane. (c) Schematic view of the binodal (4,4)-connected 3D framework of 7 with (62·84)(42·82)2 topology (blue spheres, CuII atoms; pink spheres, bpt4− ligands).

syn-anti μ2-η1:η1 (Type IV). Interestingly, each six ZnII cations are connected by ten carboxylic groups to form a hexanuclear {Zn6(COO)10} unit (abbreviated as {Zn6}), just like one lengthened chair-configuration cyclohexane (Figure 3b). Each two neighboring {Zn6} units are further connected by sharing one carboxylate oxygen atom giving rise to one 1D {Zn6}-based chain along [111] orientation, which was further linked by the Hbpt3‑/bpt4‑ ligand resulting in a 3D honeycomb porous network (Figure 3c). It is worth noting that the guest molecules of 4,4′-H2bmib are included in the voids of packing diagram. From the viewpoint of structural topology, if the cations of Zn(1), Zn(2), and Zn(3) are considered as 5-connected nodes, Hbpt3− as 6-connected nodes, and bpt4− as 9-connected nodes, the whole 3D structure exhibits a rare (5,5,5,6,9)-connected topology with the Schläfli symbol of (410.65)(419.616.8)(46.64)(47.63)2 (Figure 3d), never documented to date. Structure of {[Cu(bpt)0.5(4,4′-bimb)]·H2O}n (7). Singlecrystal X-ray diffraction analysis reveals that complex 7 crystallizes in the monoclinic system, space group P2(1)/c. As shown in Figure 4a, there are one crystallographically independent CuII atom, a half of bpt4−, and one 4,4′-bimb in the asymmetric unit. The CuII cation is penta-coordinated by two N atoms from two 4,4′-bimb [Cu(1)−N(1) = 1.961(4) and Cu(1)− N(3) = 1.978(4) Å] and two O atoms from two bpt4− [Cu(1)− O(4) = 1.987(4) and Cu(1)−O(1)A = 1.932(3) Å]. In 7, the four carboxyl groups of H4bpt are completely deprotonated and

(Figure 2b) parallel to the ac plane consisting of rectangular cavities with the sizes of 10.49 × 13.18 Å2. The Hpptp ligand acts as a pillar to connect the grids, leaving a pillared-layer 3D network (Figure 2c). The void volume of 5 is 42.2% of the crystal volume, calculated by PLATON.13 From a topological perspective, MnII and bpt4− act as 3-connected and 4-connected nodes, respectively, giving rise to a (3,4)-connected 3D network with the Schläfli symbol of (62.8)2(62.82.102) (Figure 2d). Structure of {[Zn3(Hbpt)(bpt)(H2O)2][(4,4′-H2bmib)0.5]· H2O}n (6). Single-crystal X-ray diffraction analysis reveals that complex 6 is an unprecedented 3D host-framework based on Zn6 clusters with the flexible N-donor 4,4′-H2bmib as a guest molecule. Compound 6 crystallizes in the triclinic system, space group P̅1. As shown in Figure 3a, the asymmetric unit consists of three independent ZnII atoms, one Hbpt3−, one bpt4−, two associated water molecules, one lattice water molecule, and a half of 4,4′-H2bmib as the guest molecule. The three unique zinc cations including Zn(1), Zn(2), and Zn(3) are hexacoordinated by six oxygen atoms. Zn(1) is coordinated by six oxygen atoms from one Hbpt3−, four bpt4−, and one water molecule. Both Zn(2) and Zn(3) are coordinated by six oxygen atoms from three Hbpt3−, two bpt4−‑, and one water molecule. The Zn−O bond lengths are in the range of 2.086(8)− 2.503(7) Å. In 6, bpt4− exhibits the coordination modes synsyn μ2-η1:η1, μ3-η2:η2, syn-syn μ2-η1:η1, and syn-anti μ2-η1:η1 (Type III); Hbpt3−, μ1-η1:η0, syn-syn μ2-η1:η1, μ1-η1:η0, and 799



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Figure 5. (a) Coordination environment of CoII atom in 8 (symmetry codes: A, x, −y, 0.5 + z; B, −0.5 + x, 1.5 − y, −0.5 + z). (b) The 4-connected 2D layer of 8. (c) The view of a 6-fold 3D interpenetrating network of 8. (d) Schematic view of the 4-connected 3D 6-fold interpenetrating nets of 8 with 66 topology (green spheres, MnII atoms; blue spheres, bpt4− ligands).

adopt the coordination modes of μ1-η1:η0, μ1-η1:η1, μ1-η1:η0, and μ1-η1:η1 in a clockwise direction (Type II) to link four CuII ions forming a 2D net along the bc plane (Figure 4b). Such 2D nets are further linked by the flexible N-donor 4,4′-bimb to form a 3D framework, consisting of 1D right-handed helix chains (Figure 4b). From a topology view, the network of 7 can be rationalized to a (4,4)-connnected topology with the Schläfli symbol of (62.84)(42.82)2 by denoting the CuII atoms as 2connected nodes and bpt4− as 4-connected nodes, respectively (Figure 4d), which represents the first (4,4)-connected coordination framework with a (62.84)(42.82)2 topology. Structure of {[Co(H2bpt)(2,7-dfo)]·H2O}n (8). Single-crystal X-ray diffraction analysis reveals that complex 8 crystallizes in the monoclinic system, space group C2/c. As shown in Figure 5a, there are one crystallographically independent CoII atom, one H2bpt2−, one 2,7-dfo, and one free water molecule in the asymmetric unit. Each CoII center is hexa-coordinated by two N atoms from two 2,7-dfo ligands [Co(1)−N(1) = 2.058(4) and Co(1)−N(4) = 2.072(6) Å] and four O atoms from two H2bpt2− ligands [Co(1)−O(3) = 2.007(4), Co(1)−O(4) = 2.470(3), Co(1)−O(7) = 2.117(3), and Co(1)−O(8) = 2.391(5) Å], showing a distorted octahedral coordination geometry. The two deprotonated carboxyl groups of H2bpt4− exhibit μ1-η1:η1 coordination mode linking two neighboring

CoII ions along the c axis to form a 1D zigzag chain [Co(H2bpt)]n. Such chains are linked by 2,7-dfo along [110] orientation to form 2D nets, which are mutually interpenetrated via the bridge of 2,7-dfo to form a 6-fold 3D interpenetrating network (Figure 5c). It is worth noting that each channel is enclosed by three intertwined helices with the same handedness. These triple-stranded helices in the 2D double layer is built up from three identical righthanded single-helical chains with a pitch of 22.93 Å, alternately arranged in a right- and left-handed sequence (Figure 5c). From a topology view, the network of 8 can be rationalized to a 4-connnected diamond topology with the Schläfli symbol of 66 by denoting the CoII atoms as four-connected nodes. (Figure 5d). Structure of {[Ni2(bpt)(4,4′-bibp)2.5(H2O)]·3(H2O)}n (9). Single-crystal X-ray diffraction analysis reveals that complex 9 crystallizes in the monoclinic system, space group P2(1)/c. As shown in Figure 6a, there are two crystallographically independent NiII atoms, one bpt4− ligand, two and a half of 4,4′-bibp ligands, one terminal water molecule, and three free water molecules in the asymmetric unit. Ni(1) is hexacoordinated by three nitrogen atoms from three different 4,4′-bibp ligands and three oxygen atoms from two individual bpt4− ligands, leaving an distorted octahedral geometry. Ni(2) shows octahedral coordination geometry, completed by three oxygen atoms from two bpt4− ligands, two nitrogen atoms from 800



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Figure 6. (a) Coordination environment of NiII atom in 9 (symmetry codes: A, 1 − x, 1 − y, −z; B, 2 − x, 1 − y, 1 − z; C, 2 − x, 3 − y, −z; D, 1.5 − x, 0.5 + y, 0.5 − z). (b) The view of the 4-connected 2D layer of 9. (c) The 3D frameworks based on 4-connected 2D nets linked via 4,4′-bibp. (d) Schematic view of the trinodal (4,4,5)-connected 3D frameworks with point Schläfli symbol of (64.82)(65.8)(68.82) of 9 (green spheres, MnII atoms; blue spheres, bpt 4− ligands).

for ZnO, 11.8%) for 4, and 18.2% (calcd for MnO2, 16.8%) for 5. Different from 1−5, the TG curves for compounds 6−9 indicate that two weight loss steps took place, which prove that the rodlike binuclear [M2(Hpptp)2] subunits in 1−5 are much stable. The removal of the water molecules can be observed with the weight loss of 4.6% (calcd 5.2%) for 6, 3.0% (calcd 3.2%) for 7, 2.2% (calcd 2.5%) for 8, and 3.4% (calcd 3.9%) for 9, respectively. The second weight loss observed is attributed to the release of the ancillary ligands, which took place around 400 °C. The residual weight is 22.5% (calcd for ZnO, 23.4%) for 6, 14.5% (calcd for CuO, 11.2%) for 7, 14.0% (calcd for Co2O3, 11.6%) for 8, and 16.0% (calcd for NiO, 12.2%) for 9. Photoluminescent Investigation. The fluorescence spectrum of 4 and 6 was examined in the solid state at room temperature, shown in Figure 7. The intense emissions occur at 431 and 457 nm for compounds 4 and 6 with the excitation wavelength of 380 nm. The free organic ligands are nearly nonfluorescent in the range 350−550 nm for excitation wavelength of 380 nm at ambient temperature. The emissions are neither metal-to-ligand charge transfer (MLCT) nor ligand-to-metal transfer (LMCT) in nature since ZnII is difficult to oxidize or reduce due to its d10 configuration.14 Thus, they may be assigned to intraligand (π* → n or π* → π) emission. The enhancement of luminescence in d10 complexes may be attributed to ligand chelation to the metal center, which effectively increases the rigidity of the ligand and reduces the loss of energy by radiationless decay.15 The observation indicates that

two 4,4′-bibp ligands, and one oxygen atom from the coordinated water molecule. The Ni−O and Ni−N distances are in the ranges of 1.994−2.311 and 2.048−2.085 Å, respectively. Ni(1) and Ni(2) are linked by 4,4′-bibp ligands to form a 1D ladder chain (Figure 6a). The carboxyl groups of H4bpt ligand in compound 9 are completely deprotonated and exhibit μ1-η1:η0 and μ1-η1:η1 coordination modes to link four NiII ions, forming a 4-connected 2D nets (Figure 6b), which are further linked by 4,4′-bibp ligands to form a 3D framework (Figure 6c). From a topology view, the network of 9 can be rationalized to a novel (4,4,5)-connected 3D framework with the point Schläfli symbol of (64.82)(65.8)(68.82), in which Ni(1) and Ni(2) act as four-connected and five-connected nodes (Figure 6d). PXRD and Thermal Analysis. In order to check the phase purity of these complexes, the powder X-ray diffraction (PXRD) patterns were checked at room temperature. As shown in Figure S1 (Supporting Information), the peak positions of the simulated and experimental PXRD patterns are in agreement with each other, demonstrating the good phase purity of the title complexes. The thermal behaviors of 1−9 were studied on the crystal samples under N2 atmosphere with a heating rate of 10 °C min−1, shown in Figure S2 (Supporting Information). The TGA curves of 1−9 suggested that their host frameworks were stable up to ∼360, ∼345, ∼385, ∼315, ∼360, ∼380, ∼290, ∼390, and ∼365 °C, respectively. For compounds 1−5, the whole structure began to collapse around 350 °C with the residual weight at ca. 15.1% (calcd for MnO2, 12.8%) for 1, 15.0% (calcd for Fe2O3, 11.7%) for 2, 15.5% (calcd for Co2O3, 12.1%) for 3, 15.0% (calcd 801



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the polymeric complexes of 4 and 6 may be excellent candidates for potential photoactive materials.

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CONCLUSIONS In summary, a series of new MOFs have been isolated from the hydrothermal reactions by the employment of H4bpt and five different N-donor ancillary ligands (Hpptp, 4,4′-bmib, 4,4′bimbp, 2,7-dfo, and 4,4′-bibp). Compounds 1−9 displayed appealing structural features from 2D layers to 3D frameworks, such as novel unprecedented 3D (5,5,5,6,9)-connected hostframework of 6, binodal (4,4)-connected 3D framework of 7, and trinodal (4,4,5)-connected 3D framework of 9. The diverse coordination modes of H4bpt proved that the construction of coordination compounds depends on the important reaction environments, such as the nature of carboxylate anion, coordination geometry of central metal, ancillary ligands, pH, and so on. By applying this synthetic method, we have already prepared a large number of new MOFs with new structural features and potentially interesting physical properties that will be reported in future papers. ASSOCIATED CONTENT

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AUTHOR INFORMATION

REFERENCES

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Figure 7. Solid-state emission spectrum of 4 and 6 (λex = 380 nm) at room temperature.

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Article

* Supporting Information S

PXRD, structural data and figures, and thermal analyses data. This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author

*Tel: +86-531-66778062. E-mail: [email protected] (X.Z.); [email protected] (J.D.); [email protected] (L.H.). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The work was supported by financial assistance from the Natural Science Foundation of China (Grant Nos. 21101097 and 21071087) and Natural Science Foundation of Shandong Province (ZR2010BQ023). Qilu Normal University is acknowledged. 802



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