Lanthanide Coordination Polymers Constructed from Dinuclear

Jul 15, 2008 - Junwei Ye,† Jingying Zhang,‡ Guiling Ning,† Ge Tian,§ Yan Chen,§ and Yue Wang*,‡. State Key Laboratory of Fine Chemicals and ...
1 downloads 0 Views 3MB Size
Download PDF
Lanthanide Coordination Polymers Constructed from Dinuclear Building Blocks: Novel Structure Evolution from One-Dimensional Chains to Three-Dimensional Architectures Junwei Ye,† Jingying Zhang,‡ Guiling Ning,† Ge Tian,§ Yan Chen,§ and Yue Wang*,‡

CRYSTAL GROWTH & DESIGN 2008 VOL. 8, NO. 8 3098–3106

State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian UniVersity of Technology, 158 Zhongshan Road, Dalian 116012, P. R. China, State Key Laboratory of Supramolecular Structure and Materials, Jilin UniVersity, Changchun 130012, P. R. China, and State Key Laboratory of Inorganic Synthesis & PreparatiVe Chemistry, Jilin UniVersity, Changchun 130012, P. R. China ReceiVed March 24, 2008; ReVised Manuscript ReceiVed May 6, 2008

ABSTRACT: A series of lanthanide coordination polymers [Ln(NIPH)(HNIPH)(phen)] [Ln ) Tb (1), Ho (2), Er (3), La (4), Sm (5)], [Ln2(NIPH)3(phen)2(H2O)] · (H2O) (Ln ) Pr (6), Yb (7), [Ln2(NIPH)3(phen)2] [Ln ) Eu (8), Nd (9)] (H2NIPH ) 5-nitroisophthalic acid, phen ) 1,10-phenanthroline) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. The frameworks constructed from dinuclear lanthanide building blocks exhibit three typical structure features: 1-3 possess one-dimensional double-stranded looplike chain structures, 4-7 have two-dimensional layer structure characteristics, 8 and 9 are the three-dimensional frameworks with pcu topology. In 1-9, NIPH ligands adopt multidentate coordination modes. The supramolecular architectures of 1-9 show that the presence of phen ligands and nitro groups on NIPH induced the formation of numerous hydrogen bonds. The luminescent and magnetic properties of 8 and 9 are investigated. Introduction A great deal of effort has been invested in the design and synthesis of coordination polymers due to their intriguing network topologies and promising applications in fields such as catalysis, ion exchange, gas storage, selective adsorption and separation, optics and magnetic devices.1,2 Up to now, numerous one-, two-, and three-dimensional (1-D, 2-D, and 3-D) coordination polymers have been synthesized by the choice of appropriate metal ions and versatile bridging organic ligands.3,4 As compared with the fruitful reports of transition metal coordination polymers, the assembly of lanthanide coordination networks has had an upsurge of interest in recent years.5 For the variable coordination numbers and special chemical characteristics of lanthanide ions, they can be used to construct fascinating network topologies; in particular, some reported lanthanide coordination polymers exhibit interesting magnetism and luminescence properties arising from 4f electrons.6 Considering that the lanthanide ions have high affinities for hard donor atoms like oxygen of carboxylic groups, benzenepolycarboxylate ligands are often employed to link the nodes of the single metal ions or metal-carboxylate clusters in lanthanide-organic frameworks.5–7 For example, the use of 1,4benzenedicarboxylate has led to a series of lanthanide metalorganic frameworks with novel optical properties.5a,8 To construct novel architectures, various functional groups such as amine, sulfonate, nitro and hydroxyl groups have been attached to benzene-polycarboxylate ligands.9–11 Recently, we have systematically studied supramolecular lanthanide frameworks based on 5-nitroisophthalic acid (H2NIPH).11d The H2NIPH is a versatile ligand for the construction of coordination polymers based on the following three points: (i) its two carboxylates groups may be completely or partially deprotonated, resulting * Corresponding author. E-mail: [email protected]. † Dalian University of Technology. ‡ State Key Laboratory of Supramolecular Structure and Materials, Jilin University. § State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University.

in rich coordination modes and formation of the lanthanide clusters, which may act as secondary building units to construct frameworks with novel structural features; (ii) its nitro group can act as the hydrogen-bond acceptor to form hydrogen bonds, which is often useful for the formation of stable frameworks; (iii) its chemical and thermal stabilities are very good.10,11 In this work, we used 5-nitroisophthalic acid (H2NIPH) as the bridge ligand and 1,10-phenanthroline (phen) as the ancillary ligand to construct novel lanthanide coordination networks under hydrothermal conditions. The synthesis, crystal structures, and properties of nine lanthanide coordination polymers [Ln(NIPH)(HNIPH)(phen)] [Ln ) Tb (1), Ho (2), Er (3), La (4), Sm (5)], [Ln2(NIPH)3(phen)2(H2O)] · (H2O) (Ln ) Pr (6), Yb (7), [Ln2(NIPH)3(phen)2] [Ln ) Eu (8), Nd (9)] will be presented. Experimental Section Materials and Instruments. The lanthanide nitrate salts were prepared by dissolving the rare earth oxides in the aqueous solution of HNO3 (8.0 M). After the water was distilled off at 100 °C, the lanthanide nitrate salt was obtained. All other reagents were of reagent grade and used without further purification. Elemental analysis was performed on a Perkin-Elmer 240C elemental analyzer. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer TGA 7 unit with a heating rate of 10 °C/min. Photoluminescence spectra were measured on a Shimadzu RF-5301PC spectrophotometer. Microscopic images were observed on a OLYMPUS BX51 fluorescent microscope. The powder X-ray reflection data was collected on a Rigaku R-AXIS RAPID diffractometer (Mo kR radiation, graphite monochromated). Magnetic susceptibility data was collected over a temperature range of 4-300 K at a magnetic field of 1 kOe on a Quantum Design MPMS-7 SQUID magnetometer. Synthesis of [Tb(NIPH)(HNIPH)(phen)] (1). A mixture of Tb(NO3)3 (0.4 mmol), H2NIPH (0.4 mmol)), phen (0.4 mmol), and H2O (10 mL) was heated at 170 °C for 72 h in a Teflon-lined stainless steel autoclave (25 mL) under autogenous pressure. After the sample was cooled to room temperature, the block-shaped white color crystals were obtained, which were washed with water and dried in air. The yield was 56% based on Tb. Elemental analysis calcd (%) for C28H15N4O12Tb (758.36): C 44.35%; H 1.99%; N 7.39%; found: C 44.52%; H 1.67%; N 7.68%.

10.1021/cg800310j CCC: $40.75  2008 American Chemical Society Published on Web 07/15/2008

Lanthanide Coordination Polymers

Crystal Growth & Design, Vol. 8, No. 8, 2008 3099 Table 1. Crystallographic Data and Structure Refinements for 1-5

empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) R (°) β (°) γ (°) volume (Å3) Z DCalc (mg/m-3) µ (mm-1) F(000) Rint GOF on F2 R1 [I > 2σ(I)]a wR2 [I > 2σ(I)]a R1 (all data)a wR2 (all data)a a

1

2

3

4

5

C28H15N4O12Tb 758.36 293(2) triclinic P1j 10.228(2) 12.029(2) 12.062(2) 70.60(3) 85.77(3) 76.54(3) 1361.4(5) 2 1.850 2.674 744 0.0281 1.066 0.0254 0.0475 0.0314 0.0514

C28H15N4O12Ho 764.37 293(2) triclinic P1j 10.194(2) 12.031(2) 12.047(2) 70.69(3) 76.48(3) 85.58(3) 1355.7(5) 2 1.873 2.995 748 0.0208 1.043 0.0228 0.0629 0.0264 0.0813

C28H15N4O12Er 766.70 293(2) triclinic P1j 10.173(2) 12.012(2) 12.044(2) 70.71(3) 76.45(3) 85.45(3) 1350.4(5) 2 1.886 3.184 750 0.0306 1.032 0.0288 0.0607 0.0336 0.0625

C28H15N4O12La 738.35 293(2) triclinic P1j 10.468(2) 11.164(2) 13.177(3) 101.97(3) 111.60(3) 96.40(3) 1370.5(5) 2 1.789 1.634 728 0.0181 1.057 0.0188 0.0617 0.0209 0.0627

C28H15N4O12Sm 749.79 293(2) triclinic P1j 10.416(2) 11.110(2) 13.181(3) 102.42(3) 112.32(3) 96.10(3) 1347.9(5) 2 1.847 2.255 738 0.0223 1.043 0.0185 0.0558 0.0228 0.0620

R1 ) Σ||Fo| - |Fc||/Σ|Fo|; wR2 ) {Σ[w(Fo2 - Fc2)2]/Σ[w(Fo2)]2}1/2. Table 2. Crystallographic Data and Structure Refinements for 6-9

empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) R (°) β (°) γ (°) volume (Å3) Z DCalc mg/m-3 µ (mm-1) F(000) Rint GOF on F2 R1 [I > 2σ(I)]a wR2 [I > 2σ(I)]a R1 (all data)a wR2 (all data)a a

6

7

8

9

C48H29N7O20Pr2 1305.60 293(2) triclinic P1j 10.437(2) 12.536(3) 19.787(4) 106.21(3) 99.07(3) 100.53(3) 2383.8(8) 2 1.819 2.111 1288 0.0237 1.075 0.0256 0.0545 0.0350 0.0621

C48H29N7O20Yb2 1369.86 293(2) triclinic P1j 10.472(2) 12.322(3) 19.465(4) 105.86(3) 100.22(3) 100.17(3) 2309.5(8) 2 1.970 4.118 1332 0.0249 1.123 0.0256 0.0743 0.0326 0.0847

C48H25N7O18Eu2 1291.67 293(2) triclinic P1j 13.104(3) 14.325(3) 14.761(3) 105.50(3) 115.10(3) 90.68(3) 2393.0(8) 2 1.793 2.682 1264 0.0220 1.128 0.0279 0.0845 0.0376 0.0930

C48H25N7O18Nd2 1276.23 293(2) triclinic P1j 12.845(3) 14.724(3) 14.778(3) 103.85(3) 90.16(3) 115.30(3) 2435.7(8) 2 1.740 2.192 1252 0.0334 1.037 0.0296 0.0900 0.0393 0.1022

R1 ) Σ||Fo| - |Fc||/Σ|Fo|; wR2 ) {Σ[w(Fo2 - Fc2)2]/Σ[w(Fo2)]2}1/2.

Synthesis of [Ho(NIPH)(HNIPH)(phen)] (2). The synthesis of 2 was similar to the above description for 1 except that Tb(NO3)3 was replaced by Ho(NO3)3. The colorless crystals of 2 were collected. The yield was 55% based on Ho. Elemental analysis calcd (%) for C28H15N4O12Ho (764.37): C 44.00%; H 1.98%; N 7.33%; found: C 44.35%; H 1.70%; N 7.76%. Synthesis of [Er(NIPH)(HNIPH)(phen)] (3). The synthesis of 3 was similar to the above description for 1 except that Tb(NO3)3 was replaced by Er(NO3)3. The colorless crystals of 3 were collected. The yield was 48% based on Er. Elemental analysis calcd (%) for C28H15N4O12Er (766.70): C 43.86%; H 1.97%; N 7.31%; found: C 44.04%; H 1.77%; N 7.72%. Synthesis of [La(NIPH)(HNIPH)(phen)] (4). The synthesis of 4 was similar to the above description for 1 except that Tb(NO3)3 was replaced by La(NO3)3. The colorless crystals of 4 were collected. The yield was 65% based on La. Elemental analysis calcd (%) for C28H15N4O12La (738.35): C 45.55%; H 2.05%; N 7.59%; found: C 45.91%; H 1.79%; N 7.86%. Synthesis of [Sm(NIPH)(HNIPH)(phen)] (5). A mixture of Sm(NO3)3 (0.4 mmol), H2NIPH (0.4 mmol)), phen (0.6 mmol), and H2O (10 mL) was heated at 120 °C for 72 h in a Teflon-lined stainless steel autoclave (25 mL) under autogenous pressure. After the sample was

cooled to room temperature, block-shaped colorless crystals were obtained. The product was washed with water and dried in air. The yield was 62% based on Sm. Elemental analysis calcd (%) for C28H15N4O12Sm (749.79): C 44.85%; H 2.02%; N 7.47%; found: C 45.03%; H 1.66%; N 7.61%. Synthesis of [Pr2(NIPH)3(phen)2(H2O)] · H2O (6). The 6 was synthesized in a fashion similar to that for 5 except that Sm(NO3)3 was replaced by Pr(NO3)3. The yellow crystals of 6 were collected. The yield was 45% based on Pr. Elemental analysis calcd (%) for C48H29N7O20Pr2 (1305.60): C 44.16%; H 2.24%; N 7.51%; found: C 44.50%; H 1.96%; N 7.68%. Synthesis of [Yb2(NIPH)3(phen)2(H2O)] · H2O (7). The 7 was synthesized in a fashion similar to that for 5 except that Sm(NO3)3 was replaced by Yb(NO3)3. The colorless crystals of 7 were collected. The yield was 55% based on Yb. Elemental analysis calcd (%) for C48H29N7O20Yb2 (1369.86): C 42.08%; H 2.13%; N 7.16%; found: C 42.50%; H 1.98%; N 7.54%. Synthesis of [Eu2(NIPH)3(phen)2] (8). The procedure of 8 is similar to the synthesis of 1 except that Tb(NO3)3 was replaced by Eu(NO3)3. The yellow crystals of 8 were collected. The yield was 45% based on Eu. Elemental analysis calcd (%) for C48H25N7O18Eu2 (1291.67): C 44.63%; H 1.95%; N 7.59%; found: C 44.82%; H 1.66%; N 7.96%.

3100 Crystal Growth & Design, Vol. 8, No. 8, 2008

Ye et al.

Table 3. Selected Bond Lengths [Å] for 1-9a 1 Tb(1)-O(3)#1 Tb(1)-O(7)#2 Tb(1)-O(4)#3 Tb(1)-O(8)

2.2877(18) 2.3111(18) 2.3155(16) 2.3524(18)

Ho(1)-O(2)#1 Ho(1)-O(1) Ho(1)-O(7)#1 Ho(1)-O(8)

2.270(3) 2.289(3) 2.290(3) 2.332(3)

Er(1)-O(3)#1 Er(1)-O(7)#2 Er(1)-O(4)#3 Er(1)-O(8)

2.263(3) 2.275(3) 2.276(2) 2.317(3)

Tb(1)-O(2) Tb(1)-O(1) Tb(1)-N(3) Tb(1)-N(4)

2.4065(17) 2.4576(17) 2.533(2) 2.574(2)

2 Ho(1)-O(3)#2 Ho(1)-O(4)#2 Ho(1)-N(4) Ho(1)-N(3)

2.381(3) 2.436(3) 2.504(4) 2.559(3)

Er(1)-O(2) Er(1)-O(1) Er(1)-N(4) Er(1)-N(3)

2.372(3) 2.423(3) 2.494(3) 2.546(3)

3

4 La-O(7)#1 La-O(1) La-O(3)#2 La-N(3)

La-O(2)#1 La-O(8) La-O(10)#3 La-N(4)

2.3940(11) 2.4449(8) 2.4797(10) 2.7005(13)

2.4897(10) 2.5180(8) 2.6852(9) 2.7231(11)

5 Sm-O(1)#1 Sm-N(3) Sm-N(4) Sm-O(4)#3

2.2956(9) 2.6041(12) 2.6313(10) 2.6921(8)

Sm-O(7)#1 Sm-O(9)#2 Sm-O(8) Sm-O(2)

2.3547(7) 2.3796(9) 2.4022(9) 2.4322(7)

Pr(2)-O(9)#1 Pr(2)-O(10) Pr(2)-O(4)#4 Pr(2)-O(19) Pr(2)-O(14) Pr(2)-O(13) Pr(2)-N(7) Pr(2)-N(6)

2.3611(13) 2.3952(12) 2.4126(13) 2.4260(15) 2.4788(16) 2.5387(13) 2.6371(16) 2.6606(18)

Yb(2)-O(9) Yb(2)-O(10)#4 Yb(2)-O(19) Yb(2)-O(13) Yb(2)-O(3)#1 Yb(2)-O(4)#1 Yb(2)-N(7) Yb(2)-N(6)

2.2479(15) 2.2485(13) 2.2859(17) 2.3019(15) 2.3349(16) 2.4390(15) 2.4934(18) 2.502(2)

Eu(2)-N(6) Eu(2)-O(4)#4 Eu(2)-O(14)#5 Eu(2)-O(3)#6 Eu(2)-O(13) Eu(2)-O(10) Eu(2)-O(9) Eu(2)-N(7)

2.585(2) 2.3288(19) 2.3575(19) 2.3687(18) 2.376(2) 2.4369(19) 2.438(2) 2.590(3)

Nd(2)-O(10)#2 Nd(2)-O(15)#3 Nd(2)-O(9)#4 Nd(2)-O(16) Nd(2)-O(4)#5 Nd(2)-O(3)#5 Nd(2)-N(6) Nd(2)-N(7)

2.3573(14) 2.4052(14) 2.4174(16) 2.4227(13) 2.4371(13) 2.5193(15) 2.6098(16) 2.6612(14)

6 Pr(1)-O(1) Pr(1)-O(15)#1 Pr(1)-O(16)#2 Pr(1)-O(8) Pr(1)-O(2)#3 Pr(1)-O(7) Pr(1)-N(5) Pr(1)-N(4)

2.4137(12) 2.4168(11) 2.4630(13) 2.4670(13) 2.4801(13) 2.4807(12) 2.6584(15) 2.6851(14)

Yb(1)-O(2)#1 Yb(1)-O(16)#2 Yb(1)-O(1) Yb(1)-O(15)#3 Yb(1)-O(8) Yb(1)-O(7) Yb(1)-N(4) Yb(1)-N(5)

2.2563(14) 2.2605(14) 2.3140(14) 2.3398(15) 2.3415(15) 2.3569(14) 2.5209(17) 2.5385(17)

Eu(1)-O(16)#3 Eu(1)-O(7) Eu(1)-O(16)#1 Eu(1)-O(2)#2 Eu(1)-O(1) Eu(1)-O(8) Eu(1)-O(15)#3 Eu(1)-N(5) Eu(1)-N(4)

2.5644(18) 2.3721(19) 2.3790(17) 2.3938(17) 2.3938(17) 2.5058(19) 2.528(2) 2.615(2) 2.651(2)

Nd(1)-O(14)#1 Nd(1)-O(1) Nd(1)-O(8)#1 Nd(1)-O(7) Nd(1)-O(2) Nd(1)-O(13) Nd(1)-O(14) Nd(1)-N(5) Nd(1)-N(4)

2.4220(14) 2.4268(15) 2.4496(12) 2.4504(12) 2.5392(14) 2.5603(14) 2.6169(14) 2.6529(16) 2.7067(15)

7

8

9

a Symmetry transformations used to generate equivalent atoms: For 1: #1 -x + 2, -y + 2, -z + 1; #2 -x + 1, -y + 2, -z + 1; #3 x - 1, y, z. For 2: #1 -x + 2, -y, -z + 1; #2 x - 1, y, z. For 3: #1 -x + 1, -y, -z + 1; #2 -x + 2, -y, -z + 1; #3 x + 1, y, z. For 4: #1 -x + 2, -y, -z + 1; #2 x - 1, y, z; #3 x, y - 1, z. For 5: #1 -x + 2, -y, -z + 1; #2 -x + 1, -y, -z + 1; #3 x, y - 1, z. For 6: #1 -x + 1, -y, -z; #2 x + 1, y + 1, z + 1; #3 -x + 2, -y + 1, -z + 1; #4 x - 1, y, z - 1. For 7: #1 -x + 2, -y + 2, -z + 1; #2 -x + 2, -y + 1, -z + 1; #3 x, y + 1, z; #4 -x + 1, -y + 1, -z. For 8: #1 -x, -y + 1, -z + 1; #2 -x, -y + 1, -z; #3 x, y, z - 1; #4 -x + 1, -y + 1, -z + 1; #5 -x + 1, -y + 2, -z + 2; #6 x, y + 1, z + 1. For 9 #1 -x + 1, -y + 2, -z + 1; #2 -x + 2, -y + 2, -z + 1; #3 -x + 2, -y + 2, -z; #4 x, y, z - 1; #5 x + 1, y + 1, z.

Figure 1. Perspective view of the coordination environment of the Tb center in 1 with atoms represented by 30% thermal ellipsoids. Synthesis of [Nd2(NIPH)3(phen)2] (9). The procedure of 9 is similar to the synthesis of 1 except that Tb(NO3)3 was replaced by Nd(NO3)3. The colorless crystals of 9 were collected. The yield was 60% based on Nd. Elemental analysis calcd (%) for C48H25N7O18Nd2 (1276.23): C 44.17%; H 1.97%; N 7.68%; found: C 44.42%; H 1.69%; N 7.91%. X-Ray Crystallographic Study. The crystal structures of compounds 1-9 were determined by single-crystal X-ray diffraction experiments. The reflection data were collected on a Rigaku R-AXIS RAPID diffractometer (Mo KR radiation, graphite monochromated). Empirical absorption correction was applied for all data. The structure was solved by direct methods and refined by full-matrix least-squares program on F2 using SHELXTL97 software.12 The heaviest atoms were first found. O and C atoms were subsequently located in difference Fourier maps. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms of 1-9 were calculated by geometrical models. Experimental details for the structure analysis of 1-9 are given in Tables 1 and 2, the selected bond distances for 1-9 are listed in Table 3, and the selected bond angles and hydrogen bonds for 1-9 are listed in Supporting Information, Tables S1 and S2, respectively. The crystallographic data of 1-9 in CIF format have been deposited in the Cambridge Crystallographic Data Center (CCDC reference numbers 650101-650109). These data can be obtained free of charge via http:// www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK;fax:(internat.)+44-1223-336-033;e-mail:[email protected]].

Results and Discussion Coordination polymers 1-9 have been successfully synthesized under hydrothermal conditions. It was demonstrated that the reaction temperature was crucial for the formation of 1-9. For the synthesis of 1-4 and 8-9, the reaction temperature must be controlled at 170 ((2) °C and the convenient reaction period was 120 h. If the temperature was below 160 °C, highquality crystals 1-4, and 8-9 could not be obtained. In contrast, high-quality crystals 5-7 were obtained with good yields when the reaction temperature was maintained at 120 ((2) °C. Singlecrystal X-ray diffraction studies reveal that 1-9 could be classified into three types of frameworks constructed from dinuclear lanthanide building blocks (Supporting Information, Scheme S1): 1-D double-stranded looplike chains for 1-3; 2-D layer structures for 4-7; and 3-D frameworks for 8 and 9. These different structural features may be attributed to the different coordination environments of lanthanide ions and abundant coordination modes of NIPH. Scheme 1 summarizes the coordination modes of NIPH anions in compounds 1-9. 1-D Chains of [Ln(NIPH)(HNIPH)(phen)] [Ln ) Tb (1), Ho (2), Er (3)]. Single crystal X-ray diffraction reveals that 1-3 are isostructural; thus 1 is taken as an example to

Lanthanide Coordination Polymers

Crystal Growth & Design, Vol. 8, No. 8, 2008 3101 Scheme 1. The Coordination Modes of NIPH Ligand

discuss in detail. Framework 1 is a 1-D chainlike coordination polymer consisting of dinuclear lanthanide building blocks. The asymmetric unit of 1 consists of one Tb ion, two NIPH ligands, and one phen ligand. The geometry around the Tb1 can be described as a distorted triangle-dodecahedral and Tb1 is coordinated with six oxygen atoms from five different NIPH ligands, two nitrogen atoms from a chelating phen ligand (Figure 1). The Tb-O distances are in the range from 2.288 to 2.458 Å, and the Tb-N bond distances are 2.533 and 2.574 Å, which are similar to the reported Tb-O and Tb-N bond distances.7b,13 The average distance of Tb-O is 2.355 Å, which is strikingly shorter than that of Tb-N (2.554 Å). The NIPH ligand adopts two kinds of coordination models (I-NIPH and II-NIPH) (Scheme 1) in 1. For I-NIPH, only one carboxyly group participated in the coordination with Tb and the other carboxyly group kept uncoordinated and protonated state. Two crystallographically equivalent Tb atoms are bridged by four carboxylate groups in dimonodentate fashion to give a dinuclear lanthanide building block [Tb2N4(CO2R)6] with shorter separations of

Figure 2. (a) Ball and stick and (b) polyhedral representation of dinuclear building block in 1. (c) View of a one-dimensional doublestranded looplike chain structure in 1.

Tb · · · Tb (4.317 Å) (Figure 2). The dinuclear lanthanide building blocks are connected to each other through NIPH leading to a 1-D double-stranded looplike chain (Figure 2). To further investigate the crystal structure of 1 reveals that the doublestranded looplike chains are linked together by the hydrogen bond interactions between the NO2 and the C-H groups on NIPH ligands resulting in the formation of the coordination sheets (see Supporting Information, Figure S1-a). The hydrogen bond distance and angles are 3.521(3) Å for C6 · · · O6 and 145.9° for C6-H6A · · · O6, respectively. Furthermore, the sheets stack together based on two kinds of hydrogen bond interactions leading to a 3-D supramolecular structure (see Supporting Information, Figure S1-b). The two kinds of interlayer hydrogen bonds are O-H · · · O (O10 · · · O1 2.730 Å) between protonated carboxyly groups and carboxylate oxygen atoms and C-H · · · O (C19 · · · O6 3.517 Å, C6 · · · O6 3.521 Å) between C-H groups on phen ligands and nitro-oxygen atoms, respectively. 2-D Layers of [Ln(NIPH)(HNIPH)(phen)] [Ln ) La (4), Sm (5)] and [Ln2(NIPH)3(phen)2(H2O)] · (H2O) [Ln ) Pr (6), Yb (7)]. The crystals 4-5 and crystals 6-7 are two pairs of isostructures, so 4 and 6 are employed as the

Figure 3. Perspective view of the coordination environment of the La center in 4 with atoms represented by 30% thermal ellipsoids.

3102 Crystal Growth & Design, Vol. 8, No. 8, 2008

Ye et al.

Figure 4. (a) Ball and stick and (b) polyhedral representation of dinuclear building blocks in 4. (c) View of a two-dimensional layer structure in 4.

Figure 5. (a, b) Perspective view of the coordination environment of the Pr centers in 6 with atoms represented by 30% thermal ellipsoids.

representations to be described in detail. The X-ray diffraction studies performed on 4 reveals that each asymmetric unit contains one eight-coordinated La ion, two NIPH ligands, and one phen ligand. As shown in Figure 3, each La is coordinated with six oxygen atoms from six different NIPH ligands and two nitrogen atoms from a phen ligand. The La-O, La-N bond distances are in the range of 2.394-2.685 Å and 2.701-2.723 Å, respectively, all of which are comparable to those reported for other La-oxygen (or nitrogen) donor compounds.6a,14

Compared with 1, NIPH adopts the other two kinds of coordination models (III-NIPH and IV-NIPH) in 4 (Scheme 1). Two La atoms are linked together by four carboxylate groups to form a dinuclear building block [La2N4(CO2R)8] with a La · · · La contact distance of 4.353 Å. The adjacent dinuclear building blocks connect to each other through NIPH ligands resulting in the formation of 2-D layer framework with 44 square lattice topology (Figure 4 and Supporting Information, Figure S2-S3). In addition, there are O-H · · · O (O9 · · · O4 2.424 Å) between protonated carboxylate groups and uncoordinated carboxylic-oxygen atoms and C-H · · · O (C26 · · · O11 3.247 Å, C25 · · · O12 3.421 Å) between C-H groups and nitro-oxygen atoms hydrogen bonds, respectively. Finally, the 3-D supramolecular network is stabilized by interlayer hydrogen bonds C-H · · · O in which C-H groups of phen act as donors (Supporting Information, Figure S4). The asymmetric unit of 6 contains two types of coordinated environments of Pr ions (Figure 5). Pr1 is eight-coordinated polyhedron made of six oxygen atoms from five NIPH ligands and two nitrogen atoms from one phen ligand. Pr2 is eightcoordinated as well, but surrounded by five oxygen atoms from five NIPH ligands, one oxygen atom from one coordinated water molecule, and two nitrogen atoms from one phen ligand. It is rare that the same metal ion has different coordination environments in one compound.15 In 6, NIPH also adopts two coordination modes: II-NIPH and III-NIPH (Scheme 1). Two crystallographically equivalent Pr1 and two crystallographically equivalent Pr2 atoms are linked, respectively, by carboxyal groups to form two different dinuclear building blocks: [Pr2N4(CO2R)6] (Pr · · · Pr: 4.105 Å) and [Pr2O2N4(CO2R)6] (Pr · · · Pr: 5.687 Å) (Figure 6). Then the two types of building blocks alternately link to each other through NIPH ligands to form a 2-D framework (Figure 6 and Supporting Information, Figure S5). In addition, weak π · · · π stacking interactions exist between the phen ligands, and the average distance between two phen planes is 3.65 Å. It appears that there are abundant hydrogen bonding interactions in the framework 6, which include the following contacts: (a) between the water molecules and nitro-oxygen, (b) between water molecules and uncoordinated carboxylic-oxygen, (c) between C-H groups of phen and nitro-oxygen, (d) between C-H groups of phen and uncoordinated carboxylic-oxygen (e) between C-H groups of NIPH and nitro-oxygen atoms (Supporting Information, Table S2). As a

Lanthanide Coordination Polymers

Crystal Growth & Design, Vol. 8, No. 8, 2008 3103

Figure 6. (a) and (c) Ball and stick, (b) and (d) polyhedral representations of dinuclear building block in 4. (e) View of a two-dimensional layer structure in 6.

result, 3-D supramolecular architecture is formed (Supporting Information, Figure S6). 3-D Frameworks of [Ln2(NIPH)3(phen)2] [Ln ) Eu (8), Nd (9)]. Compounds 8 and 9 are isostructural, and therefore only the structure of 8 will be described in detail. Each asymmetric unit of 8 consists of two crystallographically independent Eu ions, three distinct NIPH ligands, and two phen ligands (Figure 7). The Eu1 center is nine-coordinated by seven oxygen atoms from five NIPH and two nitrogen atoms from a phen ligand. The Eu2 is eight-coordinated and surrounded by six oxygen atoms from five NIPH, and two nitrogen atoms from one phen ligand. The distances of Eu-O bonds range from 2.329 to 2.564 Å, while the Eu-N bond distances range from 2.585 to 2.651 Å, all of which are comparable to those reported Eu compounds.11a It is noteworthy that NIPH ligand in 8 adopt three different coordination modes: V-NIPH, VI-NIPH, and VIINIPH (Scheme 1). The Eu1 centers are interconnected by four carboxylate groups resulting in the dinuclear paddle-wheel building block with the Eu · · · Eu separation of 3.975 Å, which is similar to those found in compounds 1-5. Interestingly, the Eu2 centers are also bridged by four carboxylate groups to give other types of dinuclear paddle-wheel building blocks with a Eu · · · Eu separation of 4.326 Å (Figure 8). These dinuclear building blocks are interconnected through the phenyl groups of NIPH to generate an extended 3-D framework (Figure 8). To better understand the structure of 8, the topological analysis approach was employed, which is standard procedure for reducing multidimensional structures to a simple node-andlinker.16 As discussed above, each building block in 8 is connected to adjacent six building blocks through six biphenyl groups of NIPH as shown in Figure 9, Therefore, two types of dinuclear building blocks are defined as 6-connected nodes, and NIPH can act as a bridging ligands that have not been considered in the topological analysis. On the basis of this simplification, the structure of 8 can be described as an six-connected 3-D network with the Schla¨fli symbol (412 · 63), which corresponds to a pcu topology.17 Structural Comparison of the Frameworks 1-9. For the nine frameworks reported in this study, the common structural feature is that they are constructed by the dinuclear lanthanide building blocks (Supporting Information, Scheme S1), and belong to the same crystal system (triclinic) and space group (P1j). The frameworks 1-5 are formed by one kind of dinuclear building block, respectively, and the structures of the dinuclear

Figure 7. (a, b) Perspective view of the coordination environment of the Eu centers in 8 with atoms represented by 30% thermal ellipsoids.

3104 Crystal Growth & Design, Vol. 8, No. 8, 2008

Ye et al.

Figure 8. (a) and (c) Ball and stick, (b) and (d) polyhedral representation of dinuclear building blocks in 4. (e) View of a two-dimensional layer structure and (f) three-dimensional framework in 8; the phen molecules are omitted for clarity.

Figure 10. Solid-state emission spectra of 8 excited at 361 nm.

Figure 9. (a) Each building block (cyan circle) of 8 is connected to six adjacent building blocks of other type (yellow circle). (b) Schematic representation of the pcu topology of the six-connected framework of 8.

building blocks in 1-5 are very similar to each other. Therefore, the crystals 1-5 display very similar crystal cell parameters (Table 1). The frameworks 6-9 are composed of two kinds of dinuclear building blocks, respectively, in which one is similar to that in 1-5 and the other one exhibits different structural characteristics compared with that in 1-5. The crystal cell parameters of 1-5 are similar to each other (Table 1). The nine frameworks could be divided into four sets: Set-1 includes 1-3, Set-2 includes 4-5, Set-3 includes 6-7, and Set-4 includes 8-9. In the four sets, the NIPH or HNIPH bridged ligands adopt different coordinated modes (Scheme 1), which have been

Lanthanide Coordination Polymers

Crystal Growth & Design, Vol. 8, No. 8, 2008 3105

Figure 11. Microscopic images under daylight (a and b) and under UV light (c and d upon excitation at 365 nm) of luminescent complex 8.

described above and should be the main structural difference between the four sets. Thermal Behaviors and Photoluminescent Properties. The thermal behaviors of compounds 1, 4, 6, and 8 were studied by thermogravimetric analysis (TGA) under air atmosphere (Supporting Information, Figure S7). The TGA result indicates that 1, 4, and 8 begin to decompose at 349, 252, and 236 °C, respectively, and all display almost one stage of weight loss. The TGA result of 6 displays two steps weight losses. The first weight loss of 3.15% from 109 to 203 °C should be attributed to the loss of water molecules (calcd. 2.76%), and the second weight loss is ascribed to the loss of NIPH and phen ligands. The decomposition of the coordination framework occurred immediately when the temperature is above 284 °C. Taking into account the excellent luminescent properties of Eu(III) ion, the luminescence of 8 was investigated (Figure 10). The emission spectrum of 8 upon excitation at 361 nm exhibits the characteristic transition of Eu(III) ion and the emission bands appear in the range of 570-705 nm, which are due to the 5D0 f 7FJ transitions of Eu(III) ion. The emission spectrum is dominated by the characteristic 5D0 f 7F2 transition of Eu(III) ion that is much more intense than the 5D0 f 7F3 transition at 648 nm and 5D0 f 7F4 transition at 701 nm. Therefore, the solid sample 8 exhibits strong red color emission (Figure 11). Magnetic Properties. The temperature dependence properties of χm and χmT of 8 are shown in Figure 12a. The observed value of χmT at room temperature is 3.13 cm3 mol-1 K, which is close to the value (3.0 cm3 mol-1 K) for two Eu free ions calculated by Van Vleck allowing for population of the excitedstate with higher values of J at 293 K. Upon the decrease of the temperature, χmT drops gradually and reaches to 0.28 cm3 mol-1 K at 4 K. When the temperature is above 50 K, the magnetic susceptibility follows the Curie-Weiss law due to the presence of thermally populated excited states. The decrease characteristic of χmT indicates that the antiferromagnetic interac-

Figure 12. Temperature dependence of χm and χmT of 8 (a) and 9 (b).

3106 Crystal Growth & Design, Vol. 8, No. 8, 2008

tion between the Eu3+ ions dominated the magnetic properties of 8. For compound 9, the temperature dependence of the magnetic susceptibility is displayed in Figure 12b. The plot of χm-1 vs T over the whole temperature range obeys the Curie-Weiss law [χ ) C/(T - θ)] with C ) 3.57 cm3 K mol-1 and θ ) -22.43 K. At room temperature, the value of χmT is 3.38 cm3 mol-1 K, which is slightly higher than the calculated value for two Nd free ions (3.28 cm3 mol-1 K).18 The χmT decreases to 1.32 cm3 mol-1 K at 4 K. These features are consistent with antiferromagnetic interactions between the Nd3+ ions in 9.

Ye et al.

(4)

(5)

Conclusions In summary, we have successfully assembled the lanthanide ions, 5-nitroisophthalic acid (H2NIPH) and 1,10-phenanthroline (phen) into nine lanthanide coordination polymers: [Ln(NIPH)(HNIPH)(phen)] [Ln ) Tb (1), Ho (2), Er (3), La (4), Sm (5),], [Ln2(NIPH)3(phen)2(H2O)] · (H2O) (Ln ) Pr (6), Yb (7), [Ln2(NIPH)3(phen)2] [Ln ) Eu (8), Nd (9)]. Single-crystal X-ray diffraction analysis revealed that different coordination modes of the organic bridge ligand and different coordination numbers of lanthanide atoms could promote different topologies structures, which are constructed from dinuclear lanthanide building blocks. The coordination polymers 1-3 possess 1-D doublestranded looplike chain structures that are further interlinked into a 3-D supramolecular network based on hydrogen bonding interactions. 4-5 and 6-7 are two pairs of 2-D layer frameworks. 8 and 9 are two 3-D frameworks with pcu topology. The coordination polymers 1-4 are constructed by one kind of dinuclear lanthanide building blocks, respectively, while 6-9 are composed of two kinds of dinuclear lanthanide building blocks, respectively. The supramolecular architectures of 1-9 show that combining different coordination modes of ligands and different coordination numbers of lanthanide atoms can effectively influence network dimensionality. Compound 8 exhibits strong red emission and compounds 8 and 9 display antiferromagnetic interactions, suggesting that these compounds may be efficient solid emitting and antiferromagnetic materials.

(6)

(7)

(8)

(9)

(10)

(11)

Acknowledgment. This work was supported by the National Natural Science Foundation of China (50733002 and 20772014). Supporting Information Available: IR data, extensive figures, thermogravimetric curves, tables of selected bond distances and angles, and crystallographic information fillies (CIF) of 1-9. This material is available free of charge via the Internet at http://pubs.acs.org.

(12) (13)

References (14) (1) (a) Moulton, B.; Zaworotko, M. J. Chem. ReV. 2001, 101, 1629–1658. (b) Uemura, K.; Kitagawa, S.; Fukui, K.; Saito, K. J. Am. Chem. Soc. 2004, 126, 3817–3828. (c) Rao, C. N. R.; Natarajan, S.; Vaidhyanathan, R. Angew. Chem., Int. Ed. 2004, 43, 1466–1496. (d) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31, 474–484. (e) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D. T.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469–472. (2) (a) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, G.; Williams, I. D. Science 1999, 283, 1148–1150. (b) Barthelet, K.; Marrot, J.; Riou, D.; Ferey, G. Angew. Chem., Int. Ed. 2002, 41, 281– 284. (c) Kitagawa, S.; Kitaura, R.; Noro, S. I. Angew. Chem., Int. Ed. 2004, 43, 2334–2375. (3) (a) Hagrman, P. J.; Hagrman, D.; Zubieta, J. Angew. Chem., Int. Ed. 1999, 38, 2638–2684. (b) Uemura, K.; Kitagawa, S.; Kondo, M.; Fukui, K.; Kitaura, R.; Chang, H. C.; Mizutani, T. Chem. Eur. J. 2002, 8, 3586–3600. (c) Zhang, Z. H.; Shen, Z. L.; Okamura, T.; Zhu, H. F.; Sun, W. Y.; Ueyama, N. Cryst. Growth Des. 2005, 5, 1191–1197. (d)

(15) (16)

(17)

(18) (19)

Li, J. R.; Bu, X. H.; Zhang, R. H. Inorg. Chem. 2004, 43, 237–244. (e) Sun, Y. Q.; Zhang, J.; Chen, Y. M.; Yang, G. Y. Angew. Chem., Int. Ed. 2005, 44, 2–5. (a) Wan, Y. H.; Zhang, L. P.; Jin, L. P.; Gao, S.; Lu, S. Z. Inorg. Chem. 2003, 42, 4985–4994. (b) Chu, D. Q.; Xu, J. Q.; Duan, L. M.; Wang, T. G.; Tang, A. Q.; Ye, L. Eur. J. Inorg. Chem. 2001, 1135– 1137. (c) Shi, Q.; Cao, R.; Sun, D. F.; Hong, M. C.; Liang, Y. C. Polyhedron 2001, 20, 3287–3293. (a) Zhou, Y. F.; Hong, M. C.; Wu, X. T. Chem. Commun. 2006, 135– 143. (b) Cheng, J. W.; Zhang, J.; Zheng, S. T.; Zhang, M. B.; Yang, G. Y. Angew. Chem., Int. Ed. 2006, 45, 73–77. (c) Figuerola, A.; Diaz, C.; Ribas, J.; Tangoulis, V.; Granell, J.; Lloret, F.; Mahia, J.; Maestro, M. Inorg. Chem. 2003, 42, 641–649. (d) Pan, L.; Adams, K. M.; Hernandez, H. E.; Wang, X. T.; Zheng, C.; Hattori, Y.; Kaneko, K. J. Am. Chem. Soc. 2003, 125, 3062–3067. (e) Gheorghe, R.; Cucos, P.; Andruh, M.; Costes, J. P.; Donnadieu, B.; Shova, S. Chem. Eur. J. 2006, 12, 187–203. (f) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319–330. (g) De Lill, D. T.; Gunning, N. S.; Cahill, C. L. Inorg. Chem. 2005, 44, 258. (a) Daiguebonne, C.; Kerbellec, N.; Bernot, K.; Gerault, Y.; Deluzet, A.; Guillou, O. Inorg. Chem. 2006, 45, 5399–5406. (b) Zhao, B.; Chen, X. Y.; Cheng, P.; Liao, D. Z.; Yan, S. P.; Jiang, Z. H. J. Am. Chem. Soc. 2004, 126, 15394–15395. (c) Osa, S.; Kido, T.; Matsumoto, N.; Re, N.; Pochaba, A.; Mrozinski, J. J. Am. Chem. Soc. 2004, 126, 420– 421. (d) Mishra, A.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. J. Am. Chem. Soc. 2004, 126, 15648–15649. (a) Zheng, X. J.; Wang, Z. M.; Gao, S.; Liao, F. H.; Yan, C. H.; Jin, L. P. Eur. J. Inorg. Chem. 2004, 43, 2968–2973. (b) Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B. L.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 1504–1518. (a) Reineke, T. M.; Eddaoudi, M.; O’Keefe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. 1999, 38, 2590. (b) Reneike, T. M.; Eddaoudi, M.; Fehr, M.; Kelley, D.; Yaghi, O. M. J. Am. Chem. Soc. 1999, 121, 1651–1657. (d) Pan, L.; Zheng, N.; Wu, Y.-M.; Han, S.; Yang, R.; Huang, X.; Li, J. Inorg. Chem. 2001, 40, 828–830. (a) Sun, D. F.; Cao, R.; Sun, Y. Q.; Bi, W. H.; Yuan, D. Q.; Shi, Q.; Li, X. Chem. Comm. 2003, 1528–1529. (b) Tao, J.; Yin, X.; Jiang, Y. B.; Huang, R. B.; Zheng, L. S. Inorg. Chem. Commun. 2003, 6, 1171–1174. (c) Sun, Z. M.; Mao, J. G.; Sun, Y. Q.; Zeng, H. Y.; Clearfield, A. Inorg. Chem. 2004, 43, 336–341. (a) Tao, J.; Yin, X.; Wei, Z. B.; Huang, R. B.; Zheng, L. S. Eur. J. Inorg. Chem. 2004, 125–133. (b) Z.; Wang, H. Q.; Nfor, E. N.; You, X. Z. CrystEngComm 2005, 7, 578–585. (c) Ye, J. W.; Zhang, P.; Ye, K. Q.; Yin, W. R.; Ye, L.; Yang, G. D.; Wang, Y. Inorg. Chem. Commun. 2006, 9, 744–747. (a) Luo, J. H.; Hong, M. C.; Wang, R. H.; Cao, R.; Han, L.; Yuan, D. Q.; Lin, Z. Z.; Zhou, Y. F. Inorg. Chem. 2003, 42, 4486–4488. (b) Luo, J. H.; Hong, M. C.; Wang, R. H.; Cao, R.; Han, L.; Lin, Z. Z. Eur. J. Inorg. Chem. 2003, 2705–2710. (c) Abourahma, H.; Moulton, B.; Kravtsov, V.; Zaworotko, M. J. J. Am. Chem. Soc. 2002, 124, 9990–9991. (d) Ye, J. W.; Wang, J.; Zhang, J. Y.; Zhang, P.; Wang, Y. CrystEngComm 2007, 9, 515–523. (e) Ren, Y. X.; Chen, S. P.; Gao, S. L.; Shi, Q. Z. Inorg. Chem. Commun. 2006, 9, 649–653. Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Solution; University of Go¨ttingen: Go¨ttingen, Germany, 1997. Guo, X. D.; Zhu, G. S.; Sun, F. X.; Li, Z. Y.; Zhao, X. J.; Li, X. T.; Wang, H. C.; Qiu, S. L. Inorg. Chem. 2006, 45, 2581–2587. Liu, C. B.; Sun, C. Y.; Jin, L. P.; Lu, S. Z. New J. chem. 2004, 28, 1019–1026. Wan, Y. H.; Jin, L. P.; Wang, K. Z.; Zhang, L. P.; Zheng, X. J.; Lu, S. Z. New J. Chem. 2002, 1590–1596. (a) Blake, A. J.; Champness, N. R.; Hubberstey, P.; Li, W. S.; Withersby, M. A.; SchrVder, M. Coord. Chem. ReV. 1999, 183, 117– 138. (b) Friedrichs, O. D.; O’Keeffe, M.; Yaghi, O. M. Acta Crystallogr., Sect. A 2003, 59, 22–24. (c) Fang, Q. R.; Zhu, G. S.; Jin, Z.; Xue, M.; Wei, X.; Wang, D. J.; Qiu, S. L. Angew. Chem., Int. Ed. 2006, 45, 6126–6130. (a) He, J. H.; Yu, J. H.; Zhang, Y. T.; Pan, Q. H.; Xu, R. R. Inorg. Chem. 2005, 44, 9279–9282. (b) Wen, Y. H.; Zhang, J.; Wang, X. Q.; Feng, Y. L.; Cheng, J. K.; Lia, Z. J.; Yao, Y. G. New J. Chem. 2005, 29, 995–997. Gao, H. L.; Yi, L.; Zhao, B.; Zhao, X. Q.; Cheng, P.; Liao, D. Z.; Yan, S. P. Inorg. Chem. 2006, 45, 5980–5988. Serezhkin, V. N. J. Struct. Chem. 1985, 26, 618–628.

CG800310J