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Structural Diversity Modulated by the Ratios of a Ternary Solvent Mixture: Syntheses, Structures and Luminescent Properties of Five Zinc (#) MOFs Xiuyan Wan, Feilong Jiang, Lian Chen, Ming-yan Wu, Ming-Jian Zhang, Jie Pan, Kongzhao Su, Yan Yang, and Mao-Chun Hong Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg501828u • Publication Date (Web): 27 Jan 2015 Downloaded from http://pubs.acs.org on January 30, 2015

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Crystal Growth & Design

Structural Diversity Modulated by the Ratios of a Ternary Solvent Mixture: Syntheses, Structures and Luminescent Properties of Five Zinc (Ⅱ) MOFs Xiuyan Wanab, Feilong Jianga, Lian Chena*, Mingyan Wua, Mingjian Zhanga, Jie Panab, Kongzhao Suab, Yan Yangab and Maochun Honga*

a

State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the

Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China b

University of the Chinese Academy of Sciences, Beijing, 100049, China

ABSTRACT. A series of metal-organic frameworks (MOFs) were systematic synthesized

through

a

solvent-ratio-controlled

assembly:

{[Et2NH2]2[Zn5(L)2(H2O)4]·2C2H5OH·2H2O}n

(1),

{[Et2NH2]4[Zn7(HL)2(H2L)2]·4C2H5OH·6H2O}n

(2),

{[Et2NH2]4[Zn6(L)2(H2L)(H2O)2]·2C2H5OH·2H2O}n

(3),

{[Et2NH2]4[Zn4(L)2(H2O)2]·4H2O}n (4) and {[Et2NH2]2[Zn2(L)]·C2H5OH}n (5) (H6L = [1,1';4',1'']terphenyl-3,5,2',5',3'',5''-hexacarboxylic

acid,

DEF

=

N,N-diethylformamide). Along with the altering of ratios of the ternary mixed-solvent DEF/H2O/C2H5OH used in the synthetic processes, the coordination modes of ligand change, which further leads to the different structures of resultant complexes. Owing to

ACS Paragon Plus Environment


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diverse metal centres/clusters and ligands’ dinstrict coordination modes, these five complexes exhibit totally different and novel topologies: complex 1 displays a (5,8)-connected 3D net, in which the 8-connected nodes are based on trinuclear metal clusters; complexes 2-4 all exhibit 3D 4-nodal net based on two kinds of metal centers and two kinds of ligands’ coodination modes; complex 5 shows a 6-connected unidoal 3D net. These five complexes have been characterized by single-crystal X-ray diffraction, thermogravimetric (TG) analyses, elemental analyses (EA), and powder X-ray diffraction (PXRD). Luminescent properties of complexes 1-5 at room temperature and 77 K show that all the five complexes exhibit temperature-dependent emission properties. The calculation of density of states (DOS) were carried out to get a better insight into the nature of the luminescence. The obvious change of spectral colors of 3 at different temperatures suggests that it may be well applied in the temperature-sensing devices. INTRODUCTION The rational design and synthesis of coordination polymers (CPs) or metal-organic frameworks (MOFs) with preferred structures and good properties have been extensively developed in recent years, due to their crystallographic diversities and intriguing topologies as well as their excellent properties with promising applications such as magnetism, gas/vapor separation, non-linear optics, drug delivery, and luminescence.1 During the obtaining of desirable frameworks, many factors can influence the construction progresses, for instance: coordinated tendency of metal centers, nature of organic ligands, ligand-to-metal ratios, reagent concentration,


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reaction temperatures, solvents, pH values and so on.2 In crystal engineering, the majority of supramolecular coordination polymers are synthesized in solvent media. Therefore, solvent effect is one of the most significant factors which affect the structures and properties of final resultants. Discussions about how the solvents impact on the crystalline products have been summarized by Du et al.3a According to this review, solvents can influence the reaction progress in different ways: (ⅰ) solvent as ligand; (ⅱ) solvent as guest; (ⅲ) solvent as both ligand and guest; (ⅲ) solvent-induced polymorphism. Nevertheless, most of the studies about the effects of solvents on the resultant structure are achieved by changing the types of the solvents.3 The component ratio of a mixed-solvent as a main controlling factor to modulate the final structures has barely been reported,4 mainly due to the following reasons: 1) in crystal engineering, the changing degree of variables is always quite obvious, and it’s difficult to find a system in which the crystalline products are so sensitive to such subtle changes; 2) since the changes are very delicate, the mixed products are always obtained, which obstructs the investigation about the influence of the solvent ratios on the final structures. Herein,

we

report

five

new complexes assembled

by

Zn(NO3)2

and

[1,1';4',1'']terphenyl-3,5,2',5',3'',5''-hexacarboxylic acid (H6L) through a systematic solvent-ratio-controlled method, named {[Et2NH2]2[Zn5(L)2(H2O)4]·2C2H5OH·2H2O}n (1),



(2), (3),

{[Et2NH2]4[Zn4(L)2(H2O)2]·4H2O}n (4) and {[Et2NH2]2[Zn2(L)]·C2H5OH}n (5). Their



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structural diversities show that the solvent ratio plays an important part in the self-assembly processes. These five complexes are characterized by single-crystal X-ray crystallography, powder X-ray diffraction (PXRD), elemental analyses (EA) and thermogravimetric analyses (TGA). Furthermore, their luminescent properties are investigated at room temperature and cryogenic temperature (77 K). EXPERIMENTAL SECTION Materials and Methods. All chemicals and solvents used in the synthetic processes were purchased from commercial sources and used without further purification. Elemental analyses (C, H, and N) were performed with an Elementar Vario MICRO elemental analyzer. The IR spectra were collected from KBr pellets (5mg of sample in 500mg of KBr) on a PerkinElmer Spectrum One FT-IR spectrometer in the range of 4000−400 cm−1. The powder X-ray diffraction (PXRD) data were collected on a RIGAKU MiniFlex 600 diffractometer at room temperature with Cu Kα radiation. TGA was performed on pre-weighed samples using a NETZSCH STA 449C instrument during room temperature and 1000 ℃ under nitrogen atmosphere. Luminescence spectra were investigated on FLS980 with 450W xenon light.

Syntheses of complexes 1-5. The reacting ingredients used in the synthetic progresses of these five complexes are exactly the same. Typically, a mixture of Zn(NO3)2·6H2O (0.089 g, 0.3 mmol) and H6L (0.025 g, 0.05 mmol) was dissolved in 5 mL mixed solvent of DEF/H2O/C2H5OH, then 0.02 mL HNO3 is added. The final mixture was placed in glass vessels (20 mL) and heated at 85 ℃ for 5 days, getting the colorless crystal product. The only differences in these synthetic processes are the


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ratios of the mixed solvent DEF/H2O/C2H5OH: a ratio of 2:2:1 for complex 1, 7:1:2 for complex 2, 3:1:1 for complex 3, 8:1:1 for complex 4 and 6:1:3 for complex 5. The yields are 68% (based on H6L) for complex 1, 42% for complex 2, 34% for complex 3, 56% for complex 4, and 52% for complex 5. Elemental Analysis (EA) and IR Spectra Elemental analysis (%): Complex 1: Anal. Calc. (%) for C60H64N2O32Zn5 (Mr =1652.19): C, 42.79; H, 3.96; N, 1.72. Found (%): C, 42.81; H, 3.40; N, 1.73. Complex 2: Anal. Calc. (%) for C120H122N4O58Zn7 (Mr =3006.11): C, 47.95; H, 4.09; N, 1.86. Found (%): C, 48.02; H, 4.05; N, 1.89. Complex 3: Anal. Calc. (%) for C92H94N4O42Zn6 (Mr =2320.19): C, 47.62; H, 4.08; N, 2.41. Found (%): C, 47.68; H, 4.11; N, 2.36. Complex 4: Anal. Calc. (%) for C64H76N4O30Zn4 (Mr =1642.93): C, 46.79; H, 4.66; N, 3.41. Found (%): C, 46.75; H, 4.71; N, 3.43. Complex 5: Anal. Calc. (%) for C34H38N2O13Zn2 (Mr =813.49): C, 50.20; H, 4.71; N, 3.44. Found (%): C, 50.22; H, 4.76; N, 3.39. IR spectra (KBr, cm-1): Complex 1: 3393 (w), 1622 (s), 1578 (s), 1359 (s), 777 (m), 728 (m). Complex 2: 3388 (w), 1631 (s), 1370 (s), 1043 (s), 808 (s), 766 (m), 729 (m), 594 (w). Complex 3: 3359 (w), 2988 (w), 1632 (s), 780 (m), 596 (s). Complex 4: 2990 (w), 2741 (w), 1628 (s), 1572 (s), 1368 (s), 782 (m), 720 (m). Complex 5: 3047 (w), 2779 (w), 1627 (s), 1367 (s), 781 (m), 721 (m), 571 (w), 478 (w). Crystal Structure Determination Diffraction data for complexes 1-5 were collected on a SuperNova diffractometer at 100 K. The structures of complexes 1-5 were resolved by the direct method. And the



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full-matrix least-squares refinement on F2 was finished using SHELX-975. All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms from aromatic carbon atoms were generated geometrically, while those on the water molecules could not be determined. The final chemical formulae of 1-5 were calculated from SQUEEZE6 results combined with the result of TGA and elemental analyses data. The CCDC numbers are 1032828-1032832 for 1-5, respectively. In complex 1, one Zn(Ⅱ) cation is disordered over two sites, i.e. Zn3 and Zn4, with occupancy of 0.8 and 0.2 respectively. Accordingly, one water molecule is also disordered over two sites, i.e. O15 and O16, both their occupancy are 0.5. RESULTS AND DISCUSSION By designing the reaction of H6L ligand with Zn(NO3)2 in a ternary solvent mixture with the same composition (DEF/H2O/C2H5OH) but different ratios, and maintaining other effect factors constant during the synthetic processes, we have successfully got five new 3D coordination polymers with entirely different coordination architectures. It is worth mentioning that pure crystal products can only be obtained at the particular solvent ratios, while the other experiments result in powder forms or mixed products. The solvent volumes used in the synthetic processes and molecular formulas of 1-5 are recorded in a tabular form (Table 1). It clearly shows that the solvent ratios have effects on the final products and the simple change of mixed solvent ratio can generate quite different structures of the resultant complexes. Table 1. Molecular formulas and the solvent volumes used in the synthetic processes of 1-5.


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Complex

Molecular Formula

DEF/mL

H2O/mL

C2H5OH/mL

2

2

1

3.5

0.5

1

1

{[Et2NH2]2[Zn5(L)2(H2O)4]·2C2H5OH·2H2O}n

2


3


3

1

1

4

{[Et2NH2]4[Zn4(L)2(H2O)2]·4H2O}n

4

0.5

0.5

5

{[Et2NH2]2[Zn2(L)]·C2H5OH}n

3

0.5

1.5

The Diverse Coordination modes of the ligand in 1-5. As shown in the Scheme 1 and Table 2, H6L exhibits nine different coordination modes because of the different degrees of deprotonation, the numbers of metal centers each ligand connected and the different dihedral angles between benzene rings. In complex 1, H6L is completely deprotonated and connected with nine metal ions adopting µ9-coordination modes (named MODE Ⅰ). In complexes 2 and 3, there are both two distinct coordination modes with not only different degrees of deprotonation but also different metal numbers every ligand connected (MODE Ⅱ and MODE Ⅲ in 2, MODE Ⅳ and MODE Ⅴ in 3). For complexes 4 and 5, there are also two different coordination modes (MODE Ⅵ and MODE Ⅶ in 4, MODE Ⅷ and MODE Ⅸ in 5). Unlike 2 and 3, the two modes in 4 or 5 have only one difference: the discrepancy on dihedral angles. To sum it up, the changing of solvent ratios can lead to difference coordination modes of ligands, which have major effect on the final structures.



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Scheme 1. Diverse coordination modes of the ligand in complexes 1-5. Table 2. The coordination types of the ligand. Complex

Coordination modes

Deprotonation

1

µ9/MODE Ⅰ

L

46.622(167), 23.373(172), 4.017(179)

2

µ6/MODE Ⅱ

H2L

87.538(138), 51.630(127), 41.617(133)

µ7/MODE Ⅲ

HL

53.128(140), 51.616(135), 19.425(143)

µ8/MODE Ⅳ

L

54.458(168), 49.206(159), 5.351(182)

µ6/MODE Ⅴ

H2L

41.649(184), 41.823(186), 0.000(265)

µ8/MODE Ⅵ

L

55.557(470), 54.466(492), 3.759(399)

µ8/MODE Ⅶ

L

73.220(476), 77.126(412), 4.785(421)

µ8/MODE Ⅷ

L

57.428(394), 57.428(391), 0.000(573)

µ8/MODE Ⅸ

L

64.887(380), 64.887(375), 0.000(574)

3

4

5

Dihedral angles (°)


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Description of crystal structure Structure Description of {[Et2NH2]2[Zn5(L)2(H2O)4]·2C2H5OH·2H2O}n (1). The crystal structure determination of 1 reveals that the asymmetric unit contains two and a half Zn (Ⅱ) cations. Zn1, Zn2 and the symmetry-related specie of Zn2 form an hourglass trinuclear cluster with a Zn…Zn distance of 3.7056(0) Å (Figure S1a of the SI). Each completely deprotonated ligand with MODE Ⅰ (Scheme 1) connects with one trinuclear cluster and one Zn3 ion to give rise to a repeat unit (Figure 1b). Four of these units are linked with each other by sharing metal centers to make a circular window with the dimension of 11.467 × 12.741 Å2 (Figure 1c). The ligands extend backward and forward because of its nature of multiple connection points to form a 3D framework (Figure 1d). Topologically, the trinuclear clusters can be seen as 8-connected nodes, and the Zn3 ions can be looked as 2-connected nodes which are simplified as lines. Once the Zn3 ions are considered as lines, the ligands can be simplified as 5-connected nodes. Therefore, the structure of 1 can be symbolized as a (5, 8)-connected net with the point symbol of {3.415.54.68}{3.45.52.62}2 (Figure 1e). Based on the result given by TOPO 4.0 program, this topology turns out to be a new topology with the existence of relatively high-connected nodes.



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Figure 1. (a) The coordination environments for Zn(Ⅱ) ions in 1; (b) The repeat unit formed by one ligand connected with one trinuclear cluster and one Zn3 ion; (c) The circular window made by four repeat units; (d) The 3D framework viewed along a axis; (e) Schematic representation of topology of 1.

Structure Description of {[Et2NH2]4[Zn7(HL)2(H2L)2]·4C2H5OH·6H2O}n (2). Single-crystal X-ray diffraction analysis indicates that the three and a half crystallographically independent Zn(Ⅱ) ions in the asymmetric unit of 2 give rise to two metal centers: one is an hourglass trinuclear cluster formed by Zn1, Zn2 and


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the symmetry-related specie of Zn2 with a Zn…Zn distance of 3.2840(5) Å (Figure S1b), and the other one is a paddle-wheel binuclear cluster generated by Zn3 and Zn4 with a Zn…Zn distance of 3.4450(9) Å (Figure S1c). There are two distinct partially deprotonated H6L ligands (H2L4- (MODE Ⅱ) and HL5- (MODE Ⅲ), scheme 1) in 2. Each H2L4- is connected with two trinuclear clusters and two binuclear clusters to form a repeated unit (Figure 2b). By sharing metal clusters, the neighboring repeated units are extended to form an infinite 2D network as Figure 2c shown. Along a axis in the 2D network, the HL5- ligands link the neighboring trinuclear and binuclear clusters with two uncoordinated carboxylate groups suspended (Figure 2d). The overall structure of the layers viewed along a axis is shown in Figure 2e. The suspended uncoordinated carboxylate groups of terminate phenyl rings link the binuclear clusters of adjacent layers in a zipper mode to give rise to a 3D framework (Figure 2f). For the whole structure, viewed along a axis, there exists a rhombic channel with the dimension of 11.136 × 14.209 Å2 which is occupied by diethylamine cations, ethanol molecules and water molecules. Topologically, the hourglass trinuclear clusters and paddle-wheel binuclear clusters can be considered as 6-connected and 5-connected nodes respectively. Both the two kind ligands can be considered as 4-connected nodes. Thus, the 3D framework of 2 can be described as a 3D (4,4,5,6)-connected net with the point symbol of {44.62}4{45.65}2{46.66.82.10} (Figure 2g).



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Figure 2. (a) The coordination environments for Zn(Ⅱ) ions in 2; (b) The repeated unit formed by H2L4- connected with two trinuclear clusters and two binuclears (green: hourglass trinuclear cluster; cyan: paddle-wheel binuclear cluster); (c) The 2D layer formed by neighboring repeated units connected with each other by sharing metal clusters. (d) The view of HL5- linking the neighboring trinuclear and binuclear clusters; (e) The overall structure of the layers viewed along a axis; (f) The view of the 3D framework along a axis; (g) Schematic representation of topology of 2.

Structure Description of {[Et2NH2]4[Zn6(L)2(H2L)(H2O)2]·2C2H5OH·2H2O}n (3). Crystal structure of 3 reveals that there are three independent Zn(Ⅱ) ions, one completely deprotonated H6L ligand (L6-) (MODE Ⅳ , Scheme 1), and half


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partially deprotonated H6L ligand (H2L4-) (MODE Ⅴ,Scheme 1) in the asymmetric unit. Each Zn( Ⅱ) cation is four-coordinated forming a distorted tetrahedron geometry. Zn1 and Zn2 adopt almost the same coordination environments, both are four-coordinated by four O atoms from four carboxylate groups on distinct ligands. It is noteworthy that among the four carboxylate groups, three carboxylate groups bridging-chelate Zn1 and Zn2 to form a paddle-wheel binuclear [Zn2(COO)3] cluster with a Zn…Zn distance of 3.4636(8) Å (Figure S1d). Zn3 is four-coordinated with three O atoms from three carboxylate groups and one O atom from a coordinated water molecule. The binuclear centers and the Zn3 centers are connected by the ligands with MODE Ⅳ to generate a 2D layer as Figure 2b shown. Viewed along a axis, these layer structures are further pillared by ligands with MODE Ⅴ, giving a 3D framework (Figure 2d). Because of this braced structure, there exits three parallelogram channels along a axis: the bigger one is with the dimension of 11.170 × 12.193 Å2 , and the two smaller ones are the same with the dimension of 10.173 × 6.043 Å2. To get better insight of the structure, the topological analysis of 3 has been performed. If we consider the binuclear centers as 5-connected nodes, Zn3 centers as 3-connected nodes, and two kinds of ligands as 6-connected and 4-connected nodes respectively, the structure can be simplified as

a

(3,4,5,6)-connected

net

with

the

{42.6}2{42.84}{46.63.8}2{47.66.82}2 (Figure 3e).


point

symbol:


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Figure 3. (a) The coordination environments for Zn(Ⅱ) ions in 3; (b) The 2D layer structure formed by binuclear clusters and Zn3 centers linked together by ligands with MODE Ⅳ; (c) The 2D layer structure viewed along a axis; (d) Viewing of the 3D framework of 3 along a axis; (e) Schematic representation of topology of 3.

Structure Description of {[Et2NH2]4[Zn4(L)2(H2O)2]·4H2O}n (4). Single-crystal X-ray diffraction study of 4 presents that the asymmetric unit contains two completely deprotonated H6L ligands (L6-) with different coordination modes (MODE Ⅵ and MODE Ⅶ, Scheme 1). The two modes have almost same coordination sites, but different dihedral angles (Table 2, MODE Ⅵ and MODE Ⅶ). There are four independent Zn(Ⅱ) ions in the asymmetric unit, in which, Zn1


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and Zn3 possess four coordinated environments while Zn2 and Zn4 adopt six coordinated environments. Notably, both Zn2 and Zn4 are bridging-chelated by three carboxylate groups with their symmetry-related species, generating similar binuclear [Zn2(COO)3] clusters with a Zn…Zn distance of 3.1173(27) Å and 3.0999(27) Å, respectively (Figure S1e). The constructing course of 3D framework of 4 is analogous to 3. The binuclear centers are linked by ligands with MODE Ⅵ to generate 2D layers (Figure 4b), which are further pillared by ligands with MODE Ⅶ to give rise to a 3D framework (Figure 4d). There are also three kinds of windows with the dimensions of 12.493 × 5.586 Å2, 7.615 × 5.224 Å2 and 7.693 × 6.505Å2, respectively. If we consider the binuclear Zn centers as well as ligands as 6-connected nodes, Zn1 and Zn3 as 3-connected nodes, the overall structure of 4 can

be

rationalized

as

a

3D

network

with

the

point

symbol:

{43}2{46.66.83}{48.66.8}2 (Figure 4e). The topologies of complexes 2-4 are all 3D 4-nodal net based on two kinds of metal centers and two kinds of ligands’ coodination modes. Because of the specialty of multi-nodal net, all the three topologies have not been reported literary.



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Figure 4. (a) The coordination environments for Zn(Ⅱ) ions in 4; (b) The 2D layer structure based on binuclear Zn(Ⅱ) centers linked by ligands with MODE Ⅵ; (c) The 2D layer structure viewed along a axis; (d) Viewing of 3D open-framework of 4 along a axis; (e) Schematic representation of topology of 4.

Structure Description of {[Et2NH2]2[Zn2(L)]·C2H5OH}n (5). X-ray crystal structural analysis reveals that there are two Zn ( Ⅱ ) ions and two crystallographically independent completely deprotonated H6L ligand (L6-) with 50% occupancy (MODE Ⅷ and MODE Ⅸ, Scheme 1) in the asymmetric unit.


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Similar to complex 4, the two independent ligands in 5 adopt same coordination modes, but have different dihedral angles (Table 2, MODE Ⅷ and MODE Ⅸ). As shown in Figure 5a, both Zn1 and Zn2 are four-coordinated by four O atoms from four carboxylate groups, resembling a distorted tetrahedral geometry. Zn1 and Zn2 are bridged-chelated by two carboxylate groups to generate a binuclear cluster with a Zn…Zn distance of 3.5126(23) Å (Figure S1f), and every ligand connects with four of these clusters giving rise to a repeated unit. There are two kinds of repeated units originated from two different ligands (Figure 5b), which are arranged repeatedly along c axis creating zigzag patterns, and alternatively along a axis at two almost mutual vertical directions (Figure 5c and 5d). This way of arrangement forms a rectangular channel along a axis with the dimension of 6.976 × 6.586 Å2. Each binuclear unit connects with six carboxylate groups of six individual ligands, extending forward and backward through ligands to form a 3D structure. Topologically, the 3D framework of 5 can be simplified as a uninodal net with the point symbol of {410.65} (Figure 5e) if we consider both the binuclear units and ligands as 6-connected nodes. Although the uninodal 6-connected net is simple, this topology of 5 remains a new topology so far according TOPO 4.0 program.7



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Figure 5. (a) The coordination environments for Zn(Ⅱ) ions in 5; (b) The two kinds of repeated units originated from two different ligands (left for MODE Ⅷ, right for MODE Ⅸ); (c) The pattern of repeated units arranged along a axis and c axis; (d) The pattern of repeated units arranged along b axis and c axis; (e) Schematic representation of topology of 5.

The Effect of Solvent Ratio and Comparison of Structures


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Comparing the structures and the synthetic conditions of the five complexes, we find that the solvent ratio is the most significant factor that drives the formation of the five complexes (Scheme 2). It is of great importance to employ the precise solvent ratio of the one-pot reaction conditions for the assembly of 1-5. Some of the structure disparities observed in complexes 1-5 are summarized as below.8 At the ratio of 2:2:1, complex 1 is obtained. The completely deprotonated ligand with MODEⅠin 1 link one trinuclear metal cluster and one crystallographically independent Zn(Ⅱ) ion to generate a repeated unit. The repeated units move forward and backward by sharing metal centers to give rise to the 3D framework of 1. During the synthesis of 2, the solvent ratio is adjusted to 7:1:2. There also exists one repeated unit formed by H2L4- ligand with MODE Ⅱ linking to one trinuclear and one binuclear metal cluster in 2. Then the repeated units and HL5- with MODE Ⅲ connect each other to generate a 2D layer structure with two uncoordinated carboxylate groups suspended, which link the binuclear clusters of adjacent layers in a zipper mode to give rise to a 3D framework. Complexes 3 and 4 are obtained at the solvent ratios of 3:1:1 and 8:1:1 respectively. The structures of 3 and 4 are similar: the ligands with one coordination mode (MODE Ⅳ for 3 and MODE Ⅵ for 4) link metal centers to generate 2D layers, which are further pillared by ligands with another coordination modes (MODE Ⅴ for 3 and MODE Ⅶ for 4) to give rise to 3D frameworks. Complex 5, obtained with a DEF:H2O:C2H5OH volume ratio of 6:1:3, exhibits 3D framework formed by two kinds of repeated units linking together and extending forward and backward. The ligands in the two kinds of repeated units adopt



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same coordination modes but with different dihedral angles (MODE Ⅷ and MODE Ⅸ). Based on the discussion above, we come to the conclusion that the coordination modes of the ligands alter as the solvent ratios change during synthetic processes. So the difference of the 3D frameworks and topologies of the resultant complexes can be attributed to the alteration of the ratios of the mixed solvent.

Scheme 2. Schematic drawing of the synthetic processes of complexes 1-5.

Thermal Analysis and PXRD Results. To investigate the thermal stability of these frameworks, the thermogravimetric analysis (TGA) was performed under N2 atmosphere. The TGA curves are shown in Figure S2. For complexes 1, 3, and 5, the whole structure began to collapse at around 320 ℃ with one weight loss step observed. Complex 1 and complex 3 lose lattice water and ethanol molecules at 135℃ (obsd: 7.79%; calcd: 7.76%) and 113 ℃


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(obsd:5.53%; calcd: 5.527% ), respectively. The weight loss of complex 5 occurred at 105 ℃ corresponds to the loss of ethanol molecules (obsd: 5.62%; calcd: 5.67%). For complexes 2 and 4, after the weight loss at around 120 ℃ the remaining frameworks remain thermally stable until ca. 180 ℃. The weight loss at 128 ℃ of 2 is attributed to the removal of lattice water and ethanol molecules (obsd: 9.66%; calcd: 9.7%). And for 4, the loss of water molecules (obsd: 4.38%; calcd: 4.39%) occured at 122 ℃. Powder X-ray diffraction (PXRD) experiments for complexes 1-5 have been carried out at room temperature to identify if the crystal structures can represent the bulky samples. As shown in Figures S3, the peak positions of the PXRD patterns are closely matched the simulated ones, which indicates that the as-synthesized bulk materials are pure products. Luminescent Properties. Because the luminescent coordination polymers containing d10 transition metals have various potential applications in photochemistry, drug delivery, and chemical sensors, they have attracted much attention.9 Thus, in this work, we examined the luminescent properties of the five complexes in the solid state at room temperature and low temperature (77 K). As shown in Figure 6a, at room temperature, the free H6L ligand exhibits an intense emission at 418 nm upon being excited at 360 nm, which may be attributed to the n→π* or π→π* electronic transitions.10 The emission spectra of complexes containing metal ions produce high energy emission peaks at 387 nm (λex=329 nm) for 1, 377 nm (λex=332



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nm) for 2, 392 nm (λex=350 nm) for 3, 389 nm (λex=347 nm) for 4, and 400nm (λex=350 nm) for 5, which can all be assigned to the interligand charge transfer because of the similar peak position and characteristic.11 Compared with the emission spectra of the free ligand, the peaks of complexes become much broader, showing the tendency to give rise to peaks at the low energy emission bands. To confirm the tendency we speculate, the studies of solid-state luminescent properties at 77 K were carried out. As illustrated in Figure 6b, the spectrum of free ligand shows no significant change. But for all the complexes, the spectra have changed more or less. Just as we speculated, all the complexes produce peaks at ~500nm either weak or strong, which can be due to the metal-ligand-charge-transfer (MLCT) and/or ligand-metal-charge-transfer (LMCT), according to the reported results on coordination polymers with aromatic polycarboxylate ligands12. The difference of luminescent properties at room temperature and 77 K demonstrate that complexes 1-5, especially 3, show high sensitivity to temperature. Table 3. Luminescence data of H6L and complexes 1-5 in the solid state at room temperature (RT) and 77 K.

λex/nm

Complex

λem/nm

RT

77 K

RT

77 K

H6 L

360

360

418

419

1

329

329

387

386, 538

2

347

347

389

389, 509

3

332

332

377

401, 510


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4

350

350

392

380, 503

5

350

350

400

400, 520

Figure 6. (a) Solid-state luminescence spectra of H6L and complexes 1-5 at room temperature. (b) Solid-state luminescence spectra of H6L and complexes 1-5 at 77K.

To further elucidate the electron-transfer process, the optimized structures for 1-5 were theoretically calculated by evaluation of the density of states (DOS), which were calculated with the CASTEP code based on density functional theory (DFT) using a plane expansion of the wave functions.13 The total and partial DOS for complexes 1-5 are illustrated in Figure 6-7 and Figure S4-S6. As we can see, the five complexes exhibit similar valance bands (VBs) and two kinds of conduction bands (CBs). Take complexes 3 and 5 for example, the VBs between -2.5 eV and the Fermi level (0.0 eV) for both 3 and 5 are mainly dominated by the p-π orbitals of the ligands (H6L), mixed with a small amount of 3d orbitals of Zn (Ⅱ) ions. The CBs for 5 are almost all contributed by the p-π* antibonding orbitals of H6L while the CBs of 3 containing mostly p-π* antibonding orbitals of H6L and a little contribution of 3p orbitals of Zn (Ⅱ) ions. Accordingly, it can be considered that the main emission peak at ~400 nm



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mainly originates from interligand π→π* transition H6L ligands. The small contribution of Zn (Ⅱ) ions to the VBs or CBs explains the tendency of emission peak at ~500 nm at room temperature, which can be attributed to the MLCT and/or LMCT. The appearance of peaks at ~500 nm at 77 K can be attributed to the significant reduction of the rate of nonradiative decay in the process of a π→π* transition of H6L at cryogenic temperature.14

Figure 7. The total and partial DOS of complex 3.


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Figure 8. The total and partial DOS of complex 5.

To visually display the thermochromic properties, the CIE-1931 (Commission International de L’Elairage 1931) coordinates of 1-5 were calculated from the fluorescence emission spectra (Table 4), and marked as shown in Figure 9. At room temperature, the ligand (H6L) and all the five complexes are located in the blue region. The CIE coordinate of H6L at 77 K is almost the same with that at room temperature whereas those of complexes 1-5 change more or less. For complexes 1, 2 and 5 at 77 K, they remain in the blue region but move to the green and white region slightly. Complex 4 appears at the edge of the blue, green and white regions. It is worth nothing that the change of complex 3 from room temperature to 77 K is quite obvious. At room temperature, the emission of 3 is located at pure blue region. With the temperature drops to 77 K, the CIE chromaticity value moves to pure green region.



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The obvious change of spectral colors of 3 indicates that it may be a potential candidate for applications in temperature-sensing devices.15 Table 4. CIE coordinates of H6L and complexes 1-5 at room temperature (RT) and 77 K.

Complex

CIE coordinates RT

77 K

H6 L

0.16, 0.07

0.17, 0.09

1

0.17, 0.09

0.22, 0.18

2

0.18, 0.10

0.21, 0.18

3

0.18, 0.16

0.24, 0.35

4

0.18, 0.13

0.22, 0.26

5

0.17, 0.10

0.19, 0.16


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Figure 9. (a) CIE-1931 chromaticity diagram for H6L and complexes 1-5 at room temperature. (b) CIE-1931 chromaticity diagram for H6L and complexes 1-5 at 77 K.

Conclusions In summary, we successfully report a synthetic method of coordination polymers in a ternary solvent mixture through low-temperature solvothermal reactions with the single and subtle variable: the ratio of mixed solvent. Using this method, we have synthesized five new complexes by self-assembly of H6L and Zn (Ⅱ), which represents the most complicated system that can be tuned by the ratio of the mixed solvent so far. This study widens the exploration of the synthetic strategy in crystal engineering. The temperature-dependent luminescence properties of these five complexes were investigated at room temperature and cryogenic temperature (77 K). The result shows that compared with the emission spectra at room temperature, the spectra at 77 K exhibit obviously new peaks at the low energy bands which can be attributed to MLCT and/or LMCT. The density of states of complexes 1-5 was calculated to further elucidate the electron-transfer processes. According to the result of the CIE chromaticity calculations, these complexes, especially complex 3, are potential candidates for applications in temperature-sensing devices.

ASSOCIATED CONTENT

Supporting Information. The metal clusters, XRD patterns, TGA curves, crystal data and structure refinements, selected bond lengths and angles of complexes 1-5,



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and the total and partial DOS of 1, 2 and 4. This information is available free of charge via the Internet at http://pubs.acs.org/.

AUTHOR INFORMATION

Corresponding Author Tel.: +86-591-83792460. Fax: +86-591-83794946.

E-mail: [email protected]

(M.-C. H.), [email protected] (L. C.)

ACKNOWLEDGMENTS

We are thankful for financial support from the 973 Program (2011CB932504), National Natural Foundation of China (21390392, 21131006), and The CAS/SAFEA International Partnership Program for Creative Research Teams.

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Tables of Contents Synopsis Structural Diversity Modulated by the Ratios of a Ternary Solvent Mixture: Syntheses, Structures and Luminescent Properties of Five Zinc (Ⅱ) MOFs Xiuyan Wanab, Feilong Jianga, Lian Chena*, Mingyan Wua, Mingjian Zhanga, Jie Panab, Kongzhao Suab, Yan Yangab and Maochun Honga* Five new complexes with distinct structures and topologies have been synthesized by systematic tuning the ratios of a ternary solvent mixture. The photoluminescence experiments of as-synthesized complexes at ambient temperature and cryogenic temperature show that all the five complexes exhibit temperature-dependent emission properties.


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Syntheses, Structures, and Luminescent Properties of - American

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