MetalâOrganic Frameworks Based on a Bent Triazole Dicarboxylic

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Metal–Organic Frameworks Based on a Bent Triazole Dicarboxylic Acid: Magnetic Behaviors and Selective Luminescence Sensing Properties Yu-Xiao Zhang, Hua Lin, Yuehong Wen, and Qi-Long Zhu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01589 • Publication Date (Web): 08 Jan 2019 Downloaded from http://pubs.acs.org on January 11, 2019

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Crystal Growth & Design

Metal–Organic Frameworks Based on a Bent Triazole Dicarboxylic Acid: Magnetic Behaviors and Selective Luminescence Sensing Properties Yu-Xiao Zhang,†,‡ Hua Lin,† Yuehong Wen,† and Qi-Long Zhu*,† †State

Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,

Chinese Academy of Sciences, Fuzhou 350002, China ‡University

of Chinese Academy of Sciences, Beijing 100049, China

KEYWORDS: metal–organic framework, crystal structure, luminescence sensing, magnetic property

ABSTRACT: Four new metal–organic frameworks constructed from bent triazole dicarboxylic acid ligand, 3,5-bis(4'-carboxyphenyl)-1,2,4-triazole (H2bct), have been discovered by a solvothermal method. These

MOFs,

[M5(μ2-H2O)2(μ3-OH)2(bct)4(H2O)8]·4H2O}n

(1,

M

=

Co;

2,

M

=

Ni),

{[Cd2(bct)2(bipy)]·5H2O}n (3) (bipy = 4,4'-bipyridine) and {[Cd(bct)(tib)]·H2O·DMF}n (4) (tib = 1,3,5tris(1-imidazolyl)benzene) exhibit diverse coordination modes and fascinating crystal structures. The crystallographic structures, thermal stabilities, photoluminescence and magnetic properties have been studied. 1 and 2 share the semblable structural features based on planar pentanuclear clusters except for the central ions, where the 1D chain structures are constructed from the pentanuclear secondary building units linked with bct2– ligands. While 3 and 4 have similar layered structures. Magnetic analyses of 1 and 2 reveal that an overall antiferromagnetic coupling within the pentanuclear Co(II) cluster nodes are observed, which can be switched to strong ferromagnetic coupling when using Ni(II) to replace the Co(II) sites. Both 3 and 4 show intense blue emission under ultraviolet excitation. Moreover, 4 can be applied as

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a selective sensor for quantitative testing the concentration of acetone in water based on luminescence quenching effect, with a quenching constant (Ksv) value of 12.89 L mol–1 in water.

INTRODUCTION Metal-organic frameworks (MOFs) feature structural and compositional diversity with exploitable properties,1-2 making them versatile functional materials for various applications, such as gas adsorption and separation,3-5 drug delivery and release,6-8 luminescence sensing,9-12 energy storage,13-15 catalysis,1617

etc. The structures and functionalities of such MOFs are strongly depended on the geometries and

properties of ligands or coordination modes of central metal ions/secondary building units (SBUs).18-20 Thus, exploring the relationship between the geometries of ligands and the structures of resulting MOFs is of great significance. Differing from the higher-symmetric linear ligands, the selection of bent ligands, such as 1,3benzenedicarboxylic acid,21-23 3,5-pyridinedicarboxylic acid24 and other,25-26 could lead to the formation of the MOFs with low symmetries and more structural diversity, which may be not easily amenable with linear linkers. Due to their versatile coordination configurations, the bent ligands have been widely applied to build the MOFs with various dimensions and topologies. So far, a number of works involving bent ligands have been reported. A series of work reported by Fujita et al. have attracted widespread attention.27-29 The rigid bent ligands, such as 2,5-di(pyridin-4-yl)furan and 1,3-di(pyridin-4-yl)benzene, were assembled with Pd(II) to construct a family of coordination spheres. Huge caves in these spheres can be utilized to encapsulate guest molecules even protein. The V-type ligand, 4,4'-dicarboxybiphenyl sulfone, has been utilized to synthesize a 2D MOF containing a [Co3(μ3-OH)2]n infinite chain, which shows interesting magnetic properties.30 The two-fold interpenetrated MOF constructed from 1,3-di(4carboxyphenyl)benzene and exhibits the luminescence sensing properties for nitroaromatic explosives.31


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Meanwhile, introducing functional groups into the ligands could have marked impacts on the structures and properties of the resulting MOFs due to their additional coordination sites and electronwithdrawing/donating effects. Bharadwaj et al. reported a MOF constructed with Zn8O cluster and curved ligand 1,3-bis(4-carboxyphenyl)imidazolium. With the decoration of the channels by the aligned imidazolium groups of the ligands, this compound exhibit high proton conductivity with the imidazolium groups acting as proton carriers.32 Sumby et al. reported a 3D interpenetrated MOF comprised of the in situ growth of [Cu(L)2] (L = N-heterocyclic carbene) connectors for the hydroboration of CO2. The hydroboration was catalyzed by the unique [Cu(L)2] linkers, which was constructed by the N-heterocyclic carbene groups of the ligands and Cu(I) centers.33 Therefore, the selection of the bent ligands to study the structural diversity and corresponding functionalities of the resulting MOFs is significant. A new bent ligand containing a triazole group, namely 3,5-bis(4'-carboxyphenyl)-1,2,4-triazole (H2bct, Scheme 1), has multiple coordination sites and slightly electron-withdrawing capacity, and thus is a wise choice for constructing novel MOFs. Herein, a series of new MOFs have been constructed by employing H2bct as the bent ligand, in which the multiple coordination arrangements of the ligand play a vital influence on the structures. These MOFs exhibit fascinating structural chemistries and physical properties. The different magnetic behaviors depending on the metal ions in the planar penta-nuclear clusters have been observed in 1 and 2. In addition, 3 and 4 are both highly emissive at room temperature. Particularly, 4 possess highly selective fluorescence quenching action for acetone and can be used for quantitative detecting the concentration of acetone in water.

EXPERIMENTAL SECTION



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Materials and Methods. All chemicals were obtained from commercial sources. Elemental analyses were recorded on Elementar Vario MICRO CHNOS. Powder X-ray diffraction (PXRD) was tested on Rigaku Desktop MiniFlexII (Cu-Kα radiation). IR spectra were obtained through a PerkinElmer Spectrum One FT-IR spectrometer. Thermogravimetric analyses (TGA) were measured with NETZSCH STA449C equipment under N2 atmosphere. The magnetic properties were performed on Quantum Design PPMS9T. The luminescence spectra were collected on Hitachi F-7000 FL Spectrophotometer. Synthesis. {[Co5(μ2-H2O)2(μ3-OH)2(bct)4(H2O)8]·4H2O}n (1). A total of H2bct (15.5 mg), Co(NO3)2·6H2O (21.8 mg) and NaOH (1.2 mg) in DMF/H2O (2 mL: 2 mL, DMF = N,N’-Dimethylformamide) was mixed into a glass vial. The mixture held at 373 K for 48 h, then cooled to 300 K at 3 K h–1. The violet block crystals with a yield of about 89% (based on H2bct) for 1 were obtained after washing with DMF. {[Ni5(μ3-OH)2(μ2-H2O)2(bct)4(H2O)8]·4H2O}n (2). 2 using a similar synthetic method with 1 and the yield is 84% based on H2bct. {[Cd2(bct)2(bipy)]·5H2O}n (3). A total of H2bct (61.9 mg), Cd(NO3)2·4H2O (61.7 mg), bipy (31.2 mg) and triethylamine (TEA, 28 μL) in DMF/H2O (2 mL: 10 mL) was mixed into a Teflon-lined autoclave. These mixtures were heated at 393 K for 2 d, and then cooled to 300 K at 3 K h–1. The colorless prismatic crystals with a yield of about 74% (based on H2bct) for 3. {[Cd(bct)(tib)]·H2O·DMF}n (4). A total of H2bct (30.9 mg), Cd(NO3)2·4H2O (30.8 mg) and tib (18.5 mg) in DMF/H2O (3 mL: 3 mL ) was mixed into a glass vial. The mixture was keeping in 373 K for 3 d and then cooled to 300 K at 3 K h–1. The yellow block crystals with a yield of about 67% (based on H2bct) for 4. Single-crystal X-ray diffraction (SCXRD) Study. SCXRD data were collected at 293 K on Rigaku Saturn 724HG CCD instrument (Mo-Kα radiation). The structures were solved by SHELXTL-2017 and


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OLEX234 program package,34,35SQUEEZE program in the PLATON software36 was used in 3. Ultimately, the molecule formulas of MOFs 1–4 were calculated by the squeezed SCXRD data together with the results of elemental analyses and TGA. Topology analyses were calculated by ToposPro program.37 Detailed crystallographic data are shown in Table 1 and S1–2. RESULTS AND DISCUSSION Crystal Structure Description {[M5(μ2-H2O)2(μ3-OH)2(bct)4(H2O)8]·4H2O}n (1, M = Co; 2, M = Ni). 1 and 2 are isotype and belong to monoclinic system (space group: P21/n) and shows a 4-connected uninodal grid with Schläfli symbol of (45.6). SCXRD data revealed that there are two and a half crystallographically unique Co atoms and two distinct bct2– ligands, along with four monodentate H2O molecules, one μ2-H2O molecule, one μ3-OH– ion and two free H2O molecules in 1 (Figure 1a). 1 is constructed in the 1D coordination chain structure via the intriguing pentanuclear Co(II) clusters [Co5(μ3-OH)2(μ2-H2O)2(μ2-CO2)4(CO2)4(H2O)8], which consists of a rectangular array of 4 Co(II) ions (Co1, Co3, Co1c, Co3c) with inner angles of 89.05º and 90.95º, and a centered Co2 ion (Figure 1b,c). The central Co2 lies on a crystallographic inversion center connecting four adjacent Co(II) centers via two μ3OH groups, and therefore all the five Co(II) ions are coplanar. The short edge Co1–Co3 of the rectangle is 3.224 Å, while the long edge Co1–Co3c is 6.413 Å. The distances between the central Co2 and the peripheral Co1 and Co3 are 3.613 and 3.565 Å, respectively. The elegant structure features with almost perfect rectangular arrangement and short Co–Co distances could indicate the possibility of a strong Co– Co magnetic interaction within the planar pentanuclear units. All the Co(II) ions are 6-fold coordinated distorted octahedral with normal Co−O distances (2.022(3)–2.184(4) Å).38 The pentanuclear clusters as the SBUs are linked through eight carboxyl groups of the bct2– ligands to build the 1D chains, such chains are further bonded to form the layered structure together via π–π



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interactions (Figures S2 and S3). Contiguous layers are accumulated by hydrogen bonds with the help of uncoordinated H2O molecules (Figure 1e). {[Cd2(bct)2(bipy)]·5H2O}n (3). 3 adopts monoclinic system (space group: P21/c) and there are 2 crystallographically unique Cd atoms, 2 bct2– ligands, 2 bipy ligands and several free H2O molecules. Cd1 shows a distorted octahedra with 5 carboxylic O atoms from bct2– ligands and 1 pyridine N atom, while Cd2 adopts a distorted pentagonal bipyramid with 6 carboxylic O atoms and 1 pyridine N atom (Figure 2a) in the structure. The normal Cd–O lengths between 2.194(6) and 2.611(7) Å.39 The Cd1 and Cd2 are interconnected by these μ2-O atoms, forming the tetranuclear Cd(II) clusters with the adjacent Cd–Cd lengths from 3.736 to 3.984 Å. The crystallographic symmetry operation leads to a parallelogram configuration of the 4 Cd(II) ions in the tetranuclear cluster (Figure 2b). The tetranuclear Cd(II) clusters are interlinked via the bct2– ligands forming the chains, and then further to construct a layer structure by the bipy ligands (Figure 2c). The layers can be stacked together with π–π interactions and form a supramolecular 3D framework (Figures 2d and S4). The Schläfli symbol of 3 is (4.52)2(42.52.64.7.8)(43.52.62.72.8)(43.52.7) (Figure S5).37 {[Cd(bct)(tib)]·H2O·DMF}n (4). 4 adopts triclinic space group Pī and the crystallographically independent Cd atom exhibits a pentagonal bipyramid coordination geometry with 5 carboxylic O atoms constituting an equatorial plane and 2 pyridine N atoms of tib ligands in the fixed points (Figure 3a). The chelating– bridging tridentate coordination types of the carboxyl groups result in the edge-shared dinuclear [Cd2(η2CO2)2] SBUs, in which the distance of neighboring Cd(II) centers is 3.884 Å (Figure 3b). The normal Cd−N and Cd−O distances are 2.2712(19)–2.292(2) Å and 2.3260(18)−2.5160(18) Å, respectively.40 Each dinuclear SBU is connected by four bct2– ligands to form chains, and then form a layer structure via the tib ligands (Figure 3c), which is quite similar with the structure of 3. The 2D layers present good configuration for π–π interactions between the triazole rings (Figure S6), extending to a 3D network with

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DMF and water molecules located in the void space (Figure 3d). The pore window size of the void space is ca. 5  5 Å2. 4 exhibits a new topology with a 3,5-connected 2-nodal grid, and the Schläfli symbol is (42.67.8)(42.6) (Figure S7).37 PXRD, Thermal Analyses and Magnetic Properties The purity of 1–4 was confirmed by PXRD, as shown in Figure S9. The experimental PXRD matches well with the simulated SCXRD. In addition, TGA cures of 1–4 are also given in Figure S10. Take 4 as an example, we can see three platforms: first, the mass loss of 2.69% at 110 °C due to the release of H2O molecule (theoretical value: 2.29%); then continue to lose 9.54% at 300 °C ascribed to the decompose of DMF (theoretical value: 9.31%); and above that, the weight loss suggests the decomposition of the organic component. The temperature-dependent χMT and χM–1 curves of 1 and 2 were given in Figure 4. The experimental χMT values are match well with the calculated values at 300 K, such as, 15.01 vs 14.65 cm3 K mol–1 for 1 and 5.57 vs 5.51 cm3 K mol–1 for 2. In 1, with decreasing temperature, χMT value decreases gradually to 9.46 cm3 K mol–1 at 28 K, and then increases to 10.27 cm3 K mol–1 at 9.5 K. Upon further cooling, the χMT value continues to decline to 7.75 cm3 K mol–1 at 2 K. The χM–T curve in 75−300 K can be well described by Curie−Weiss rule. The calculated C and θ are 17.06 cm3 K mol–1 and = −43.27 K, respectively, which indicates an overall antiferromagnetic interaction. The increase of χMT value below 28 K could be attributed to ferrimagnetism or spin-canting. For 2, the maximum value of χMT is 9.12 cm3 K mol–1 at 3.47 K, suggest a ferromagnetic (FM) coupling between the Ni(II) ions within the planar pentanuclear clusters. Further cooling resulted in the decrease of the value to 8.16 cm3 K mol–1 at 2 K, which could be caused by the zero-field splitting (ZFS) effects and/or the antiferromagnetic interaction between adjacent clusters at low temperature. Based on



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the Curie−Weiss law in 75–300 K, the calculated θ is 18.64 K. Such positive θ confirms that the FM interactions between Ni(II) ions. Luminescence Properties and Luminescence Sensing of Small Organic Molecules MOFs based on d10 metal centers usually exhibit luminescence properties, thus could be used as luminescent materials.41-42 Accordingly, solid-state luminescence spectra of 3 and 4, as well as ligands H2bct, bipy and tib, were measured at room temperature. The emissions at 376, 415 and 407 nm were observed for H2bct, bipy and tib ligand, with excitation wavelength of 273, 344 and 360 nm, respectively (Figure S11). Such emissions could be attributed to π*→π or π*→n transitions.43-44 With excitation maximum at 369 and 368 nm, the emission spectra of 3 and 4 at room temperature give intense blue emission bands centered at 425 and 450 nm, respectively (Figure 5). Due to the similar emission bands for both samples, the emissions of 3 and 4 can be attributed to metal-perturbed intraligand charge transfers (ILCT) and/or ligand-to-ligand charge transfers (LLCT). Taking advantage of the porous structure and luminescence properties of 4, further study on luminescence sensing of small molecules was undertaken. It was anticipated that free DMF and H2O molecules located in the void space of 4 could be replaced by other different common solvents. We have firstly recorded the room-temperature emission and excitation spectra of 4 suspended in water with the concentration of 0.5 mg mL–1. As shown in Figure 6a, 4 in water gave an intense λem(max) = 375 nm (λem = emission wavelength) in water, under λex = 300 nm (λex = excitation wavelength). To investigate the feasibility of luminescence sensing, the solid powder of 4 was immersed in different solvents, keeping still for 1–2 min to reach equilibrium, to carry out the solvent-dependent emission spectra. These solvent molecules have appropriate sizes for entering the pores of 4. Figure 6b gives the luminescence responses of 4 for the various solvents, showing the solvent-dependent emission intensity. All emission spectra in these solvents were measured under the same experimental conditions. Among all the tested solvents,


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acetone exhibited the drastic luminescence quenching effect to 4, leading to the disappearance of the emission. Nevertheless, except for the enhancing effect of DMF, the other tested solvents only resulted in quite moderate reduction of the luminescence of 4. The phenomena suggest that 4 exhibits highly selective fluorescence quenching effect for acetone and therefore can be used as a convenient sensor simply coupled with a handy UV lamp to detect acetone. Such phenomenon could be attributed to the energy transfer from the organic ligands of 4 to acetone molecules.45 Moreover, the quenching effect of acetone in aqueous solution was also evaluated. The solutions with different concentrations of acetone were chosen to be the solvent for emission test, with other measurement conditions remained the same (Figure 6c). It can see clearly that the intensity of luminescence decreased significantly with the addition of acetone, the luminescence intensity was decreased to ca. 50% at an acetone content of 0.5 vol%. when the volume ratio of acetone was increased to 4 vol%, the luminescence was almost quenched. Consequently, the highly quenching sensitivity indicates that 4 could be applied as potential luminescence probe to facilely identify the existence of a small amount of acetone in aqueous solution. Moreover, to evaluate the quenching effect, quenching constant (Ksv) was estimated by the Stern– Volmer equation,46-47 as follows: 𝐼0

( )= 𝐾 𝐼

𝑠𝑣

[𝑀] + 1

(1)

where the luminescence intensity before (I0) and after (I) the addition of acetone was obtained by experiment, [M] is molar concentration of acetone. A linear relation can be found at low concentrations (0–0.15 mol L–1), and Ksv value can be calculated to be 12.89 L mol–1 (Figure 6d), further attesting the luminescence sensing ability of 4 for acetone in aqueous solution.

CONCLUSIONS 9 ACS Paragon Plus Environment


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In summary, four MOFs based on a bent ligand H2bct were discovered by the solvothermal technology. Among them, 1 and 2 feature the same 1D chain structure, with the planar pentanuclear [M5(μ3-OH)2(μ2H2O)2(H2O)8]8+ (M = Co for 1, Ni for 2) clusters as SBUs, while 3 and 4 exhibit the similar layered structures. In spite of the same planar pentanuclear cluster configuration, the different metal centers of 1 and 2 lead to the quite different magnetic interactions. Moreover, the highly selective and sensitive sensing function in 4 indicates its promising application for the sensing of small molecules. ASSOCIATED CONTENT Supporting Information. CIF data together with additional figures and tables. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We are grateful for the financial support of the One Thousand Young Talents Program under the Recruitment Program of Global Experts, the NSFC (21771179 and 21233009), the Strategic Priority Research Program of CAS (XDB20010200), and the 973 Program (2014CB845603).

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HOOC

COOH N

HN

N

Scheme 1. Structure of H2bct ligand

Figure 1. (a) Co(II) coordination environment of 1. Symmetry codes: (A) 1+x, –1+y, z; (B) 3–x, –1–y, – z; Hydrogen atoms are omitted for clarity. (b) Pentanuclear Co(II) cluster. (c) View of the 1D chain structure. (e) View of the 3D hydrogen-bonded coordination network of 1 viewed down the a-axis.



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Figure 2. (a) Cd(II) coordination environment of 3. Symmetry codes: (A) –1+x, y, z; (B) 1–x, 1–y, 1–z; (C) –x, 2–y, 1–z. Hydrogen atoms are omitted for clarity. (b) Tetranuclear Cd(II) cluster. (c) View of the 2D layer along c-axis. (d) View of the 3D stacked supramolecular structure along a-axis.


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Figure 3. (a) Cd(II) coordination environment of 4. Symmetry codes: (A) –1+x, y, 1+z; (B) –x, 1–y, 1–z; (C) –1+x, 1+y, z. Hydrogen atoms are omitted for clarity. (b) Edge-shared dinuclear Cd(II) cluster. (c) View of the 2D layer along [1 1 1] orientation. (d) View of the stacked network along [1 0 –1] orientation. The DMF and water molecules located in the void space are omitted for clarity.



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Figure 4. Temperature dependence χM and χMT curves of 1 (a) and 2 (b) at an applied field of 1000 Oe. The insets show the plot of χM–1 versus T.


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Figure 5. Photoluminescence spectra of 3 (a) and 4 (b). Solid lines: emission; dash lines: excitation. λex = 369 nm for 3 and λex = 368 nm for 4; λem =

425 nm for 3 and λem =

450 nm for 4.

Figure 6. (a) Excitation and emission spectra of 4 in water. (b) Solvent-dependent emission intensity of 4 (λex =

300 nm). (c) Emission spectra of 4 suspension with different concentration of acetone in water

(λex =

300 nm). (d) Stern–Volmer plots for acetone.



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Table 1. Crystallographic data and structural refinements for MOFs 1–4 Identification code Empirical formula

1 Co5C64H66N12O3

2

3

4

Ni5C64H66N12O32

Cd2C42H32N8O13

CdC34H30N10O6

2

Formula weight

1809.93

1808.83

1081.55

787.08

Crystal system

monoclinic

monoclinic

monoclinic

triclinic

P21/n

P21/n

P21/c

P1

a/Å

8.204(3)

8.235(4)

18.141(3)

8.736(3)

b/Å

16.917(6)

16.879(10)

14.685(2)

11.972(3)

c/Å

24.960(10)

24.942(13)

16.062(3)

17.130(5)

α/°

90

90

90

72.856(8)

β/°

95.062(8)

95.394(14)

101.248(2)

81.463(9)

γ/°

90

90

90

80.998(9)

3451(2)

3452(3)

4196.7(11)

1680.9(9)

2

2

4

2

ρcalc/g cm–3

1.74

1.74

1.71

1.56

M/mm–1

1.3

1.4

1.1

0.7

F(000)

1850

1860

2160

800

Reflections collected

29444

29635

35674

23657

Unique reflections

7882

7854

9577

7731

Goodness-of-fit

1.200

1.084

1.098

1.092

0.0752

0.1432

0.0384

0.0467

0.1270

0.2315

0.0771

0.0788

0.5

0.6

0.5

0.7

Space group

Volume/Å3 Z

R1a

Final

indexes

[I>=2σ (I)] wR2b

Final

indexes

[I>=2σ (I)] Largest diff. peak aR1

–

= Σ||Fo| – |Fc||/Σ|Fo|.

bwR2

= |Σw(|Fo|2 – |Fc|2)|/Σ|w(Fo)2|1/2, where w = 1/[2(Fo2) + (aP)2+bP]. P = (Fo2 + 2Fc2)/3.


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For Table of Contents Use Only Metal–Organic Frameworks Based on a Bent Triazole Dicarboxylic Acid: Magnetic Behaviors and Selective Luminescence Sensing Properties Yu-Xiao Zhang,†,‡ Hua Lin,† Yuehong Wen,† and Qi-Long Zhu*,† †State

Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,

Chinese Academy of Sciences, Fuzhou, 350002, China ‡University

of Chinese Academy of Sciences, Beijing, 100049, China

Synopsis A series of metal–organic frameworks (MOFs) constructed with a bent ligand, 3,5-bis(4'carboxyphenyl)-1,2,4-triazole (H2bct), have been synthesized and characterized, which exhibit intriguing magnetic behaviors and selective luminescence sensing properties.


MetalâOrganic Frameworks Based on a Bent Triazole Dicarboxylic

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