Tunability in Metal Coordination Sphere, Ligand Coordination Mode

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Tunability in Metal Coordination Sphere, Ligand Coordination Mode, Network Topology and Magnetism via Stepwise Dehydration Induced Single-crystal to Single-crystal Transformation Juan-Juan Hou, Xiao-Qing Li, Ping Gao, Han-Qi Sun, and Xian-Ming Zhang Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 12 Jun 2017 Downloaded from http://pubs.acs.org on June 13, 2017

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Crystal Growth & Design

Tunability in Metal Coordination Sphere, Ligand Coordination Mode, Network Topology and Magnetism via Stepwise Dehydration Induced Single-crystal to Single-crystal Transformation Juan-Juan Hou, Xiao-Qing Li,‡ Ping Gao,‡ Han-Qi Sun, and Xian-Ming Zhang*

School of Chemistry & Material Science, Shanxi Normal University, Linfen 041004, P. R. China

Supporting Information

ABSTRACT: Stimuli-responsive solid-state crystal dynamics or flexibility in metal-organic frameworks (MOFs) showing multiple structure changes is arising interest for understanding the structure-property relationship and designing functional materials. In this article, dehydration-induced stepwise single-crystal to single-crystal (SC−SC)

transformations

coordination

are

observed

in

polymer [Co(H2L)(H2O)2]⋅H2O

two-dimensional (1),

where

63-topological

H4L is

3,5-bis(3′,

5′-dicarboxylphenyl)-1H-1,2,4-triazole. Upon thermal dehydration at 130 °C for 2h, half lattice water in 1 can be released to form [Co(H2L)(H2O)2]⋅0.5H2O (2). Increase of dehydration temperature to 150 °C for three hours, the third phase [Co(H2L)(H2O)2] (3) that is free of lattice water molecule is gained. Further

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increasing the dehydration temperature to 160 °C for 6 h, one of coordination water molecule can be released, giving rise to dicobalt-based 2D (3,6)-connected kgd double layer [Co(H2L)(H2O)] (4). During stepwise dehydration SC-SC transformation courses, coordination sphere of Co(II) changes from penta-coordinate trigonal bipyramid to hexa-coordinate octahedra; H2L2− ligates from (κ1)–(κ1)–(κ1)–µ3–H2L2–, (κ1)–(κ1)–(κ2)–µ3–H2L2– to (κ1–µ2)–(κ1)–(κ2)–µ4–H2L2–; network topology ranges from 3-connected 63-hcb to (3,6)-connected kgd; magnetism changes from single-ion behavior of Co(II) to intra-dicobalt ferromagnetism.

INTRODUCTION

Metal−organic frameworks (MOFs) or coordination polymers (CPs) have received considerable attention in the past few decades owing to their potential applications in the fields of gas separation,1-6 catalysis,7 sensing,8,

9

chirality,10 magnetism,11 and

optics etc.12, 13, 14 Since the first reported of single-crystal to single-crystal (SC–SC) transformation for MOFs/CPs in 2002,15-21 an arising interest in these crystalline materials is the stimuli-responsive single-crystal to single-crystal (SC–SC) transformation between solid phases which maintains the integrity before and after the transformation. This provides opportunities to understand solid-state transformations and to prepare new functional materials under exogenous stimuli such as thermal,22-27 light,28 humidity,29 redox,30 solvent molecules,31-40 mechanical forces,41, 42 and anions or cations.43-45 These dynamic SC–SC transformations involving solid-state reactivity and structural transformation are rarely observed because the molecules are rigidly


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and steadily fixed within the crystal lattices.20,

46-48

That is to say, SC–SC

transformations mostly occur through the minor movement of atoms as large changes of atoms or groups within lattice often destroy single crystals and yield polycrystalline powder. So far, SC–SC transformation induced by guest removal/inclusion without bond cleavage has been studied extensively.49,

50

In contrast, examples involving

cleavage and formation of covalent or coordinative bonds, which results in a change of coordination number,51 geometry, dimensionality, chirality, and interpenetration etc. are less common.52-54 Experimentally, powder X-ray diffraction (PXRD), single-crystal X-ray diffraction (SCXRD) and atomic force microscopy (AFM), as well as spectroscopic analytical tools such as nuclear magnetic resonance (NMR), thermogravimerty (TG), have been applied to monitor solid-state structural transformations.55, 56 Among them, SCXRD is the most reliable method of determining the precise structures before and after the structural transformation. Compared to SCXRD, PXRD provide much less structural information due to the serious overlapping of diffraction peaks, which hamper observation of subtle structural changes such as atomic positions, atomic coordinates, bond lengths, bond angles and guest molecules that play important roles on the measurable physical properties. Herein, we report a systematic study on a CoII coordination

polymer,

namely

[Co(H2L)(H2O)2]⋅H2O

(1)

(H4L

=

3,5-bis(3′,5′-dicarboxylphenyl)-1H-1,2,4-triazole), that exhibits stepwise SC−SC transformations upon removal of lattice and coordination water molecules to form three different stable phases.



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EXPERIMENTAL SECTION

Materials and General Methods. All starting materials were purchased of commercially reagent grade and used without further purification. Elemental analyses were performed on a Perkin-Elmer 240 elemental analyzer. The Fourier transform infrared spectroscopy (FT-IR) spectra were recorded from KBr pellets in the range 400-4000 cm−1 on a Nicolet 5DX spectrometer. Variable-temperature powder X-ray diffraction (VTPXRD) data were collected in a Rigagu Ultima IV-185 diffractometer. The purity of compound 1 was confirmed by comparison of experimental PXRD patterns with the simulated pattern derived from the X-ray single-crystal data compound. The thermogravimetric analysis (TGA) was carried under air atmosphere using SETARAM LABSYS equipment at a heating rate of 10 °C/min. The magnetic measurements were made with Quantum Design SQUID MPMS XL-5 instruments. Syntheses. [Co(H2L)(H2O)2]⋅⋅H2O (1). A mixture of CoCl2⋅6H2O (25 mg, 0.1 mmol), H4L (13 mg, 0.033 mmol) and H2O (5 mL) was placed in a 15 mL Teflon-lined stainless reactor and stirred in air for 30 min (H4L = 3,5-bis(3′, 5′-dicarboxylphenyl)-1H-1,2,4-triazole). The mixture was sealed and heated to 160 °C for 168 h, and then it was cooled to room temperature at a rate of 10 °C min−1. After cooling to room temperature, light purple crystals of 1 as a single phase were recovered in 30% yield based on H4L. Anal. Calc. For C18H15CoN3O11: C, 42.54; H, 2.97; N, 8.27. Found: C, 41.61; H, 2.86; N, 8.17. IR (KBr, cm-1): 3550-3309sb, 245s, 3097m, 2931m, 1658s, 1549s, 1386s, 1292w.


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Details follow for compound [Co(H2L)(H2O)2]⋅0.5H2O (2), [Co(H2L)(H2O)2] (3), and [Co(H2L)(H2O)] (4), respectively. Compounds 2, 3 and 4 were prepared by heating 1 at 130 °C for 2 h, at 150 °C for 3 h and at 160 °C for 6 h, respectively. Anal. Calc. for deep purple crystals 4 C18H11CoN3O9: C, 45.78; H, 2.35; N, 8.90. Found: C, 46.08; H, 2.91; N, 9.13. X-Ray Data collection and structure determination. Crystallographic data of 1-4 were collected on a Bruker SMART APEX CCD area detector diffractometer using Mo Kα radiation (λ = 0.71073 Å) by ω and φ scan mode. The program SAINT was used for integration of the diffraction profiles. All the structures were solved by direct methods using the SHELXS program of the SHELXTL package and refined by full-matrix least-squares methods with SHELXL.57 All non-hydrogen atoms were refined with anisotropic thermal parameters. All hydrogen atoms of organic ligands were generated theoretically onto the specific carbon atoms and refined isotropically with fixed thermal factors. Drawings of the molecules were performed with the program Diamond.58 Further details for structural analysis are summarized in Table 1. Selected bond lengths and bond angles of 1-4 are shown in Table S1 and Table S2. RESULTS AND DISCUSSION Crystal Structure of [Co(H2L)(H2O)2]⋅⋅H2O (1). Compound 1 was synthesized by hydrothermal treatment of CoCl2⋅6H2O and H4L in H2O. X-ray single-crystal structural determination reveals that compound 1 crystallizes in the monoclinic space group C2/c. The asymmetric unit consists of one crystallographically independent cobalt (II) ion, two coordinated water molecules, one H2L2− anion and one lattice



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water molecule (Fig. 1a). The central Co(1) ion adopts five coordinated geometry, which is surrounded by three carboxylate oxygen atoms from three individual H2L2− groups and two coordinated water molecules to give a geometry intermediate between square pyramid (sp) and trigonal bipyramid (tbp) (Fig. 1a). For the five coordinated structure, there is a geometric parameter τ defined as τ = (β −α) / 60 to describe an index of the degree of trigonality (Fig. S1), within the structural continuum between tbp and sp.59 For a perfectly trigonal-bipyramidal geometry τ is equal to 1 (α = 120°, and β = 180°), while for a perfectly tetragonal geometry τ is equal to zero. From the bond lengths and angles table, the τ value equals to 0.35 in compound 1. It should be noted that one of the carboxyl oxygen atom (O5b) is bridged to the Co(1) center with a weak contact (Co···O, 2.428 Å, in Fig. 3a). The Co(1)–O distances are in the range of 2.022(2)–2.121(3) Å (Table S1). The cis–O–Co(1)–O bond angles are in the range of 86.76(12)–151.79(9)°, and the trans–O–Co(1)–O bond angle is 173.00(11)°. The coordination mode of ligand H2L2− in 1 is shown in Scheme 1 (mode I), in which three of the carboxyl groups adopt (κ1)–(κ1)–(κ1)–µ3–H2L2– coordination mode. The remaining carboxyl group (O7–C18–O8) is protonated. In this way, each penta-coordinated Co(II) is surrounded by three H2L2− anions, and each H2L2− anion links three Co(II) ions, giving a 2D 3-connected 63 layer (Fig. 1b and Fig. 4a). Adjacent layers are linked by van der Waals and weak intermolacular hydrogen bonds with the nearest Co···Co and Co1···O1 distances 5.491 Å and 4.992 Å in adjacent two layers respectively (Fig. 1c).


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Thermogravimetry and Variable Temperature Powder X-ray Diffraction of 1. Thermogravimetric analysis under air flow shows there are three mass loss steps in the temperature range from 30 to 850 °C (Fig. S2). The first mass loss is about 2.4% between 90 °C and 140 °C, which corresponds to removal of one lattice water molecule per formula unit (expected 3.5%). The second loss of 8.0% in the range of 170 °C to 380 °C corresponds to further removal of the two coordination water molecules per formula unit (expected 7.1%). The third loss between 380 °C to 810 °C corresponds to the removal of the organic components of the ligand. Variable temperature PXRD patterns were collected for checking the phase purity and further exploring the thermal stability on the bulky samples. As shown in Fig. 5, the experimental PXRD patterns of compound 1 at 30 °C is in good agreement with the simulated data, indicating the good phase purity. With increasing the temperature up to 375 °C, the variable temperature PXRD patterns are almost the same, indicating the short time during measurement didn’t trigger dyhydration and phase transition completely. In addition, the overlap of diffraction peaks and resolution of diffractometer are the other important factor, which lead to unsuccessful monitoring the subtle structural changes. Single-Crystal to Single-Crystal Transitions of 1. An interesting feature in 1 is that network may offer suitable conditions for a solid-state reaction to take place, due to the geometric proximity between the Co(II) centers and existence of O−H···O hydrogen bonds between water molecule and monodentate carboxylate oxygen atom (e.g., Co1···O1c, 4.992 Å, seen Fig. 1c) from adjacent layers.16 It is expected that the



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uncoordinated carboxylate oxygen atoms may take up the vacant sites in neighboring layer to form covalent bond when the coordinated water molecules are removed. Following the thermogravimetric analysis and previously reported of SC−SC transitions by removal of solvent molecules from host frameworks,49, 51, 60 the loss of lattice water and coordination water molecules can be achieved by heating 1 at different temperatures for different hours. Upon heating to 130 °C for 2h, compound 1

experiences

a

SC−SC

structural

transformation

to

form

neutral

[Co(H2L)(H2O)2]⋅0.5H2O (2) without apparent color change (Fig. 6). Single crystal X-ray diffraction analysis reveals that 2 maintains original monoclinic space group C2/c (Table 1). The cell volume is decreased by 1.1% in the measured temperature, from 3765.5 to 3746.5 Å3. Different from 1, the asymmetric unit of 2 only contains a lattice water molecule with the occupancy of 0.5 (Fig. S3). The important structure change before and after SC−SC transition is the coordination mode of central Co(1) ion and H2L2−. The central Co(1) ion in 2 changes to six coordinated distorted octahedral geometry which is surrounded by four carboxylate oxygen atoms from three individual (κ1)–(κ1)–(κ2)–µ3–H2L2– groups (Scheme 1, mode II) and two coordinated water molecules (Fig. S3). The coordination mode of the ligand H2L2− is shown in Scheme 1 (mode II), in which one of the carboxylate groups (O5−C17−O6) is chelated to Co(1). The detailed changes of Co(1)–O distances and O–Co(1)–O angles are shown in Fig. 3b. Overall, 2D 63 layer is again observed with the nearest Co···Co and Co1···O1 distances decreased to 5.465 Å and 4.988 Å in adjacent two layers respectively (Fig. S4).


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The lattice water molecule in 1 can be removed completely in a SC−SC manner by heating at 150 °C for 3 hours, resulting in [Co(H2L)(H2O)2] (3) without apparent color change (Fig. 6). Compound 3 also crystallizes in the monoclinic space group C2/c (Table 1), and the asymmetric unit is shown in Fig. S5. The cell volume is decreased by 1.6% in the measured temperature, from 3765.5 to 3706.5 Å3. Compared to 2, the important structure change in compound 3 is loss of the lattice water completely. The coordination mode of central Co(1) ion and H2L2− is remained, but the Co(1)–O distances and O–Co(1)–O angles are slightly changed (Fig. 3c). Corresponding the nearest Co···Co and Co1···O1 distances in adjacent two layers further decreased to 5.387 Å and 4.964 Å, respectively (Fig. S6).

When the temperature was increased to 160 °C and held for 6 h, compound 1 experiences loss a lattice water and a coordination water molecule, forming the ligand-replaced compound [Co(H2L)(H2O)] (4) with a significant color change of crystal from lavender to violet (Fig. 6). Compound 4 still maintains original monoclinic space group I2/a (Table 1) with the cell volume is decreased by 4.7% in the measured temperature, from 3765.5 to 3588.2 Å3. Unlike compound 3, the asymmetric unit of 4 only consists of one coordinated water molecule, one cobalt (II) center, and one H2L2− anion (Fig. 2a). The coordination mode of central Co(1) ion in 4 is similar to that in 3 except that one coordination site of cobalt occupied by one coordination water molecule is now replaced by one carboxylate oxygen atom from adjacent layer. In this way, two adjacent Co(II) were bridged by carboxyls to generate



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an edge-sharing dimer. For ligand H2L2−, the coordination mode is changed into (κ1–

µ2)–(κ1)–(κ2)–µ4 (shown in Scheme 1, mode III). Each dinuclear unit is surrounded by six (κ1–µ2)–(κ1)–(κ2)–µ4–H2L2− anions, and each H2L2− anion links three dinuclear Co2 units, giving a 2D (3, 6)-connected kgd-topological double layer (Fig. 4b). Adjacent double layers are further extended into a 3D superamolecule framework by van der Waals and weak hydrogen bond interactions (Fig. 2b). Further increasing dehydration temperature and/or enlongating reaction time, no new phase was gained. Attempts to resolvate 4 to obtain the pure product 1 have not been successful yet, indicating that desolvation transformation is irreversible.

Magnetism Variable-temperature magnetic susceptibility measurements were performed on crystalline samples of 1 and 4 in the temperature range of 300-2 K with a field of 1000 Oe. The χmT versus T and χm versus T curves of 1 and 4 are shown in Fig. 7. As shown in Figure 7a, the χmT of 1 per Co is 3.85 cm3 K mol−1, which is substantially higher than the spin-only value for a high-spin Co(II) center (S = 3/2, 1.875 cm3 K mol−1), ascribing to the contribution of Co(II) ions. Similar to the magnetic behavior of other reported Co(II),51, 61 the χmT value decreases slowly to a minimum value of 2.66 cm3 K mol−1 at about 16 K, which is a typical manner of spin-orbital coupling and is mainly attributed to the single-ion behavior of Co(II).62 Below 16 K, the χmT value increases abruptly to 3.42 cm3 K mol−1 at 2 K, which may be due to the reminiscent of the onset of magnetic order.62 The temperature dependence of the


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reciprocal susceptibilities (1/χm) above 20 K obeys the Curie–Weiss law with [χm = C/(T–θ)], with Curie constant C = 3.98 cm3 K mol−1 and Weiss constant θ = −15.85 K. The M vs H curve at 2 K displays the magnetization increase rapidly to 2.78 Nβ at 15 kOe and further reached gently 3.09 Nβ per Co at 50 kOe (Fig. S7), close to the expected value of 3.0 Nβ for one Co(II) ions. The magnetic behaviors of 4 are distinctly different from those of 1 owing to the presence of the edge-sharing dimer. As shown in Figure 7b, the χmT value of 4 at room-temperature per Co is 3.91 cm3 K mol

−1

, which is already higher than the

expected value of 2.0 cm3 K mol −1 for one spin-only Co(II) ion with S = 3/2 and g = 2.00. Upon cooling of sample, the χmT values increase continuously to a maximum 6.91 cm3 K mol −1 at 3 K and then decreases to 6.83cm3 K mol −1 at 2 K. The increase in χmT value with lowering temperature represents a characteristic feature of intra-dimer ferromagnetic interaction.63 In 4, there exists edge-sharing dimer Co2 linked by two µ2-η2-carboxylate groups, in which the Co–O–Co angle equals 102.35°. It has been generally observed that µ2-η2-carboxylate groups often provide more opportunities for generating ferromagnetism,64, 65 and there is a critical angle (~110°) for the magnetic interaction of M–O–M anti- or ferromagnetic coupling. Therefore, a small Co–O–Co angle is thought to be one of the probable factors in showing a ferromagnetic interaction between Co(II) ions. The decrease of χmT value at very low temperature region may be attributed to either zero-field splitting factor or inter-dimer antiferromagnetic interactions. The magnetic data in the range of 20–300 K followed



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the Curie–Weiss law with Curie constant of C = 3.89 cm3 K mol−1 and Weiss constant of θ = 7.12 K. The positive θ value indicates the presence of ferromagnetic interaction between Co ions. For 4, the saturated magnetization of 3.55 Nβ per Co at the highest field of 50 kOe, is close to the expected value of 3.0 Nβ for one ferromagnetic Co(II) ions ( Fig. S8).

CONCLUSIONS

In this work, we have successfully synthesized a coordination polymer with 2D 63 layer, which undergoes a stepwise SC−SC transformations upon heating to give three phases. During the course, not only stepwise the lattice water and/or coordination water molecules could be removed, but also the carboxylates from adjacent layer take up the vacant site result in structural transformation from monolayer into double layer. Besides, local coordination geometries of Co(II) ions and coordination modes of ligand are also changed, which further induced magnetic change from single-ion behavior of Co(II) into intra-dimer ferromagnetism. These findings should be instructive for understanding solid state structural transformation.

ASSOCIATED CONTENT

Supporting Information.

Structural data at room temperature in CIF format (CCDC 1532386, 1532387, 1532388, and 1532389) contain the supplementary crystallographic data for this


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paper., selected bond distances, additional structural figures, M−H curve and TG curve.

AUTHOR INFORMATION Corresponding Author * Fax: +86 357 2051402. E-mail: [email protected]

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ‡X.-Q. Li and P. Gao contributed equally to this work. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by 973 Program (2012CB821701), and the Ministry of Education of China (Grant IRT1156) and the National Science Fund for Young Scholars (NSFC 21201114), Sanjin Scholarship and the Plan for 10 000 Talents in China.

FIGURES



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Figure 1. Views of the coordination environments of CoII atoms in 1 (a), single layer (b), and 3D framework with Co···Co and Co−O1 distances in adjacent layers, 5.491Å and 4.992Å, respectively. Hydrogen atoms have been omitted for clarity.


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Figure 2. Views of the coordination environments of CoII atoms in 4 (a), and packing view double layer of 4 with the Co···Co distances in adjacent layers (3.393Å). The Co−O1 bond length is 2.340Å (Hydrogen atoms have been omitted for clarity).



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Figure 3. Details for the CoII−O bond lengths in 1 (a), 2 (b), 3 (c) and 4 (d).

Figure 4. Schematic representations of the 2D 63 net in 1 (both the H2L2− ligand and CoII center act as 3-connected nodes), and 2D (3,6)-connected kgd net in 4 (the H2L2− ligand act as 3-connected nodes, dinuclear Co2 act as 6-connected nodes), respectively.


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Figure 5. The temperature-dependent powder X-ray diffraction patterns in the process of crystal transformation of 1.

Figure 6. Color change details in stepwise dehydration from 1 to 4.



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Figure 7. The χmT versus T and χm versus T curves measured under an applied field of 1000 Oe for 1 (a) and 4 (b). The solid lines represent the best-fit results with the parameters described in the text.

SCHEME


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Scheme 1. Schematic views of the coordination modes seen in compounds 1-4 (mode I in 1, mode II in 2 and 3, and mode III in 4).

Table 1. Summary of crystal data and structure refinement parameters for 1-4.

Compound

1

2

3

4

Empirical formula

C18H15CoN3O11

C18H14CoN3O10.50

C18H13CoN3O10

C18H11CoN3O9

Fw

508.26

499.25

490.24

472.23

Crystal System

Monoclinic

Monoclinic

Monoclinic

Monoclinic



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Space group

C2/c

C2/c

C2/c

I2/a

a (Å)

13.5320(15)

13.4867(5)

13.4440(17)

12.9355(17)

b (Å)

17.0563(18)

17.0277(7)

16.9265(17)

16.943(2)

c (Å)

16.7398(18)

16.7224(7)

16.6769(18)

16.6689(16)

α (°)

90

90

90

90

β (°)

102.942(2)

102.6880(10)

102.397(3)

100.829(8)

γ (°)

90

90

90

90

V (Å3)

3765.5(7)

3746.5(3)

3706.5(7)

3588.2(7).

Z

8

8

8

8

Density (Mg/m3)

1.793

1.770

1.757

1.748

µ (mm-1)

0.986

0.988

0.995

1.020

F(000)

2072

2032

1992

1912

Crystal Size(mm)

0.380x0.190x

0.220 x 0.120 x 0.17 x 0.16 x 0.20 x 0.18 x 0.05

0.100

0.100

0.08

θ(°)

1.952 to 26.997

1.956 to 26.997

1.96 to 27.00

1.73 to 28.570

Reflections

9565 / 4070

10583 / 4082

10811 / 4046

9821 / 4202


Page 21 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Tmax/Tmin

0.9078 / 0.7056

0.9077 / 0.8120

0.9247 / 0.8491

0.951 / 0.822

Data/restraints/par

4070 / 0 / 338

4082 / 0 / 326

4046 / 0 / 301

4202 / 0 / 280

S

1.047

1.139

1.038

1.010

R1a,wR2b[I>2σ(I)]

0.0490,

0.0391, 0.1086

0.0471, 0.1260

0.0730, 0.1791

R1a,wR2b (all data)

0.0660, 0.1321

0.0425, 0.1112

0.0638, 0.1363

0.1446, 0.2165

∆ρmax/∆ρmin(eA-3)

0.608 / -0.390

0.468 / -0.300

0.540 / -0.445

0.8451/-0.492

ameters

0.1206

a

R1 = ∑||Fo|-|Fc||/∑|Fo|, bwR2 = [∑w(Fo2-Fc2)2/∑w(Fo2)2]v1/2

REFERENCES (1) Qiu, S.; Xue, M.; Zhu, G., Metal-organic framework membranes: from synthesis to separation application. Chem. Soc. Rev. 2014, 43, (16), 6116-6140.

(2) He, Y.; Zhou, W.; Qian, G.; Chen, B., Methane storage in metal-organic frameworks. Chem. Soc. Rev. 2014, 43, (16), 5657-5678.

(3) Barea, E.; Montoro, C.; Navarro, J. A. R., Toxic gas removal - metal-organic frameworks for the capture and degradation of toxic gases and vapours. Chem. Soc. Rev. 2014, 43, (16), 5419-5430.

(4) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R., Carbon Dioxide Capture in Metal–Organic Frameworks. Chem. Rev. 2012, 112, (2), 724-781.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(5) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W., Hydrogen Storage in Metal– Organic Frameworks. Chem. Rev. 2012, 112, (2), 782-835.

(6) Li, J.-R.; Sculley, J.; Zhou, H.-C., Metal–Organic Frameworks for Separations. Chem. Rev. 2012, 112, (2), 869-932.

(7) Liu, J.; Chen, L.; Cui, H.; Zhang, J.; Zhang, L.; Su, C.-Y., Applications of metal-organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev. 2014, 43, (16), 6011-6061.

(8) Hu, Z.; Deibert, B. J.; Li, J., Luminescent metal-organic frameworks for chemical sensing and explosive detection. Chem. Soc. Rev. 2014, 43, (16), 5815-5840.

(9) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T., Metal–Organic Framework Materials as Chemical Sensors. Chem. Rev. 2012, 112, (2), 1105-1125.

(10) Yoon, M.; Srirambalaji, R.; Kim, K., Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis. Chem. Rev. 2012, 112, (2), 1196-1231.

(11) Kurmoo, M., Magnetic metal-organic frameworks. Chem. Soc. Rev. 2009, 38, (5), 1353-1379.

(12) Ramaswamy, P.; Wong, N. E.; Shimizu, G. K. H., MOFs as proton conductors - challenges and opportunities. Chem. Soc. Rev. 2014, 43, (16), 5913-5932.


Page 22 of 33

Page 23 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(13) Wang, C.; Zhang, T.; Lin, W., Rational Synthesis of Noncentrosymmetric Metal–Organic Frameworks for Second-Order Nonlinear Optics. Chem. Rev. 2012, 112, (2), 1084-1104.

(14) Hou, J.-J.; Zhang, R.; Qin, Y.-L.; Zhang, X.-M., From (3,6)-Connected kgd, chiral anh to (3,8)-connected tfz-d Nets in Low Nuclear Metal Cluster-Based Networks with Triangular Pyridinedicarboxylate Ligand. Cryst. Growth & Des. 2013, 13, (4), 1618-1625.

(15) Ferey, G.; Serre, C., Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences. Chem. Soc. Rev. 2009, 38, (5), 1380-1399.

(16) Kole, G. K.; Vittal, J. J., Solid-state reactivity and structural transformations involving coordination polymers. Chem. Soc. Rev. 2013, 42, (4), 1755-1775.

(17) Biradha, K.; Hongo, Y.; Fujita, M., Crystal-to-Crystal Sliding of 2D Coordination Layers Triggered by Guest Exchange. Angew.

Chem.

Int.

Ed.

2002, 41, (18), 3395-3398.

(18) Suh, M. P.; Ko, J. W.; Choi, H. J., A Metal−Organic Bilayer Open Framework with a Dynamic Component: Single-Crystal-to-Single-Crystal Transformations. J. Am. Chem. Soc. 2002, 124, (37), 10976-10977.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 33

(19) Zhang, J. P.; Liao, P. Q.; Zhou, H. L.; Lin, R. B.; Chen, X. M., Single-crystal X-ray diffraction studies on structural transformations of porous coordination polymers. Chem. Soc. Rev. 2014, 43, (16), 5789-5814.

(20) Kaneko, W.; Ohba, M.; Kitagawa, S., A Flexible Coordination Polymer Crystal Providing Reversible Structural and Magnetic Conversions. J. Am. Chem. Soc. 2007, 129, (44), 13706-13712.

(21) Chen, C.-L.; Goforth, A. M.; Smith, M. D.; Su, C.-Y.; zur Loye, H.-C., [Co2(ppca)2(H2O)(V4O12)0.5]: A Framework Material Exhibiting Reversible Shrinkage and Expansion through a Single-Crystal-to-Single-Crystal Transformation Involving a Change in the Cobalt Coordination Environment. Angew.

Chem.

Int.

Ed. 2005,

44, (41), 6673-6677.

(22) Ghosh, S. K.; Zhang, J.-P.; Kitagawa, S., Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer. Angew.

Chem.

Int.

Ed. 2007, 46, (42), 7965-7968.

(23) Ma, J.-P.; Liu, S.-C.; Zhao, C.-W.; Zhang, X.-M.; Sun, C.-Z.; Dong, Y.-B., Reversible

visual

thermochromic

single-crystal-to-single-crystal

transformation.

coordination CrystEngComm

304-307.


polymers 2014, 16,

via (3),

Page 25 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(24) Lusi, M.; Barbour, L. J., Temperature-dependent guest reorientation: a reversible order–disorder transformation in a single crystal. CrystEngComm 2014, 16, (1), 36-38.

(25) Medishetty, R.; Yap, T. T.; Koh, L. L.; Vittal, J. J., Thermally reversible single-crystal to single-crystal transformation of mononuclear to dinuclear Zn(II) complexes by [2+2] cycloaddition reaction. Chem. Commun. 2013, 49, (83), 9567-9569.

(26) Chisca, D.; Croitor, L.; Coropceanu, E. B.; Petuhov, O.; Baca, S. G.; Kramer, K.; Liu, S.-X.; Decurtins, S.; Rivera-Jacquez, H. J.; Masunov, A. E.; Fonari, M. S., From pink to blue and back to pink again: changing the Co(II) ligation in a two-dimensional coordination network upon desolvation. CrystEngComm 2016, 18, (3), 384-389.

(27) Ghosh, S. K.; Kaneko, W.; Kiriya, D.; Ohba, M.; Kitagawa, S., A Bistable Porous Coordination Polymer with a Bond-Switching Mechanism Showing Reversible Structural and Functional Transformations. Angew.

Chem.

Int.

Ed.

2008, 47, (46), 8843-8847.

(28) Shu, Y. B.; Tu, N.; Shi, H. T.; Yin, Y. G.; Liu, W. S., Photodimerization behaviour of 1D-3D Zn(II) coordination polymers with tetrazolyl styrylpyridine. Dalton Trans. 2015, 44, (16), 7131-7134.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(29) Cai, Z. S.; Bao, S. S.; Wang, X. Z.; Hu, Z.; Zheng, L. M., Multiple-Step Humidity-Induced Single-Crystal to Single-Crystal Transformations of a Cobalt Phosphonate: Structural and Proton Conductivity Studies. Inorg. Chem. 2016, 55, (7), 3706-3712.

(30) Huang, C.; Wu, J.; Song, C.; Ding, R.; Qiao, Y.; Hou, H.; Chang, J.; Fan, Y., Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction. Chem. Commun. 2015, 51, (51), 10353-10356.

(31) Costa, J. S.; Rodriguez-Jimenez, S.; Craig, G. A.; Barth, B.; Beavers, C. M.; Teat, S. J.; Aromi, G., Three-way crystal-to-crystal reversible transformation and controlled spin switching by a nonporous molecular material. J. Am. Chem. Soc. 2014, 136, (10), 3869-3874.

(32) Du, M.; Li, C. P.; Chen, M.; Ge, Z. W.; Wang, X.; Wang, L.; Liu, C. S., Divergent kinetic and thermodynamic hydration of a porous Cu(II) coordination polymer with exclusive CO2 sorption selectivity. J. Am. Chem. Soc. 2014, 136, (31), 10906-10909.

(33) Niu, Z.; Ma, J. G.; Shi, W.; Cheng, P., Water molecule-driven reversible single-crystal to single-crystal transformation of a multi-metallic coordination


Page 26 of 33

Page 27 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


polymer with controllable metal ion movement. Chem. Commun. 2014, 50, (15), 1839-1841.

(34) Cametti, M.; Bargigia, I.; Marti-Rujas, J., Dynamic single crystal to polycrystal transformation of a 1D-coordination polymer and its second harmonic generation. Dalton Trans. 2016, 45, (4), 1674-1678.

(35) Wu, W. P.; Li, Z. S.; Liu, B.; Liu, P.; Xi, Z. P.; Wang, Y. Y., Double-step CO2 sorption and guest-induced single-crystal-to-single-crystal transformation in a flexible porous framework. Dalton Trans. 2015, 44, (22), 10141-10145.

(36) Sen, S.; Neogi, S.; Rissanen, K.; Bharadwaj, P. K., Solvent induced single-crystal

to

single-crystal

structural

transformation

and

concomitant

transmetalation in a 3D cationic Zn(II)-framework. Chem. Commun. 2015, 51, (15), 3173-3176.

(37) Iturrospe, A.; San Felices, L.; Reinoso, S.; Artetxe, B.; Lezama, L.; Gutiérrez-Zorrilla, J. M., Reversible Dehydration in Polyoxometalate-Based Hybrid Compounds: A Study of Single-Crystal to Single-Crystal Transformations in Keggin-Type

Germanotungstates

Decorated

with

Copper(II)

Complexes

of

Tetradentate N-Donor Ligands. Cryst. Growth & Des. 2014, 14, (5), 2318-2328.

(38) He, Y. C.; Yang, J.; Liu, Y. Y.; Ma, J. F., Series of solvent-induced single-crystal to single-crystal transformations with different sizes of solvent molecules. Inorg. Chem. 2014, 53, (14), 7527-7533.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 33

(39) Guo, Z.-J.; Yu, J.; Zhang, Y.-Z.; Zhang, J.; Chen, Y.; Wu, Y.; Xie, L.-H.; Li, J.-R., Water-Stable In(III)-Based Metal–Organic Frameworks with Rod-Shaped Secondary Building Units: Single-Crystal to Single-Crystal Transformation and Selective Sorption of C2H2 over CO2 and CH4. Inorg. Chem. 2017, 56, (4), 2188-2197.

(40) Zheng, C.; Xu, J.; Wang, F.; Tao, J.; Li, D., Spin crossover and reversible single-crystal to single-crystal transformation behaviour in two cyanide-bridged mixed-valence {FeIII2-FeII2} clusters. Dalton Trans. 2016, 45, (43), 17254-17263. (41) Tian, J.; Saraf, L. V.; Schwenzer, B.; Taylor, S. M.; Brechin, E. K.; Liu, J.; Dalgarno, S. J.; Thallapally, P. K., Selective metal cation capture by soft anionic metal-organic frameworks via drastic single-crystal-to-single-crystal transformations. J. Am. Chem. Soc. 2012, 134, (23), 9581-9584.

(42) Spencer, E. C.; Kiran, M. S.; Li, W.; Ramamurty, U.; Ross, N. L.; Cheetham, A. K., Pressure-induced bond rearrangement and reversible phase transformation in a metal-organic framework. Angew. Chem. Int. Ed. 2014, 53, (22), 5583-5586.

(43)

Liu,

M.-M.;

Bi,

Y.-L.;

Dang,

Q.-Q.;

Zhang,

X.-M.,

Reversible

single-crystal-to-single-crystal transformation from a mononuclear complex to a fourfold interpenetrated MOF with selective adsorption of CO2. Dalton Trans. 2015, 44, (46), 19796-19799.


Page 29 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(44) Wang, Y.; Wang, X. G.; Yuan, B.; Shao, C. Y.; Chen, Y. Y.; Zhou, B. B.; Li, M. S.; An, X. M.; Cheng, P.; Zhao, X. J., Cation-Exchange Porosity Tuning in a Dynamic 4d-4f-3d Framework for Ni(II) Ion-Selective Luminescent Probe. Inorg. Chem. 2015, 54, (9), 4456-4465.

(45) Kanoo, P.; Haldar, R.; Reddy, S. K.; Hazra, A.; Bonakala, S.; Matsuda, R.; Kitagawa,

S.;

Balasubramanian,

S.;

Maji,

T.

K.,

Crystal

Dynamics

in

Multi-stimuli-Responsive Entangled Metal–Organic Frameworks. Chem. Eur. J. 2016, 22, (44), 15864-15873.

(46) Aslani, A.; Morsali, A., Crystal-to-crystal transformation from a chain polymer to a two-dimensional network by thermal desolvation. Chem. Commun. 2008, (29), 3402-3404.

(47) Wu, J. Y.; Chang, C. Y.; Tsai, C. J.; Lee, J. J., Reversible Single-Crystal to Single-Crystal Transformations of a Zn(II)-Salicyaldimine Coordination Polymer Accompanying Changes in Coordination Sphere and Network Dimensionality upon Dehydration and Rehydration. Inorg. Chem. 2015, 54, (22), 10918-10924.

(48) Aggarwal, H.; Bhatt, P. M.; Bezuidenhout, C. X.; Barbour, L. J., Direct evidence for single-crystal to single-crystal switching of degree of interpenetration in a metal-organic framework. J. Am. Chem. Soc. 2014, 136, (10), 3776-3779.

(49) Chisca, D.; Croitor, L.; Coropceanu, E. B.; Petuhov, O.; Volodina, G. F.; Baca, S. G.; Krämer, K.; Hauser, J.; Decurtins, S.; Liu, S.-X.; Fonari, M. S., Six Flexible



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

and Rigid Co(II) Coordination Networks with Dicarboxylate and Nicotinamide-Like Ligands: Impact of Noncovalent Interactions in Retention of Dimethylformamide Solvent. Cryst. Growth & Des. 2016, 16, (12), 7011-7024.

(50) Croitor, L.; Chisca, D.; Coropceanu, E. B.; Volodina, G. F.; Petuhov, O.; Fonari, M. S., Solvent-rich layered cobalt(II) 1,4-benzenedicarboxylate based on binuclear {Co2(µ-OH2)(RCOO)2} secondary building unit. J. Mol. Struct. 2017, 1137, 136-141.

(51) Su, Z.; Chen, M.; Okamura, T.-a.; Chen, M.-S.; Chen, S.-S.; Sun, W.-Y., Reversible Single-Crystal-to-Single-Crystal Transformation and Highly Selective Adsorption Property of Three-Dimensional Cobalt(II) Frameworks. Inorg. Chem. 2011, 50, (3), 985-991.

(52) Wang, Z.; Begum, S.; Krautscheid, H., Solid-State Ring-Opening Structural Transformation in Triazolyl Ethanesulfonate Based Silver Complexes. Cryst. Growth & Des. 2016, 16, (10), 5836-5842.

(53) Yan, Z. H.; Li, X. Y.; Liu, L. W.; Yu, S. Q.; Wang, X. P.; Sun, D., Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag(I) Coordination Network. Inorg. Chem. 2016, 55, (3), 1096-1101.

(54) Chisca, D.; Croitor, L.; Petuhov, O.; Coropceanu, E. B.; Fonari, M. S., MOF-71 as a degradation product in single crystal to single crystal transformation of


Page 30 of 33

Page 31 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


new three-dimensional Co(II) 1,4-benzenedicarboxylate. CrystEngComm 2016, 18, (1), 38-41.

(55) Vittal, J. J., Supramolecular structural transformations involving coordination polymers in the solid state. Coord. Chem. Rev. 2007, 251, (13–14), 1781-1795.

(56) Cheng-Peng Li; Jing Chen; Liu, C.-S.; Du, a. M., Dynamic structural transformations of coordination supramolecular systems upon exogenous stimulation. Chem. Commun. 2015, 51, 2768-2781.

(57) G. M. Sheldrick, SHELXTL-97, Program for Crystal Structure Solution and Refinement, University of Gӧttingen, Germany, 1997.

(58) Brandenburg, K., Crystal Impact GbR, Bonn, Germany. Diamond 3 2005.

(59) Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.; Verschoor, G. C., Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur

donor

ligands;

the

crystal

aqua[1,7-bis(N-methylbenzimidazol-2[prime

or

and

molecular

structure

of

minute]-yl)-2,6-dithiaheptane]

copper(II) perchlorate. J. Chem. Soc. Dalton Trans. 1984, (7), 1349-1356.

(60) Schwedler, I.; Henke, S.; Wharmby, M. T.; Bajpe, S. R.; Cheetham, A. K.; Fischer, R. A., Mixed-linker solid solutions of functionalized pillared-layer MOFsadjusting structural flexibility, gas sorption, and thermal responsiveness. Dalton Trans. 2016, 45, (10), 4230-41.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 33

(61) Zhou, H.-F.; He, T.; Yue, K.-F.; Liu, Y.-L.; Zhou, C.-S.; Yan, N.; Wang, Y.-Y., Temperature-Induced Syntheses, Iodine Elimination, Enantiomers Resolution, and

Single-Crystal-to-Single-Crystal

Transformation

of

Imidazole-Co(II)

Coordination Polymers with Amino-isophthalic Acid as Co-Ligand. Cryst. Growth & Des. 2016, 16, (7), 3961-3968.

(62) Sun, H.-L.; Wang, Z.-M.; Gao, S., Synthesis, Crystal Structures, and Magnetism of Cobalt Coordination Polymers Based on Dicyanamide and Pyrazine-dioxide Derivatives. Inorg. Chem. 2005, 44, (7), 2169-2176.

(63) Cheng, X.-N.; Zhang, W.-X.; Chen, X.-M., Single Crystal-to-Single Crystal Transformation from Ferromagnetic Discrete Molecules to a Spin-Canting Antiferromagnetic Layer. J. Am. Chem. Soc. 2007, 129, (51), 15738-15739.

(64) Shen, B.; Shi, P.-F.; Hou, Y.-L.; Wan, F.-F.; Gao, D.-L.; Zhao, B., Structural diversity and magnetic properties of five copper-organic frameworks containing one-, two-, and three-types of organic ligands. Dalton Trans. 2013, 42, (10), 3455-3463.

(65) Liu, S.-J.; Xue, L.; Hu, T.-L.; Bu, X.-H., Two new Co-II coordination polymers based on carboxylate-bridged di- and trinuclear clusters with a pyridinedicarboxylate ligand: synthesis, structures and magnetism. Dalton Trans. 2012, 41, (22), 6813-6819.

Insert Table of Contents Graphic and Synopsis Here.


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For Table of Contents Use Only

Tunability in Metal Coordination Sphere, Ligand Coordination Mode, Network Topology and Magnetism via Stepwise Dehydration Induced Single-crystal to Single-crystal Transformation

Juan-Juan Hou, Xiao-Qing Li, Ping Gao, Han-Qi Sun, Xian-Ming Zhang*

Coordination polymer based on CoII (1) exhibits SC−SC transformations upon stepwise dehydration including lattice and coordination water molecules to form three different stable phases. During stepwise dehydration SC-SC transformation courses, coordination sphere of Co(II) and coordination modes of ligand are changed, and in particular overall network topology is significantly converted from 3-connected 63-hcb to (3,6)-connected kgd, accompanied by magnetism changes from single-ion behavior of Co(II) to intra-dicobalt ferromagnetism.


Tunability in Metal Coordination Sphere, Ligand Coordination Mode

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