Coordination Polymer with Solvent- Induced Reversible Spin

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A New Porous 3D Iron(II) Coordination Polymer with Solvent-Induced Reversible Spin-Crossover Behavior Yan Meng, Yan-Jie Dong, Zheng Yan, Yan-Cong Chen, Xiao-Wei Song, Quan-Wen Li, Chuanlei Zhang, Zhao-Ping Ni, and Ming-Liang Tong Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00657 • Publication Date (Web): 23 Jul 2018 Downloaded from http://pubs.acs.org on July 25, 2018

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Crystal Growth & Design

A New Porous 3D Iron(II) Coordination Polymer with SolventInduced Reversible Spin-Crossover Behavior a,b,

a

c

b

a

Yan Meng, * Yan-Jie Dong, Zheng Yan, Yan-Cong Chen, Xiao-Wei Song, Quan-Wen Li, Chuanlei Zhang,a Zhao-Ping Ni,b,* Ming-Liang Tong b,*

b

a

Anhui Province Key Laboratory of Optoelectronic and Magnetism Functional Materials, Key Laboratory of Functional Coordination Compounds of Anhui Higher Education Institutes, Anqing Normal University, Anqing 246011, China. b

Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun YatSen University, Guangzhou 510275, China. c

College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, P. R. China

ABSTRACT: A new Hofmann-type porous coordination polymer [Fe(dpni){Ag(CN)2}2]·4CH3CN (dpni = N, N’-Di-(4pyridyl)-1,4,5,8- naphthalenetetracarboxydiimide) with the topology of pcu net has been synthesized. It exhibits two-step spin-crossover behavior. Moreover, reversible changes between incomplete and two-step spin-crossover properties were associated with the desorption/resorption of the CH3CN solvent molecules.

Introduction Porous coordination polymers (PCPs) with the properties of magnetism, conductivity, or luminescence, which associate with the absorption/desorption of guests, represent a new kind of multifunctional materials.1-6 These multifunctional PCPs can act as chemical sensors by tuning the host-guest interactions. Among them, PCPs with spin-crossover (SCO) iron(II) building blocks are attractive.7,8 SCO Iron(II) units can be switched between the high spin (HS) and low spin (LS) states with different physical properties when external perturbation is performed.9-11 Thus, desorption/sorption of guest can work as a kind of stimulus to tune the spin states of the iron(II) ions.8,12,13 The tunable ability relies on the size and chemical nature of guests. Such sensory behavior can be detected by analyzing their magnetic and optical outputs. Until now, two main series of PCPs with SCO properties have been reported. Their generic formulas are [Fe(L)2(NCS)2]·guest (L = bis-monodentate ligand)14-19 and [Fe(L){MII(CN)4}]·guest (MII = Ni, Pd, or Pt)20-26. In the former case, its permanent porosity is achieved through the interpenetration of two-dimensional (2D) [Fe(L)2(NCS)2]∞ layers.14-19 Their SCO behaviors remarkably depend on the absence or presence of guests. Typically, the absence of solvents stabilizes the HS state, whilst their presence prefer to LS with a varying degree depending on the host-guest interaction. In the latter case, it is derived from the famous Hofmann clathrates. 2D [Fe{M(CN)4}]∞ layers are pillared by the bridging ligands L to form 3D PCPs.20-26 Generally, such 3D nature gives rise to a more-cooperative SCO behavior with large thermal

hysteresis. This family provides a good platform to investigate the effects of host-guest interactions on SCO properties. Instead of square-planar [MII(CN)4]2- units, the use of linear [MI(CN)2]- (MI = Ag, Au) linkers afford 2D [Fe{M(CN)2}2]∞ net with larger meshes. The bridging ligands always thread the meshes to form the twofoldinterpenetrated 3D [Fe(L){MI(CN)2}2]·guest system, which represents a new branch of Hofmann-type PCPs.27-31 As a further step in this research, a new Hoffman-type PCP [Fe(dpni){Ag(CN)2}2]·4CH3CN (1) based on the bismonodentate pyridine-like ligand N,N’-Di-(4-pyridyl)1,4,5,8-naphthalenetetracarboxydiimide (dpni) was synthesized. It exhibits a two-step SCO behavior. Desorption of the CH3CN solvent molecules was accompanied by drastic modifications of the SCO properties. It can go back to the two-step SCO behavior upon the resorption of CH3CN molecules. Results and Discussion X-ray Crystal Structure. Single crystal X-ray diffraction measurements were performed at 100, 176 and 293 K. Compound 1 adopts the orthorhombic space group Cmca at above three temperatures and no crystallographic phase transition is observed. Details of the crystal and refinement data for 1 are displayed in Table 1. The selected bond lengths and angles are given in Table S1, Supporting Information. Table 1. Crystal Data and Structure Refinements for 1. Parameter

T/K

ACS Paragon Plus Environment

1

100

176

293

Crystal Growth & Design 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

Color

red

red

brownish red

Formula

C36H24Ag2FeN12O4

Fw.

960.26

Space group

Cmca

a /Å

19.5823(18)

19.6704(7)

19.878(4)

b /Å

11.3760(9)

11.3565(4)

11.4419(17)

c /Å

16.1870(13)

16.3578(5)

16.745(3)

V /Å3

3605.9(5)

3654.1(2)

3808.6(11)

4

4

4

ρc /g cm

1.769

1.745

1.675

Ref. collected

2083

2170

1644

Z -3

Ref. unique

1826

1816

717

Rint

0.0471

0.0563

0.1237

GOF

1.109

1.065

0.935

R1 (I > 2σ(I))

0.0395

0.0474

0.0596

wR2b (all data)

0.1084

0.1459

0.1813

a

a

R1 = ∑||Fo| − Fc2)2]/∑[w(Fo2)2]}1/2

|Fc||/∑|Fo|,

b

Page 2 of 7

At 293K, the average Fe-N bond length is 2.172 Å, suggesting the iron(II) iron is in the HS state. At 176 and 100K, they are 2.065 and 2.004 Å, respectively, clearly indicating the presence of a HS↔LS spin transition. As shown in Figure 2a, the [Ag(CN)2]− units link iron atoms to form 2D layers with {Fe4[Ag(CN)2]4} grids. The [Fe-NCAgI-CN-Fe]∞ chains in a 2D layer are undulating as the angle C8–Ag–C9 of 169.4 (6), 168.4(3) and 167.05(18)°, Fe1– N3–C8 of 176.1(14), 175.6(6) and 175.2(4)° and Fe1–N4–C9 of 154.2(12), 159.5(6) and 163.5(4)° at 293, 176, and 100K, respectively. Meanwhile, two adjacent parallel chains show the opposite undulated shapes. The dpni ligands thread the meshes of the adjacent layers and

wR2 = {∑[w(Fo2 −

Figure 2. (a) View of the 2D {Fe[Ag(CN)2]2}∞ sheets formed by {Fe4[Ag(CN)2]4} grids of 1; (b) View of two-fold interpenetrated frameworks of 1. Figure 1. Coordination geometry of 1.

As shown in Figure 1, all iron atoms are crystallographically equivalent and situated on the inversion centers in the 3D framework. The iron centre is located in the middle of a distorted octahedron with the [FeN6] coordination environment, which consists of equatorial cyanide donor groups from [Ag(CN)2]− units and axial pyridyl donors from dpni ligands. Comparing the axial and equatorial Fe-N bond distances, we notice that the former are always longer than the latter (Table 2).

bridge the iron atoms from the subsequent 2D layer, which affords two-fold interpenetrated 3D frameworks (Figure 2b and Figure 3). The Fe⋯Fe distance through the Fe–NC–Ag–CN–Fe edge is 10.14, 9.96 and 9.89Å, whereas the Fe⋯Fe distances along the Fe–dpni–Fe direction is 19.88, 19.67 and 19.58 Å for 1 at 293, 176, and 100K, respectively. Unlike other Hoffman-type systems with [Ag(CN)2]− unit,10 no obvious argentophilic interactions were observed in 1.

2


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Table 2. Fe–N bond lengths (Å) and octahedral distortion parameters Σ (°) for 1 at 100, 176 and 293 K.

T

Fe-Nax

Fe-Neq1

Fe-Neq2

FeNav

ΣFe1

100K

2.039(4)

1.990(4)

1.983(4)

2.004

16.04

176K

2.106(5)

2.046(6)

2.044(7)

2.065

14.80

293K

2.237(9)

2.160(13)

2.118(13)

2.172

10.00

Figure 4. View of the 1D channel of 1 along b axis.

Magnetic Properties.

Figure 3. Packing diagram of a fragment of the 3D interpenetrated framework of 1 along the b axis. The hydrogen bonds are represented by pink dashed lines. The Ag⋯N interactions are represented by blue dashed lines.

The topological network of 1 was checked by the Topos software.32 The iron atoms can be regarded as 6-connected nodes. Meanwhile, dpni and [Ag(CN)2]- units are defined as connectors. Then, it gives the uninodal pcu net with the Schläfli symbol of (412·63) (see Figure S4, Supporting Information). The pillared topological network results in 1D channels along the b direction, in which CH3CN molecules are located. The oxygen atoms of dpni ligand partially block the channels, leading to a real hole with the size of about 5.6 × 9.9 Å (Figure 4). After removing the CH3CN molecules, the PLATON software shows a void space that represents 36.7% (1341.4 Å3) of the unit-cell volume at 176 K, which corresponds to 335 Å3 per iron atom.33

To investigate the SCO behavior in 1, the variabletemperature magnetic susceptibility data based on the crystalline samples were recorded in the temperature range of 10-300K with a cooling rate of 2 K min-1 (Figure 5). At 300 K, the χMT value is equal to 3.35 cm3 K mol−1 suggesting the HS state of iron(II) atom. It remains constant upon cooling to 265 K. Upon further cooling, it drops in a two-step SCO process, which is confirmed by the differential data of χMT versus T. The critical temperatures are 196 and 160 K, respectively. Then, χMT slightly decreases from 0.60 cm3 K mol−1 at 100 K to 0.43 cm3 K mol−1 at 10 K, suggesting the presence of the remaining 13% HS iron atoms. The following warming data is almost identical to the cooling one and no hysteresis is observed.

3



Figure 5. Magnetic properties in the form of χMT versus T and the corresponding derivative (blue dotted line) for 1.

In order to investigate the guest effect on SCO behavior, the temperature dependence of χMT for the desorbed analogue of 1 was collected (Figure 6, curve B). The χMT value is 3.42 cm3 K mol−1 at 300 K indicating a HS iron atom at room temperature. It decreases gradually to 3.25 cm3 K mol−1 at 244 K, and then descends steadily to 1.70 cm3 K mol−1 at 22 K. Upon further cooling, it decreases rapidly to 0.95 cm3 K mol−1 at 3 K, which is probably due to zero-field splitting of the remaining HS iron species. Therefore, the desorbed sample shows an incomplete and gradual SCO behavior, which may be due to the absence of host-guest interactions. Interestingly, the recovery of two-step SCO behavior is observed for the desorbed sample with the resorption of CH3CN molecules (Figure 6 and Figure S3, Supporting Information).

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of antiferro-elastic interaction. Such antiferro-elastic effect is required in the stepwise SCO system, which competes with ferro-elastic interaction to stabilize the intermediate state.38,39 Two-step or incomplete SCO properties are dependent on the presence/absence of CH3CN molecules in the pores. The solvents is deduced to play a key role to tune the SCO property. Therefore, the host-guest interactions are explored in detail. Two main types of contacts are found between CH3CN and the framework. One is the weak intermolecular hydrogen-bonding interactions (C-H···O), and the other is the weak Ag⋯N interactions (Table S2 and Figure S5, Supporting Information). Both of them should contribute to the SCO cooperativity. As the temperature is decreased, the C11-H···O1 and C11-H···O1 (x+1/2, y, -z-1/2) interactions decrease from 3.539 and 3.442 Å at 293 K to 3.430 and 3.317 Å at 100 K. Meanwhile, the weak Ag⋯N interactions also decrease with cooling. Therefore, the weak hydrogen-bonding and Ag⋯N interactions provide ferro-elastic interactions, which are in favour of higher spin transition temperature and stronger cooperativity. As a consequence, comparing with the desorbed sample, relatively abrupt SCO behavior with higher Tc is found in 1. Conclusion In summary, a new Hoffman-type 3D PCP [Fe(dpni){Ag(CN)2}2]·4CH3CN (1) with two-step SCO behavior was reported. Moreover, reversible changes between incomplete and two-step SCO behaviors were observed upon the desorption/resorption of the CH3CN solvent molecules. The weak hydrogen-bonding and Ag⋯N interactions between CH3CN and the host are contributed to such remarkable variation of SCO properties. This PCP can be a candidate for the generation of new switchable or multifunctional materials.

Figure 6. Temperature dependence of the χMT of 1: fresh single crystals (A); the desolvated sample (B); the desolvated sample with the resorption of CH3CN solvent (C).

Discussion To better understand two-step SCO behavior in 1, the magnetostructural correlation is further explored in detail. Usually, a two-step SCO can result from structurally inequivalent SCO sites at the whole temperature range34-37 or symmetry breaking with inequivalent SCO sites only in the intermediate phase28,31,38-41. Since only one type of iron centre is observed in the LS (100 K) and HS states (293 K), the occurrence of stepwise transition in 1 should be due to symmetry breaking. However, one iron atom with the average Fe-N distance of 2.065 Å is observed in the intermediate phase (176 K). That means, unambiguous identification of LS and HS sites can not be realized, which is consist with the lack of obvious plateau in the magnetic curve. Although the mixed spin state is shown in the intermediate phase, the octahedral distortion parameters Σ gives some clue for stepwise SCO behaviors. The Σ values in 1 increase with cooling: 10.00⁰ (293 K) → 14.80⁰ (176 K) → 16.04⁰ (100 K), suggesting the presence

Experimental Section Physical measurements. The C, H, N microanalyses were performed with an Elementar Vario-ELCHNS elemental analyzer. FT-IR spectra were collected in KBr pellets in the range 4000−400 cm−1 on a Bruker-tensor 27 spectrometer. Powder X-ray diffraction (PXRD) spectra for polycrystalline samples were recorded at room temperature on a Bruker D8 Advance diffractometer (CuKα, λ = 1.54056 Å) (Figure S1, Supporting Information) by scanning over the range 5-50° with step of 0.2°/s. The calculated patterns were generated with Mercury 3.1 software. Thermogravimetric-differential thermal analysis (TG-DTA) was performed under the flowing N2 atmosphere at a scan rate of 10 K min-1. Magnetic susceptibility data were collected on a Quantum Design MPMS XL-7 instrument under a field of 1000 Oe. Samples were sealed in plastic film and then mounted in the plastic straw. The magnetic contributions of the plastic film and straw was corrected. The diamagnetic correction of 1 was calculated from Pascal’s constants.

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Crystal Growth & Design X-ray Crystallography and Data Collection. Diffraction intensities of 1 were recorded on a Rigaku RAXIS SPIDER IP diffractometer by using Mo Kα radiation (λ = 0.71073 Å) at 100, 176 and 293 K. Structures were solved by direct methods in the SHELXTL program, and all non-hydrogen atoms were then refined anisotropically through least-squares on F2.42 Hydrogen atoms on organic ligands were generated and refined by the riding mode. CCDC-1830390 (1_100 K), CCDC-1848900 (1_176 K) and CCDC-1830392 (1_293 K) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Materials and Synthesis. All of the reagents were commercially available and used without further purification. The dpni ligand was synthesized according to literature method.43 [Fe(dpni){Ag(CN)2}2]·4CH3CN (1). This compound was synthesized by using slow diffusion technique. A solution of K[Ag(CN)2] (10 mg, 0.04 mmol) and dpni (8 mg, 0.02 mmol) in DMF were placed in a 5mL test tube, while a 1 ml test tube was filled with a solution of Fe(ClO4)2·9H2O (5 mg, 0.02 mmol) in CH3CN. Two tubes were then inserted into a 30 ml vial filled with CH3CN. Brownish red block crystals for single crystal Xray diffraction were collected after two days in 67% yield based on Fe(ClO4)2·9H2O. Elemental analysis calcd (%) for 1: C, 45.03; H, 2.52; N, 17.50; Found (%): C, 44.86; H, 2.43; N, 17.62. IR data for 1: 2164 and 2079 cm−1 (C≡N).[20] The desolvated sample was obtained by placing 1 in the sample tube of automatic volumetric adsorption apparatus (BELSORP-max) and dried at 373K for 2 hours to remove the CH3CN molecules. And the resolvated sample was obtained by soaking the desolvated sample in CH3CN solvent.

ASSOCIATED CONTENT Supporting Information. Powder X-ray diffraction patterns, TG curves, selected bond lengths and angles, magnetic properties and additional structural figures for 1. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. * E-mail: [email protected]. * E-mail: [email protected].

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This article is dedicated to Professor Xin-Tao Wu on the occasion of his 80th birthday. This work was supported by the National Key Research and Development Program of China

(2018YFA0306001), the NSFC (21601002, 21773316, 21373279, 21501067), Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01C161) and the Natural Science Research Key Project of Anhui Provincial Department of Education (KJ2017A346).

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For Table of Contents Use Only A New Porous 3D Iron(II) Coordination Polymer with Solvent-Induced Reversible Spin-Crossover Behavior Yan Meng, Yan-Jie Dong, Zheng Yan, Yan-Cong Chen, Xiao-Wei Song, Quan-Wen Li, Chuanlei Zhang, Zhao-Ping Ni, and Ming-Liang Tong

A new porous coordination polymer [Fe(dpni){Ag(CN)2}2]·4CH3CN (dpni = N,N′-Di-(4-pyridyl)-1,4,5,8naphthalenetetracarboxydiimide) with two-step SCO behavior was reported. Reversible changes between incomplete and two-step spin-crossover properties were associated with the desorption/resorption of CH3CN molecules.

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Coordination Polymer with Solvent- Induced Reversible Spin

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