Zero in-Plane Thermal Expansion in Guest-Tunable 2D Coordination

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Zero in-Plane Thermal Expansion in Guest-Tunable 2D Coordination Polymers Ryo Ohtani,*,† Arnaud Grosjean,‡ Ryuta Ishikawa,§ Riho Yamamoto,† Masaaki Nakamura,† Jack K. Clegg,‡ and Shinya Hayami*,†,¶ †

Department of Chemistry, Graduate School of Science and Technology and ¶Institute of Pulsed Power Science, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan ‡ School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane St. Lucia, Queensland 4072, Australia § Department of Chemistry, Faculty of Science, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan S Supporting Information *

ABSTRACT: Zero in-plane thermal expansion (TE) in a two-dimensional (2D) coordination polymer is demonstrated. The combination of components that expand and those that shrink into zigzag layers results in no net area change in the 2D materials with temperature. Single crystals of [Mn(salen)]2[Mn(N)(CN)4(guest)] (salen = N,N′-ethylenebis(salicylideneaminato), guest = MeOH and MeCN) were prepared, and variable-temperature single-crystal X-ray structural analyses demonstrated that these compounds exhibited both anisotropic positive and negative thermal expansion depending on the guest species. The TE behavior results from distortions of the octahedral coordination geometry of [Mn(salen)]+ units in the zigzag layers. When both guests MeOH and MeCN were incorporated into one material, [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75], zero in-plane TE resulted in a range of temperature between 380 and 440 K.

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is constructed by combining [Mn(N)(CN)4]2− units43−47 with [Mn(salen)]+ units. The use of [M(CN)4]2− (M = Pt, Pd, Ni, MnN, MoO) has been demonstrated to yield structural flexibility48−53 and open axial sites to interact with guest molecules.54,55 The 2D CP shows two anisotropic structural transformations; contraction (NTE) and expansion (PTE) switched by guest species. To prepare a material showing ZTE, we combined these opposite transformations in single layers through a construction of solid-solution compounds incorporating both molecular building blocks (one that shows PTE and one that shows NTE; Figure 1). Herein, we investigated the guest-dependent TE behavior of [Mn(salen)]2[Mn(N)(CN)4(guest)] (guest = MeOH and MeCN) using variable-temperature single-crystal X-ray structural analyses. By varying the number and identity of the guest molecules we succeeded in tuning the structural transformations of the layers resulting in producing zero in-plane TE in [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75] in a range of temperature between 380 and 440 K.

INTRODUCTION Two-dimensional (2D) materials are promising candidates for incorporation into future devices due to their potential to form thin films and nanosheets.1−5 In particular, 2D coordination polymers (CPs)6−11 have attracted much attention, because they exhibit guest adsorption/desorption properties and electronic activities.12−16 To better design stable devices incorporating such 2D CPs, a fuller understanding of the mechanical responses of 2D CPs is required. The mechanical properties of frameworks including thermal expansion (TE) and compressibility are of interest in fundamental understanding of intrinsic flexibility of frameworks as well as technological applications such as nanoscale actuators and sensors.17−37 Of particular interest are materials that display either zero thermal expansion (ZTE) or large positive or negative TE. Most investigations of this type have focused on three-dimensional (3D) Prussian blue-type and hinge-type compounds, while studies on 2D layer-type CPs have received far less attention, despite observations of structural transformations induced by guest adsorption/desorption.10,38−42 For example, Goodwin and co-workers found that a 2D silver(I) tricyanomethanide shows negative area compressibility and anisotropic TE.21 Here we report a 2D CP [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75] (salen = N,N′-ethylenebis(salicylideneaminato) that shows ZTE in the plane of the polymer as well as “out-of-plane” flexibility. The 2D CP [Mn(salen)]2[Mn(N)(CN)4(guest)] (guest = MeOH and MeCN) consisting of a zigzag layer-type structure © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Synthesis. All reagents were commercially available and used without further purification. [Mn(salen)]Cl and (PPh4)2[Mn(N)(CN)4]·2H2O were synthesized according to the method described previously.43 Received: February 2, 2017

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Figure 1. Schematic images of an introduction of positive and negative TE into the zigzag layer and the mechanism of zero in-plane TE of zigzag layer.

Figure 2. Crystal structures of (a) 1·H2O·MeOH and (b) 2·H2O. Layer structures in ab plane (left) and stacking structures along c axis (right). Color code: pink (Mn), red (O), blue (N), and gray (C). H atoms are omitted for clarity. [Mn(salen)]2[Mn(N)(CN)4(MeOH)]·H2O·MeOH (1·H2O·MeOH). A solution of [Mn(salen)]Cl (20 mg, 0.055 mmol) in H2O (25 mL) added to a solution of (PPh4)2[Mn(N)(CN)4]·2H2O (25 mg, 0.028

mmol) in MeOH (25 mL) at room temperature (RT). After it was stirred for 12h, the greenish-yellow precipitation was collected by suction filtration, washed with water and methanol, and dried in air. B

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Figure 3. Zigzag layer structures of (a) 1 and (b) 2. The angles between [Mn(N)(CN)4]2− units and the width of (c) 1·H2O·MeOH and 1, and (d) 2·H2O and 2. Salen ligands and solvents are omitted for clarity.

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Yield 39.3%. Anal. Found (calcd) for C37H33Mn3N9O5.5 (856.54): C 51.81 (51.88); H 4.21 (3.88); N 14.64 (14.72)%. [Mn(salen)]2[Mn(N)(CN)4(MeCN)]·H2O (2·H2O). This compound was synthesized by the same method for 1·H2O·MeOH using MeCN instead of MeOH. Yield 33.4%. Anal. Found (calcd) for C38H36Mn3N10O6.5 (901.58): C 50.89 (50.62); H 4.05 (4.02); N 15.15 (15.54)%. [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.8(MeCN)0.2]·1.4H2O (3·H2O). This compound was synthesized by the same method for 1·H2O· MeOH using the mixed solvents of MeOH (18 mL) and MeCN (5 mL) instead of MeOH. Yield 29.1%. Anal. Found (calcd) for C37.2H34.6Mn3N9.2O6.2 (874.56): C 51.29 (51.09); H 4.17 (3.99); N 14.47 (14.73)%. [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75]·H2O (4·H2O). This compound was synthesized by the same method for 1·H2O·MeOH using the mixed solvents of MeOH (12 mL) and MeCN (12 mL) instead of MeOH. Yield 30.2%. Anal. Found (calcd) for C37.75H33.25Mn3N9.75O5.25 (872.31): C 52.21 (51.98); H 4.11 (3.84); N 15.38 (15.66)%. Physical Measurements. Single-crystal X-ray data for 1 were recorded on an Oxford Gemini Ultra diffractometer employing graphite monochromated Mo Kα radiation generated from a sealed tube (λ = 0.7107 Å). Data integration and reduction were undertaken with CrysAlisPro. Using Olex2, the structure was solved with the ShelXT structure solution program using Direct Methods and refined with the ShelXL refinement package using Least Squares minimization. Hydrogen atoms were included in idealized positions and refined using a riding model. Single-crystal X-ray data for 2 were recorded on a Rigaku/MSC Saturn CCD diffractometer with confocal monochromated Mo Kα (λ = 0.7107 Å) and processed by using Rigaku/ CrystalClear software. The structures were solved by direct methods (Sir 2004) and refined by full-matrix least-squares refinement using the SHELXL-2013 computer program. The hydrogen atoms were refined geometrically by using a riding model. Variable-temperature powder X-ray diffraction data (VT-PXRD) were collected on a RIGAKU SmartLab (40 kV/30 mA) X-ray diffractometer using Cu Kα radiation (λ = 1.5406 Å) in the 2θ range of 3°−60° with a step width of 0.02° at each temperature. Temperature was varied at 10 K min−1 and annealed 10 min before diffraction measurements at each temperature. The pattern resolution and the unit cell refinement for VT-PXRD data were determined by using the Pawley method with the Rigaku software package PDXL2. Thermogravimetric analysis (TGA) was performed at 10 K min−1 using a Rigaku Instrument Thermo plus TG 8120 in a nitrogen atmosphere. Scanning electron microscope (SEM) images were collected on JEOL JSM-7600F. Elemental analyses (C,H,N) were performed on a J-SCIENCE LAB JM10 analyzer at the Instrumental Analysis Centre of Kumamoto University. Infrared (IR) spectra measurements were performed on a PerkinElmer Spectrum Two FT-IR equipped with an ATR accessory.

RESULTS AND DISCUSSION Crystal Structures. Single crystals and powders of [Mn(salen)]2[Mn(N)(CN)4(MeOH)]·H2O·MeOH (1·H2O· MeOH) were prepared by mixing an aqueous solution of [Mn(salen)]Cl and a methanol solution of (PPh4)2[Mn(N)(CN)4]2·H2O in a 2:1 ratio. At 100 K 1·H2O·MeOH is orthorhombic (Pbcn; Table S1). The structure is a 2D CP with undulating zigzag layers constructed from two-connecting [Mn(salen)]+ units linked through the nitrogen atoms of the cyanide groups of four-connecting [Mn(N)(CN)4]2− units. The infinite 2D (4,4)-layers propagate in the ab plane and are stacked along the c axis (Figure 2a). The angles between [Mn(N)(CN)4]2− units in the zigzag layers are 160° (Figure 3c). MeOH solvent molecules are coordinated to the remaining position of the [Mn(N)(CN)4]2− units. Lattice H2O and MeOH molecules interact with oxygen atoms of the salen ligands via hydrogen bonding. In the powder sample of 1·H2O· MeOH, the lattice MeOH exchanged with water molecules in the air under ambient conditions. TGA on these samples showed that the lattice solvents were removed by 360 K and that the coordinated MeOH molecules remained until 440 K (Figure S1). [Mn(salen)]2[Mn(N)(CN)4(MeCN)]·H2O (2·H2O) was synthesized by the same procedure for 1 using acetonitrile instead of methanol. At 123 K 2·H2O is orthorhombic (Pccn; Table S1). MeCN molecules are bound to the apical site of the [Mn(N)(CN)4]2− units, producing a more pronounced “wave” in the undulating layers of 2·H2O than in 1·H2O·MeOH; the angle between [Mn(N)(CN)4]2− units being 147° (Figure 3d). Lattice H2O molecules interact with oxygen atoms in salen ligands in the same manner as 1·H2O·MeOH. The coordinated MeCN molecules could be removed at 480 K (Figure S1). Variable-Temperature SXRD for 1·H2O·MeOH and 2· H2O. The thermal expansion behavior of 1·H2O·MeOH and 2· H2O were investigated by variable-temperature single-crystal Xray structural analyses (VT-SCXRD; Figures 4 and 5). Each structure shows three distinct thermal responses in three different temperature regions. In 1·H2O·MeOH, isotropic PTE occurs from 100 to 260 K. At 280 K, the lattice water molecules are removed, and 1·MeOH results, accompanied by a phase change to a Ccca system (Table S1 and Figure S2). From 280 to 360 K, the b axis decreases, while the a and c axes increase. Between 380 and 440 K, 1·MeOH shows isotropic PTE. The lattice MeOH was removed at 490 K, producing a guest-free compound (1) that is crystallized in the tetragonal (P4/ncc) C

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Figure 4. Thermal variation of cell parameters for (a) 1·H2O·MeOH and (b) 1·H2O. The thermal variation of the angles between [Mn(N)(CN)4]2− units in the zigzag layers for (c) 1·H2O·MeOH and (d) 1·H2O.

the a and b directions and PTE along the c axis. The thermal expansion coefficients (α) along a (=b) and c axis are αa,b = +4.96 MK−1 (M = 1 × 10−6) and αc = +51.6 MK−1 for 1·H2O and αa,b = −7.75 MK−1 and αc = +94.0 MK−1 for 1, respectively (Table 1). 2·H2O shows isotropic PTE upon heating from 123 to 200 K (Figure 5a). From 220 to 320 K, the a and b axes gradually increase, while the c axis length decreases. At 340 K (Table S3) the sample undergoes a phase change to a tetragonal system

symmetry. We then cooled this sample to 100 K and repeated the VT-SCXRD measurements between 100 and 440 K. At 100 K, lattice water molecules (absorbed from the air) were observed resulting in the formula 1·H2O (Figure S3). 1·H2O shows similar TE behavior to 1·H2O·MeOH below 340 K (Figure 4b and Table S2). Between 100 and 260 K, isotropic PTE behavior is observed, while anisotropic cell parameter changes occur between 280 and 340 K (when the lattice solvent is lost). Above 360 K, 1 shows anisotropic TE involving NTE in D

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Figure 5. Thermal variation of cell parameters for (a) 2·H2O and (b) 2. (●) Refined cell parameters. (◇) Parameters obtained by quick scans. The thermal variation of the angles between [Mn(N)(CN)4]2− units in the zigzag layers for (c) 2·H2O, and (d) 2.

= +36.0 MK−1 and αc = +4.35 MK−1 in 123−260 K and αa,b = +52.2 MK−1 and αc = −28.0 MK−1 in 340−400 K, respectively (Table 1). Mechanism of the Anisotropic TE Behavior of 1 and 2. Figure 4c,d displays the thermal variation of the angles between [Mn(N)(CN)4]2− units in the zigzag layers for 1·H2O·MeOH (the first cycle) and 1·H2O, respectively. In all temperature regions, the angles decrease with increasing temperatures producing a contraction in the zigzag layers of 1. This

from orthorhombic. Further heating to 400 K results in the loss of lattice water molecules, while the a axis decreases and the c axis increases. The resulting solvent-free 2 could be cooled to 123 K without regaining the solvent molecules showing isotropic below 260 K, and anisotropic TE, in which a and b axes expand and the c axis contracts, occurs above 340 K (Figure 5b and Table S4). The direction in the anisotropic TE behavior of 2 is opposite to that observed in 1. The thermal expansion coefficients (α) along a (=b) and c axis for 2 are αa,b E

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S4). These local structural transformations of [Mn(salen)]+ units also result in reversible color changes (Figure S5). 1, which is greenish-yellow at RT, becomes brown at 440 K, and the brown color of 2 becomes significantly darker at 440 K. Tunable Anisotropic TE of the Solid-Solution Systems. We then investigated tuning the TE behavior of the zigzag layers by combining both coordinated MeOH and MeCN into the same structure. We prepared two powder samples with MeOH:MeCN ratios of 3.6:1 and 1:1, respectivley. Elemental analyses and TGA results for these resultant solid-solutions confirmed that their compositions are [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.8(MeCN)0.2]·1.4H2O (3·H2O,powder) and [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75]·H2O (4·H2O,powder), respectively (Figure S6). PXRD, IR results, and SEM images for these compounds confirms their phase purity (Figures S7−S9). VT-PXRD (Figures 7, S10, and S11) were undertaken between 300 and 500 K for each of 1·H2O,powder, 3·H2O,powder and 4·H2O,powder. In each case lattice solvent was removed by 380 K (to yield 1,powder, 3,powder, and 4,powder), and coordinated solvent was lost above 440 K. Consistent with VT-SCXRD, the layers of 1,powder show NTE behavior (αa,b = −28.9 × MK−1) between 380 and 440 K. In the same temperature range 3,powder, which contains 20% coordinated MeCN, showed markedly slower NTE (αa,b = −6.01 MK−1). Increasing the ratio of MeCN to 75% (4,powder) resulted in an excellent balance between the PTE and NTE in the plane of the layers resulting in no net thermal expansion (ZTE) in the ab plane (αa,b = −0.85 MK−1) between 380 and 440 K (Table 1 and Figure 7b). We were thus able to control the TE behavior and associated structural dynamics of the zigzag layers of [Mn(salen)]2[Mn(N)(CN)4] by manipulating the ratios of MeOH and MeCN coordinated to the [Mn(N)(CN)4]2− unit.

Table 1. Calculated Thermal Expansion Coefficients (α) along a, b Axes and c Axis for 1−4 1·H2O (100 K−220 K) 1 (360 K−460 K) 2 (123 K−260 K) 2 (340 K−400 K) 1,powder (380 K−440 K) 3,powder (380 K−440 K) 4,powder (380 K−440 K)

αa,b, MK−1

αc, MK−1

+4.96 −7.75 +36.0 +52.2 −28.9 −6.01 −0.85

+51.6 +94.0 +4.35 −28.0 +25.9 +76.9 +88.0

contraction is more pronounced between 360 and 440 K after the removal of the lattice solvent. In the case of 2·H2O, however, the angles of the zigzag layers increase with increasing temperature up to 340 K, producing flatter layer structures (Figure 5c) and their expansion. From 340 to 400 K, the removal of the lattice water results in a reversal of this trend; however, once removed, 2 shows a linear expansion of the layers upon heating. This is the opposite of the trend observed in 1 (Figure 5d). The TE behavior of each of 1 and 2 therefore has opposite signs, resulting in either the contraction or expansion of the respective zigzag layers. Close inspection of the structures shows that the distortion of the coordination geometries of the [Mn(salen)]+ units is responsible for this behavior (Figures 6 and 7). In both cases, the octahedral coordination geometries of [Mn(salen)]+ units are distorted, in which the angles of CN−Mn−benzene ring (in salen) are 77° and 103° for 1 at 100 K, while those for 2 are 97° and 82° at 123 K, respectively (Figure 6a,b). With increasing temperatures, these angles approach 90° (closer to the ideal octahedral geometry). For example, at 440 K the angles are 81° and 99° in 1, while at 400 K they are 93° and 87° degrees in 2. In both 1 and 2 a rotation of [Mn(salen)]+ units and a translation of [Mn(N)(CN)4]2− units occurs (Figure 6c,d). This produces the observed contraction within the layers of 1 and expansion in 2 (Figure

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CONCLUSION By fully understanding the mechanism of thermal expansion in a 2D CP we have been able to design a system to achieve zero

Figure 6. Thermal variation of distortion angles of [Mn(salen)]+ units for (a) 1 and (b) 2. Schematic views displaying structural transformations of (c) 1 and (d) 2 at increasing temperatures. F

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Figure 7. (a) Diffraction peak shift of (200) plane in the PXRD patterns for 1·H2O,powder (blue), 3·H2O,powder (black), and 4·H2O,powder (red) as heating from 300 to 500 K. (200) plane is located diagonally to the grids of cyanide networks in the layers (Figure S11). (b) The thermal variation of a axis parameters.

ORCID

in-plane thermal expansion. Our results demonstrate that expansion and contraction behavior of the zigzag layers in this material are controlled by the coordination of solvent species. By varying the proportion of coordinated solvents present we were able to tune the thermal expansion properties. These findings provide new insight into the control of structural dynamics, which will help the development of future applications such as molecular actuators and thermochromic sensors.

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Ryo Ohtani: 0000-0003-4840-3338 Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest. CCDC 1521085−1521094, 1521154−1521195 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_ request/cif/, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00282. Tables of crystal parameters. TGA results. Crystal structures of 1·MeOH at 280 K and 1·H2O at 100 K. Thermochromic behavior. PXRD and IR results. SEM images. (PDF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF) X-ray crystallographic information (CIF)

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ACKNOWLEDGMENTS This work was supported by JSPS Grant-in-Aid for Young Scientists (B) JP15K17833, JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Dynamical Ordering & Integrated Functions) JP16H00777, the Iketani Science and Technology Fundation 0281019-A, and the Izumi Science and Technology Fundation H27-J-094. This work was also supported by KAKENHI Grant-in-Aid for Scientific Research (B) JP26288026. This work was partially supported by the Cooperative Research Program of “Network Joint Research Centre for Materials and Devices”. The authors thank the Australian Research Council for support.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. (R.O.) *E-mail: [email protected]. (S.H.) G

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DOI: 10.1021/acs.inorgchem.7b00282 Inorg. Chem. XXXX, XXX, XXX−XXX