Home Journals Articles Updates About
CN
image
收藏切换
Four-step spin-crossover in an oxamide-decorated metal-organic framework
收藏切换
PDF
Siguo Wu1, Sukhen Bala1, Zeyu Ruan, Guozhang Huang, Zhaoping Ni*, Mingliang Tong
Chinese Chemical Letters | 2022, 33(3) : 1381 - 1384
Less
收藏切换
Chinese Chemical Letters | 2022, 33(3): 1381-1384
• Review •
Four-step spin-crossover in an oxamide-decorated metal-organic framework
Full
Siguo Wu1, Sukhen Bala1, Zeyu Ruan, Guozhang Huang, Zhaoping Ni*, Mingliang Tong
Affiliations
  • Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
Published: 2022-03-15 doi: 10.1016/j.cclet.2021.08.012
Outline
收藏切换

Spin-crossover (SCO) complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches. Here, by employing the N, Nʹ-4-dipyridyloxalamide (dpo) ligand, we synthesize two Hofmann-type metal-organic frameworks (MOFs) [Fe(dpo){Ag(CN)2}2]·3DMF (1) and [Fe(dpo){Ag(CN)2}2]·0.5MeCN·2DEF (2), which exhibit guest dependent four-step SCO behaviors with the sequences of LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS3/10HS7/10 → HS and LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS1/4HS3/4 → HS, respectively. Therefore, the incorporation of hydrogen-donating/hydrogen-accepting groups into the Hofmann-type MOFs may effectively explore the multi-step SCO materials by tuning hydrogen-bonding interactions.

Spin crossover  /  Oxamide  /  Metal-organic framework  /  Hofmann-type  /  Host-guest interaction
Siguo Wu, Sukhen Bala, Zeyu Ruan, Guozhang Huang, Zhaoping Ni, Mingliang Tong. Four-step spin-crossover in an oxamide-decorated metal-organic framework[J]. Chinese Chemical Letters, 2022 , 33 (3) : 1381 -1384 . DOI: 10.1016/j.cclet.2021.08.012
Full Text
Less
Multi-stable materials have aroused significant interests in scientific community for their potential applications in informatics. Spin-crossover (SCO) complexes, especially for iron(Ⅱ) species whose spin states can be manipulated between diamagnetic low-spin (LS, t2g6eg0) state and paramagnetic high-spin (HS, t2g4eg2) state via external stimuli (such as temperature, pressure, light irradiation and guest molecules), are conceivable elements for memory devices and opto-magnetic switches [1-5]. When the competitions of long-range ferro- and antiferro-elastic interactions occur between SCO units, elastic frustrations may lead to multi-step SCO behaviors, which can act as the multi-stable materials with the potential applications in high-order data storage and multi-switches [6-8].
Hofmann-type clathrates, consist of iron-cyanometalate meshes and pillar ligands, are promising candidates for constructing high-performance SCO materials [9-11]. Extensive efforts have been devoted to promote the SCO cooperativity via fine-tuning the hydrogen-bonding interactions [12-14] and π-π interactions [15, 16]. By means of guest exchange, the implementations of guest programmable multistep switches, gate-opening with multiplex responses and bidirectional chemo-switching have been achieved in porous 2D/3D Hofmann-type frameworks [17-20]. However, the synergetic effects of host-guest interactions are complicated since SCO dynamics are influenced by the size, distribution and geometry of the guests, the porous capacity and characteristic of the host as well as the direction and strength of host-guest interactions [11]. Integration of hydrogen-donating/hydrogen-accepting groups (imide [21], amide [22], amino [18], hydroxyl [14, 23], urea [24], etc.) into pillar ligands would be a judicious choice for achieving strong host-guest interactions in Hofmann-type metal-organic frameworks (MOFs).
Since hydrogen-bonding interactions play an important role in multi-step SCO behaviors [12-14, 18], an oxamide-decorated ligand N, Nʹ-4-dipyridyloxalamide (dpo, Scheme 1) is firstly employed to construct two SCO Hofmann-type MOFs [Fe(dpo){Ag(CN)2}2]·3DMF (1) and [Fe(dpo){Ag(CN)2}2]·0.5MeCN·2DEF (2), in which the oxamide unit can act as hydrogen bond donor as well as acceptor. Hence, four-step SCO behaviors with two new sequences are observed, although the reported four-step spin transition properties are extremely rare so far [12, 14, 16, 18, 22, 25-27]. Moreover, spin transition temperatures and thermal hysteresis loops are altered by different solvent guests.
Complexes 1 and 2 were prepared by slow diffusion methods and isolated as the yellow block crystals. The crystalline samples were assessed by elemental analysis, powder X-ray diffraction (Figs. S1 and S2 in Supporting information), thermogravimetric (TG) measurements (Figs. S3 and S4 in Supporting information) and infrared spectra (Figs. S5 and S6 in Supporting information). TG analyses reveal that the guest molecules in 1 and 2 can be completely removed upon heating to around 435 and 473 K, respectively.
Temperature-dependent magnetic susceptibility measurements for 1 and 2 were performed over the range of 10−300 K with a sweep rate of 2 K/min (Fig. 1). At room temperature, the χMT value of 1 is close to 3.75 cm3 K/mol, indicating a pure HS state. It slightly decreases to 3.65 cm3 K/mol at 230 K and then declines gradually. An inclined plateau is observed in the middle of SCO curve, corresponding to a HS1/2LS1/2 intermediate state. Upon further cooling, the χMT value reaches to 0.11 cm3 K/mol at 10 K, which is consistent with a LS state. The 1st derivative plot of magnetic data suggests four-step SCO behavior with a sequence of LS→~LS2/3HS1/3→LS1/2HS1/2→~LS3/10HS7/10→HS, although their magnetic plateaus are not obvious. The critical temperatures for the peaks/valleys are at 139/160/191/203 K and 143/164/191/203 K in the cooling/warming modes, respectively. Therefore, the largest width of thermal hysteresis (∆T) loop is only ~4 K.
For 2, the cooling and warming SCO curves with hysteresis loop shift to the higher temperature region. A gradual four-step SCO behavior with the sequence of LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS1/4HS3/4 → HS can be inferred from the differential magnetic curve, although no obvious magnetic plateaus are observed in 2. The related 1st derivative peaks/valleys locate at 189/200/226/235 K and 193/205/230/237 K in the cooling/warming modes, indicating the thermal hysteresis width is up to 5 K. The four-step SCO behaviors of 1 and 2 are further confirmed by two cycles of magnetization measurements (Figs. S7 and S8 in Supporting information).
To corroborate the multi-step SCO behaviors, DSC measurements were carried out with a sweeping rate of 10 K/min. As shown in Fig. S9 (Supporting information), four pairs of exothermic/endothermic peaks locate at 136/149/186/195 K and 144/158/189/199 K in the cooling/warming modes, respectively, which confirms the four-step SCO behavior in 1. These DSC peaks slightly deviate from the Tc peaks from the magnetic data, which should be due to the different scanning rates. Analogously, four sets of exothermic (193/201/226/235 K) and endothermic (195/204/228/238 K) peaks are found in the cooling and warming modes, confirming the four-step SCO behavior in 2 (Fig. S10 in Supporting information). The total enthalpy changes (∆H) of 1 and 2 are around 13.21 and 9.84 kJ/mol, which are in the normal range for SCO FeⅡ compounds [28].
Complex 1 crystalizes in triclinic space group and retains the geometric symmetry at 120, 182 and 298 K (Table S1 in Supporting information). The asymmetry unit consists of a FeⅡ ion, a dpo pillar ligand, two [Ag(CN)2]− linkers and three DMF molecules (Fig. 2a). Each FeⅡ center adopts a distorted octahedral geometric fashion with [FeN6] coordination environment. The equatorial positions are occupied by CN groups of linear [Ag(CN)2]− ligands, giving rise to the [Fe{Ag(CN)2}2]∞ network. The FeⅡ ions between the adjacent layers are axially linked by the bidentate dpo ligands, which results a two-fold interpenetration framework (Fig. 2c). Permanent 1D channels along the diagonal direction of the a and b axis are found, wherein three DMF guests are housed (Fig. S11 in Supporting information). Two DMF molecules are involved into the strong N−H···O hydrogen bonds on either side of the dpo ligand (green dotted lines in Fig. 2a). Meanwhile, the remaining DMF molecule is engaged in the weak intermolecular interactions with the neighboring DMF guest (purple dotted line in Fig. 2b) and dpo ligand.
The detailed structural parameters of 1 can give a clue of the stepped SCO behavior, although only one unique FeⅡ ion is solved in the intermediate state (Table S3 in Supporting information). At 120 and 298 K, the average Fe−N bond length is 1.963 and 2.178 Å, in line with the LS and HS FeⅡ ions, respectively. In contrast, the < Fe−N > av distance is 2.099 Å at 182 K, which is close to the LS1/2HS1/2 state. Meanwhile, the octahedral distortion parameter (∑) changes from 11.67° (120 K) to 11.49° (182 K) and then to 16.00° (298 K). Since the HS FeⅡ ions favor higher ∑ values than their LS counterparts, the unusual ∑ at 182 K hints the presence of antiferro-elastic interaction, which is required for the stepped SCO system to stabilize the intermediate states according to the elastic model [6]. Upon warming, the monotonic increases of the unit cell volume and the Fe···Fe distances along the dpo and [Ag(CN)2]− linkers as well as the Ag···Ag distance are consistent with the SCO process, which represent the ferro-elastic interactions. The N3···O3 distance and N3−H3···O3 angle are monotonically increased and decreased. Meanwhile, the unusual trend of the N2···O4 distance change and the monotonic increase of N2−H2···O4 angle are found. Hence, the complicated hydrogen-bonding interactions between host and guest hint the competition between antiferro- and ferro-elastic interactions [29].
Complex 2 possesses a similar two-fold interpenetration framework with 1D channel along the b axis (Fig. S12 in Supporting information) but crystalizes in orthorhombic space group Pca21 at 120, 215 and 300 K. Unlike 1, the asymmetric unit in 2 contains two crystallographically inequivalent FeⅡ ions, two dpo ligands as well as four [Ag(CN)2]− linkers belonging to two sets of 3D frameworks. Meanwhile, one MeCN and four DEF serve as the guest molecules (Fig. 3). Most importantly, one DEF form a bifurcated H-bond (N3−H3···O7···H10−N10) with two dpo ligands from two 3D frameworks, which may contribute to the asymmetry of two-fold interpenetration framework and improve their effective transmission via host-guest interactions. The remaining amide groups in two dpo ligands separately generate the strong hydrogen-bonding interactions (N2−H2···O5 and N11−H11···O8) with two DEF molecules. The remaining DEF and MeCN molecules are only involved into the van der Waals interactions with the neighboring DEF guests.
After carefully checking the single-crystal diffraction patterns, no superstructures [30] are found in 2 amid spin transition. The structural parameters of two inequivalent FeⅡ sites in 2 are further explored in detail. The < Fe1−N > av/ < Fe2−N > av distances are 1.960/1.968, 2.056/2.077 and 2.171/2.184 Å at 120, 215 and 300 K, matching well with the LS, LS1/2HS1/2 and HS states, respectively, (Table S4 in Supporting information). Despite the similar variation of the < Fe−N > av distance, the octahedral distortion parameters ∑ show different tendency for Fe1 and Fe2 ions. ∑Fe2 increases monotonically in the order of 14.38° → 15.9° → 19.1° upon warming. However, ∑Fe1 decreases from 13.92° at 120 K to 13.3° at 215 K and then increases to 14.8° at 300 K, indicating the contribution of antiferro-elastic interaction in the LS1/2HS1/2 state. The unit cell volume, the Fe···Fe distances within the 3D framework and the Ag···Ag distances between two 3D frameworks increase monotonically upon warming, which contribute to the ferro-elastic interactions. The N···O distances and N−H···O angles in the bifurcated H-bond are monotonically increased and decreased, respectively, suggesting the ferro-elastic interactions between this guest and two 3D frameworks. Meanwhile, the other two strong hydrogen-bonding interactions are complicated, in which the N···O distances increase while the N−H···O angles show abnormal changes.
By introducing different guest molecules, complexes 1 and 2 exhibit four-step SCO behaviors with different spin transition temperatures and thermal hysteresis loops. To explore the magnetostructural relationship between 1 and 2, the structural data in the HS state are compared in detail. 1 and 2 possess the same structural components and topological network for the twofold-interpenetrated frameworks and the similar < Fe−N > av distance at the room temperature. However, the total guest volume in 2 is larger than that in 1, which should empirically result in the lower Tc value if only considering the effect of guest size [11]. Meanwhile, in order to adapt to the different sizes of solvent guests and host-guest interactions, the structural parameters of the framework are regulated accordingly. The average Fe−N≡C angles of 172.10° and 171.68° for Fe1 and Fe2 ions in 2 are larger than that in 1 (170.57°), which should result in the higher Tc value [14]. Therefore, the competition of the effects of larger guest size and Fe−N≡C angle gives rise to the higher Tc value in 2. In addition, the shorter Ag···Ag distance between two 3D frameworks in 2 contributes positively to the SCO cooperativity. When comparing the strong hydrogen- bonding interactions, the longer N···O distances and the smaller N−H···O angles are found in 2, which give negative contributions to SCO cooperativity. However, the bifurcated H-bond in 2 can directly link two sets of 3D frameworks and build new path to transmit the SCO cooperativity. Therefore, the improved hysteresis loop in 2 may result from the contributions of the stronger argentophilic interactions and the bifurcated H-bond.
In summary, we successfully constructed two Hofmann-type SCO complexes [Fe(dpo){Ag(CN)2}2]·3DMF (1) and [Fe(dpo){Ag(CN)2}2]·0.5MeCN·2DEF (2) by utilizing oxamide-functionalized ligand, which provided a platform to tune SCO behavior via hydrogen-bonding interactions. Accordingly, the framework adapted to the different guests and then exhibited different SCO behaviors. The magnetic data displayed four-step SCO behaviors with the sequence of LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS3/10HS7/10 → HS and LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS1/4HS3/4 → HS for 1 and 2 respectively. The higher Tc in 2 resulted from the competitive contributions of guest size effect and the larger Fe−N≡C angle. Meanwhile, the improved SCO cooperativity in 2 resulted from the contributions of the argentophilic interactions and bifurcated H-bond. In the future, this oxamide-decorated ligand can extend to other Hofmann-type system by altering the cyanometallate, which may yield fruitful SCO behaviors via hydrogen-bonding interactions.
Declaration of competing interest
Less
The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.
Acknowledgment
Less
This work was supported by the National Key Research and Development Program of China (No. 2018YFA0306001), the National Natural Science Foundation of China (Nos. 21950410521, 21771200 and 21773316), and the Pearl River Talent Plan of Guangdong (No. 2017BT01C161).
Supplementary materials
Less
Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2021.08.012
References
Less
[1]
P. Gütlich, H.A. Goodwin, Spin crossover in transition metal compounds Ⅰ-Ⅲ. In Top. Curr. Chem., Springer-Verlag: Berlin, 2004, pp. 233-235.
[2]
M.A. Halcrow, Spin-Crossover Materials: Properties and Applications, John Wiley and Sons Ltd. : West Sussex, 2013
[3]
S.I. Ohkoshi, K. Imoto, Y. Tsunobuchi, et al., Nat. Chem. 3 (2011) 564-569
[4]
H. Zheng, Y.S. Meng, G.L. Zhou, et al., Angew. Chem. Int. Ed. 57 (2018) 8468-8472
[5]
R.W. Hogue, S. Singh, S. Brooker, Chem. Soc. Rev. 47 (2018) 7303-7338
[6]
M. Paez-Espejo, M. Sy, K. Boukheddaden, J. Am. Chem. Soc. 138 (2016) 3202-3210
[7]
J. Cruddas, B.J. Powell, J. Am. Chem. Soc. 141 (2019) 19790-19799
[8]
L. Piñeiro-López, F.J. Valverde-Muñoz, E. Trzop, et al., Chem. Sci. 12 (2021) 1317-1326
[9]
T. Kitazawa, Y. Gomi, M. Takahashi, et al., J. Mater. Chem. 6 (1996) 119-121
[10]
P.D. Southon, L. Liu, E.A. Fellows, et al., J. Am. Chem. Soc. 131 (2009) 10998-11009
[11]
Z.P. Ni, J.L. Liu, M.N. Hoque, et al., Coord. Chem. Rev. 335 (2017) 28-43
[12]
J.E. Clements, J.R. Price, S.M. Neville, et al., Angew. Chem. Int. Ed. 55 (2016) 15105-15109
[13]
C.H. Pham, J. Cirera, F. Paesani, J. Am. Chem. Soc. 138 (2016) 6123-6126
[14]
N.F. Sciortino, K.A. Zenere, M.E. Corrigan, et al., Chem. Sci. 8 (2017) 701-707
[15]
T. Delgado, M. Meneses-Sánchez, L. Piñeiro-López, et al., Chem. Sci. 9 (2018) 8446-8452
[16]
C.J. Zhang, K.T. Lian, G.Z. Huang, et al., Chem. Commun. 55 (2019) 11033-11036
[17]
M.J. Murphy, K.A. Zenere, F. Ragon, et al., J. Am. Chem. Soc. 139 (2017) 1330-1335
[18]
W. Liu, Y.Y. Peng, S.G. Wu, et al., Angew. Chem. Int. Ed. 56 (2017) 14982-14986
[19]
R. Turo-Cortés, C. Bartual-Murgui, J. Castells-Gil, et al., Chem. Sci. 11 (2020), 11224-11234
[20]
M. Ohba, K. Yoneda, G. Agusti, et al., Angew. Chem. Int. Ed. 48 (2009) 4767-4771
[21]
Y. Meng, Y.J. Dong, Z. Yan, et al., Cryst. Growth Des. 18 (2018) 5214-5219
[22]
F.J. Valverde-Muñoz, C. Bartual-Murgui, L. Piñeiro-López, et al., Inorg. Chem. 58 (2019) 10038-10046
[23]
A.T. Brennan, K.A. Zenere, C.J. Kepert, et al., Inorg. Chem. 60 (2021) 3871-3878
[24]
D.J. Mondal, S. Roy, J. Yadav, et al., Inorg. Chem. 59 (2020) 13024-13028
[25]
C.J. Zhang, K.T. Lian, S.G. Wu, et al., Inorg. Chem. Front. 7 (2020) 911-917
[26]
M. Nihei, H. Tahira, N. Takahashi, et al., J. Am. Chem. Soc. 132 (2010) 3553-3560
[27]
A. Sugaya, S. Ueno, J. Okabayashi, et al., New J. Chem. 38 (2014) 1955-1958
[28]
P. Gütlich, A. Hauser, H. Spiering, Angew. Chem. Int. Ed. 33 (1994) 2024-2054
[29]
M. Feng, Z.Y. Ruan, Y.C. Chen, et al., Chem. Commun. 56 (2020) 13702-13718
[30]
N.F. Sciortino, K.R. Scherl-Gruenwald, G. Chastanet, et al., Angew. Chem. Int. Ed. 51 (2012) 10154-10158
Appendix
Less
Year 2022 volume 33 Issue 3
PDF
44
25
Cite this Article
BibTeX
Article Info
doi: 10.1016/j.cclet.2021.08.012
  • Receive Date：2021-05-31
  • Online Date：2025-12-12
  • Published：2022-03-15
Article Data
Affiliations
History
  • Received：2021-05-31
  • Revised：2021-06-18
  • Accepted：2021-08-05
Affiliations
    Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
References
Share
https://castjournals.cast.org.cn/joweb/ccl/EN/10.1016/j.cclet.2021.08.012
Share to
QR

Scan QR to access full text

Cite this article
BibTeX
Citations
表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
关闭全屏
  • BibTeX
  • EndNote
  • RefWorks
  • TxT
Links
Articles
Latest Articles
Most Read
Collections
Updates
Events
News
Multimedia
About
About Us
Contact
No. 86 Xueyuan South Road, Haidian District, Beijing
100081
010-62199257
qkjq@cast.org.cn

Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House