journal article·2022-09-07Open access

Thickness-dependent spin bistable transitions in single-crystalline molecular 2D material

John Koptur-Palenchar, Miguel Gakiya-Teruya, Duy Le, Jun Jiang, Rui Zhang, Xuanyuan Jiang, Hai-Ping Cheng, Talat S. Rahman, Michael Shatruk, Xiao-Xiao Zhang

Abstract

Abstract The advent of two-dimensional (2D) crystals has led to numerous scientific breakthroughs. Conventional 2D systems have in-plane covalent bonds and a weak out-of-plane van-der-Waals bond. Here we report a new type of 2D material composed of discrete magnetic molecules, where anisotropic van-der-Waals interactions bond the molecules into a 2D packing. Through mechanical exfoliation, we can obtain single-crystalline molecular monolayers, which can be readily integrated into other 2D systems. Optical spectroscopy suggests the few-layered molecules preserve the temperature-induced spin-crossover switching observed in the bulk form but show a drastic increase in thermal hysteresis unique to these thin 2D molecule assemblies. The trapping of spin bistability with decreasing layer number can arise from domain wall dynamics in reduced dimensions. Our results establish molecular solids with strong anisotropy of intermolecular interactions as precursors to a new class of 2D materials, affording possibilities to control molecular functionalities through substrate and interlayer interactions.
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Research context

OpenAlex topics: 2D Materials and Applications · Graphene research and applications · Perovskite Materials and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (38)

Show source-provided references
1. Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).10.1126/science.aac9439 ↗
2. Geim, A. K. & Grigorieva, I. V. Van der Waals heterostructures. Nature 499, 419–425 (2013).10.1038/nature12385 ↗
3. Gibertini, M., Koperski, M., Morpurgo, A. F. & Novoselov, K. S. Magnetic 2D materials and heterostructures. Nat. Nanotechnol. 14, 408–419 (2019).10.1038/s41565-019-0438-6 ↗
4. Zhou, J. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).10.1038/s41586-018-0008-3 ↗
5. Manzeli, S., Ovchinnikov, D., Pasquier, D., Yazyev, O. V. & Kis, A. 2D transition metal dichalcogenides. Nat. Rev. Mater. 2, 17033 (2017).10.1038/natrevmats.2017.33 ↗
6. Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43 https://www.nature.com/articles/nature26160#supplementary-information (2018).10.1038/nature26160 ↗
7. Lu, X. et al. Superconductors, orbital magnets and correlated states in magic-angle bilayer graphene. Nature 574, 653–657 (2019).10.1038/s41586-019-1695-0 ↗
8. Liu, Y. et al. Van der Waals heterostructures and devices. Nat. Rev. Mater. 1, 16042 (2016).10.1038/natrevmats.2016.42 ↗
9. Feng, X. & Schlüter, A. D. Towards macroscopic crystalline 2D polymers. Angew. Chem. Int. Ed. 57, 13748–13763 (2018).10.1002/anie.201803456 ↗
10. Zhong, Y. et al. Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices. Science 366, 1379 (2019).10.1126/science.aax9385 ↗
11. Wang, C. et al. Monolayer atomic crystal molecular superlattices. Nature 555, 231–236 (2018).10.1038/nature25774 ↗
12. López-Cabrelles, J. et al. Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization. Nat. Chem. 10, 1001–1007 (2018).10.1038/s41557-018-0113-9 ↗
13. Gobbi, M., Orgiu, E. & Samorì, P. When 2D materials meet molecules: opportunities and challenges of hybrid organic/inorganic van der Waals heterostructures. Adv. Mater. 30, 1706103 (2018).10.1002/adma.201706103 ↗
14. Liu, Y., Huang, Y. & Duan, X. Van der Waals integration before and beyond two-dimensional materials. Nature 567, 323–333 (2019).10.1038/s41586-019-1013-x ↗
15. Torres-Cavanillas, R. et al. Spin-crossover nanoparticles anchored on MoS2 layers for heterostructures with tunable strain driven by thermal or light-induced spin switching. Nat. Chem. https://doi.org/10.1038/s41557-021-00795-y (2021).10.1038/s41557-021-00795-y ↗
16. Dong, R., Zhang, T. & Feng, X. Interface-assisted synthesis of 2D materials: trend and challenges. Chem. Rev. 118, 6189–6235 (2018).10.1021/acs.chemrev.8b00056 ↗
17. Boix-Constant, C. et al. Strain switching in van der Waals heterostructures triggered by a spin-crossover metal–organic framework. Adv. Mater. 34, 2110027 (2022).10.1002/adma.202110027 ↗
18. Dong, J. et al. Free-standing homochiral 2D monolayers by exfoliation of molecular crystals. Nature 602, 606–611 (2022).10.1038/s41586-022-04407-8 ↗
19. Cinchetti, M., Dediu, V. A. & Hueso, L. E. Activating the molecular spinterface. Nat. Mater. 16, 507–515 (2017).10.1038/nmat4902 ↗
20. Coronado, E. Molecular magnetism: from chemical design to spin control in molecules, materials and devices. Nat. Rev. Mater. 5, 87–104 (2020).10.1038/s41578-019-0146-8 ↗
21. Gaita-Ariño, A., Luis, F., Hill, S. & Coronado, E. Molecular spins for quantum computation. Nat. Chem. 11, 301–309 (2019).10.1038/s41557-019-0232-y ↗
22. Wasielewski, M. R. et al. Exploiting chemistry and molecular systems for quantum information science. Nat. Rev. Chem. 4, 490–504 (2020).10.1038/s41570-020-0200-5 ↗
23. Atzori, M. & Sessoli, R. The second quantum revolution: role and challenges of molecular chemistry. J. Am. Chem. Soc. 141, 11339–11352 (2019).10.1021/jacs.9b00984 ↗
24. Schwartz, D. K. Mechanisms and kinetics of self-assembled monolayer formation. Annu. Rev. Phys. Chem. 52, 107–137 (2001).10.1146/annurev.physchem.52.1.107 ↗
25. Gakiya-Teruya, M. et al. Asymmetric design of spin-crossover complexes to increase the volatility for surface deposition. J. Am. Chem. Soc. 143, 14563–14572 (2021).10.1021/jacs.1c04598 ↗
26. Li, Y. & Heinz, T. F. Two-dimensional models for the optical response of thin films. 2D Mater. 5, 025021 (2018).10.1088/2053-1583/aab0cf ↗
27. Hauser, A. Light-induced spin crossover and the high-spin→ low-spin relaxation. Spin Crossover Transition Metal Compounds II, 155–198 (2004).10.1007/b95416 ↗
28. Chakraborty, P., Enachescu, C., Walder, C., Bronisz, R. & Hauser, A. Thermal and light-induced spin switching dynamics in the 2D coordination network of {[Zn1-xFex(bbtr)3](ClO4)2}∞: the role of cooperative effects. Inorg. Chem. 51, 9714–9722 (2012).10.1021/ic301006c ↗
29. Phan, H. V. et al. Heteroleptic feii complexes of 2,2′-biimidazole and its alkylated derivatives: spin-crossover and photomagnetic behavior. Chemistry 18, 15805–15815 (2012).10.1002/chem.201202045 ↗
30. Chergui, M. & Collet, E. Photoinduced structural dynamics of molecular systems mapped by time-resolved X-ray methods. Chem. Rev. 117, 11025–11065 (2017).10.1021/acs.chemrev.6b00831 ↗
31. Ohkoshi, S.-i., Imoto, K., Tsunobuchi, Y., Takano, S. & Tokoro, H. Light-induced spin-crossover magnet. Nat. Chem. 3, 564–569 (2011).10.1038/nchem.1067 ↗
32. Kipgen, L., Bernien, M., Tuczek, F. & Kuch, W. Spin-crossover molecules on surfaces: from isolated molecules to ultrathin films. Adv. Mater. 33, 2008141 (2021).10.1002/adma.202008141 ↗
33. Dai, Z., Liu, L. & Zhang, Z. Strain engineering of 2D materials: issues and opportunities at the interface. Adv. Mater. 31, 1805417 (2019).10.1002/adma.201805417 ↗
34. Li, W., Qian, X. & Li, J. Phase transitions in 2D materials. Nat. Rev. Mater. https://doi.org/10.1038/s41578-021-00304-0 (2021).10.1038/s41578-021-00304-0 ↗
35. Onuki, A. Phase Transition Dynamics (Cambridge University Press, 2002).10.1017/CBO9780511534874 ↗
36. Enachescu, C., Stoleriu, L., Stancu, A. & Hauser, A. Model for elastic relaxation phenomena in finite 2D hexagonal molecular lattices. Phys. Rev. Lett. 102, 257204 (2009).10.1103/PhysRevLett.102.257204 ↗
37. Stoleriu, L., Chakraborty, P., Hauser, A., Stancu, A. & Enachescu, C. Thermal hysteresis in spin-crossover compounds studied within the mechanoelastic model and its potential application to nanoparticles. Phys. Rev. B 84, 134102 (2011).10.1103/PhysRevB.84.134102 ↗
38. Castellanos-Gomez, A. et al. Deterministic transfer of two-dimensional materials by all-dry viscoelastic stamping. 2D Mater. 1, 011002 (2014).10.1088/2053-1583/1/1/011002 ↗