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Concomitant Photoresponsive Chiroptics and Magnetism in Metal-Organic Frameworks at Room Temperature.

ABSTRACT: Stimulus-responsive metal-organic frameworks (MOFs) can be used for designing smart materials. Herein, we report a family of rationally designed MOFs which exhibit photoresponsive chiroptical and magnetic properties at room temperature. In this design, two specific nonphotochromic ligands are selected to construct enantiomeric MOFs, {Cu₂(L-mal)₂(bpy)₂(H₂O)·3H₂O}_n (1) and {Cu₂(D-mal)₂(bpy)₂(H₂O)·3H₂O}_n (2) (mal = malate, bpy = 4, 4' - bipyridine), which can alter their color, magnetism, and chiroptics concurrently in response to light. Upon UV or visible light irradiation, long-lived bpy^- radicals are generated via photoinduced electron transfer (PET) from oxygen atoms of carboxylates and hydroxyl of malates to bpy ligands, giving rise to a 23.7% increase of magnetic susceptibility at room temperature. The participation of the chromophores (-OH and -COO^-) bound with the chiral carbon during the electron transfer process results in a small dipolar transition; thus, the Cotton effects of the enantiomers are weakened along with a photoinduced color change. This work demonstrates that the simultaneous responses of chirality, optics, and magnetism can be achieved in a single compound at room temperature and may open up a new pathway for designing chiral stimuli-responsive materials.

SUBMITTER: Xia B

PROVIDER: S-EPMC7894082 | biostudies-literature | 2021

REPOSITORIES: biostudies-literature

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Concomitant Photoresponsive Chiroptics and Magnetism in Metal-Organic Frameworks at Room Temperature.

Xia Bin B Gao Qian Q Hu Zhen-Peng ZP Wang Qing-Lun QL Cao Xue-Wei XW Li Wei W Song You Y Bu Xian-He XH

Research (Washington, D.C.) 20210210

Stimulus-responsive metal-organic frameworks (MOFs) can be used for designing smart materials. Herein, we report a family of rationally designed MOFs which exhibit photoresponsive chiroptical and magnetic properties at room temperature. In this design, two specific nonphotochromic ligands are selected to construct enantiomeric MOFs, {Cu2(L-mal)2(bpy)2(H2O)·3H2O}n (1) and {Cu2(D-mal)2(bpy)2(H2< ...[more]

PMID: 33644763

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Project description:We use first-principles calculations to show that the square symmetry of two-dimensional (2D) metal-organic frameworks (MOFs) made from octaamino-substituted phthalocyanines and square planar Ni2+ ions, which enable strong conjugation of π electrons, has a critical impact on the magnetic properties of the lattice. In particular, we predict the unexpected emergence of a rare high-temperature ferromagnetic half-metallic ground state in one case. Among charge neutral MOFs made from (2,3,9,10,16,17,23,24)-octaiminophthalocyanine (OIPc) metallated with divalent first-row transition metal ions (M-OIPc; M = Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) and connected through square planar Ni-bisphenylenediimine moieties, NiMn-OIPc exhibits a half-metallic and ferromagnetic ground state with a large exchange energy resulting from the unique strong hybridization between the d/π orbitals of Mn, the Pc ring, and the Ni-bisphenylenediimine nodes. Notably, we show that for NiMn-OIPc there is a considerable difference between the ferromagnetic ordering temperature (Tc) predicted by a 2D Ising model, which exceeds 600 K, and a Tc of 170 K predicted by our more realistic Monte Carlo simulation that includes magnetic anisotropy. Critically, our simulations adopt two spin models that incorporate magnetic anisotropy in the form of exchange anisotropy and single-ion anisotropy. We further show that in the bulk, 2D layers of NiMn-OIPc adopt a slipped-parallel stacking configuration, and exhibit interlayer magnetic coupling that is sensitive to the relative in-plane displacement between adjacent layers. These results highlight the critical role of magnetic anisotropy in modeling the properties of 2D magnetic systems. More generally, it demonstrates that strong hybridization between open-shell ions and delocalized aromatic π systems with appropriate symmetry, combined with large magnetic anisotropy, will be an effective design strategy to realize ferromagnetic 2D MOFs with high Tc.

Dataset Information

Concomitant Photoresponsive Chiroptics and Magnetism in Metal-Organic Frameworks at Room Temperature.

Publications

Concomitant Photoresponsive Chiroptics and Magnetism in Metal-Organic Frameworks at Room Temperature.

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