Screening for high-spin metal organic frameworks (MOFs): density functional theory study on DUT-8(M₁,M₂) (with M_i = V,…,Cu)

Abstract

We present a first principles study of low-spin (LS)/high-spin (HS) screening for 3d metal centers in the metal organic framework (MOF) DUT-8(Ni). Various density functional theory (DFT) codes have been used to evaluate numerical and DFT related errors. We compare highly accurate all-electron implementations with the widely used plane wave approach. We present electronically and magnetically stable DUT-8(Ni) HS secondary building units (SBUs). In this work we show how to tune the magnetic and electronic properties of the original SBU only by changing the metal centers.

Toward an automated analysis of exchange pathways in spin‐coupled systems

“…The energy differences considered in both models, and the way they enter eqs. (6) and (4), are illustrated in Figure 2.…”

“…Electron spin coupling plays an important role in systems such as organic diradicals and transition-metal complexes. For transition-metal complexes, substitutions of the metal centers [1][2][3][4] or modifications in the ligand sphere [5][6][7] affect the spin coupling, and understanding such structure-property relationships is relevant for designing molecules with desired magnetic properties. This also applies to active sites in enzymes, [8][9][10][11] and to spin coupling in magnetic metal organic frameworks.…”

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

“…Density functional theory (DFT) is one of the most commonly used electronic structure methods. Its popularity comes from its efficiency to calculate properties with reasonable accuracy for a range of systems including atoms, molecules, clusters, and condensed matter . While DFT is in principle exact, the exchange‐correlation functional E xc needs to be approximated to solve the Kohn–Sham (KS) equations in practical calculations.…”

“…Its popularity comes from its efficiency to calculate properties with reasonable accuracy for a range of systems including atoms, molecules, [3][4][5][6] clusters, [7] and condensed matter. [8][9][10][11][12][13][14][15] While DFT is in principle exact, the exchange-correlation functional E xc needs to be approximated to solve the Kohn-Sham (KS) equations in practical calculations. These density functional approximations (DFAs) often work well, but are known to produce incorrect results for rather simple cases like the dissociation of the H 2 molecule [16] or band gaps in semiconductors that are far from experimental values.…”

A Ligand Field Molecular Mechanics Study of CO2‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

“…Motivated by its outstanding properties, DUT-8(Ni) is being investigated extensively recently. [12][13][14][15][16][17][18][19][20][21][22][23] Some examples of the properties of interest are the enormous volume change upon opening (more than 140 %), [14] its isomorphism, [22] the property dependence on the metal center, [14] and crystallite size effects. [19] Alzahrani and Deeth [24] already employed LFMM to investigate clusters of Zn 2 (bdc) 2 (dabco) and showed the applicability to this structurally related flexible MOF.…”