3d Transition Metal-Metallofullerene-Ligand Molecular Wires: Robust One-Dimensional Antiferromagnetic Semiconductors

Abstract

The structures and properties of one-dimensional (1D) sandwich molecular wires constructed with altering 3d transition metal (TM) and the metallofullerene (TM@C 60 ) entities, [TM&(TM@C 60 )] ∞ , are studied using density functional theory calculations. Different from the bonding character insensitivity to TM of previously reported 1D [TMBz] ∞ and [TMCp] ∞ analogues, the bonding characters of the investigated 1D [TM&(TM@C 60 )] ∞ molecular wires depend heavily on the identity of metal elements. In 1D [TM&(TM@C 60 )] ∞ , molecular wires with early TMs like Ti and V, TM-η 5 coordinate bonds are favored. In contrast, TM-η 6 bonding conformations are energetically preferred for those with later TMs, for example, Cr−Ni. Bader charge analysis reveals that valence electrons are transferred from both encapsulated and sandwiched TM atoms to the C 60 ligand. More importantly, all the molecular wires in ground states are robust antiferromagnetic semiconductors because of the peierls distortion of the configurations and the moderate binding energies. Therefore, the fabrication of endohedral metallofullerenes offers an effective route to regulate the magnetism and electronic properties of C 60 −ligand sandwich complexes.

Catalysis to discriminate single atoms from subnanometric ruthenium particles in ultra-high loading catalysts

“…As a consequence in our models we will retain only the wire configuration. 47 This result is consistent with the fact that the -(D-Ru 1 @C 60 ) npolymer does not swell in CH 2 Cl 2 , so that the additional Ru atoms cannot be incorporated in the structure due to diffusional limitations, and nucleation occurs on the surface of the nanospheres. The polymer swelling could favor the incorporation of additional Ru in the structure, and cluster/NP formation.…”

Uniaxially Aligned 1D Sandwich-Molecular Wires: Electronic Structure and Magnetism

“…, they can act as spin filters. Half-metal and spin-filter properties have also been discussed by theory for transition-metal-cyclopentadien complexes − or complexes containing larger molecules such as cyclononatetraenyl or metallofullerenes . Recently, also cyclopentadienyl-titanium-cyclooctatetraene double deckers have even been discussed in the context of molecular spin qubits …”

“…Half-metal and spin-filter properties have also been discussed by theory for transitionmetal-cyclopentadien complexes 25−27 or complexes containing larger molecules such as cyclononatetraenyl 28 or metallofullerenes. 29 Recently, also cyclopentadienyl-titanium-cyclooctatetraene double deckers have even been discussed in the context of molecular spin qubits. 30 Here, we focus on sandwich-molecular wires consisting of an alternating sequence of lanthanide (Ln) atoms and the eightmembered carbon ring cyclooctatetraene (C 8 H 8 , Cot).…”

Ab Initio Study of Structural, Electronic and Magnetic Properties of TM&(B@C60) (TM = V, Cr) Sandwich Clusters and Infinite Molecular Wires

“…Different from organic planar ligands (C n H n , n = 5-8) [16][17][18][19][20][21][22], the cage configuration of fullerenes enable their large spaces to accommodate other atoms or molecules for forming various core/shell complexes [23][24][25][26][27][28][29][30][31][32], which endows novel electronic properties on them and their TM-fullerene sandwich derivatives. For example, 1D infinite molecular wires, [TM&(TM@C 60 )] ∞ (TM = Ti-Ni), composed of metallofullerene (TM@C 60 ) [23,33,34] and 3d TM atoms, were identified as displaying robust antiferromagnetic (AFM) semiconducting properties [20]. Unfortunately, the physical and chemical properties of sandwich isomers with different endoped fullerenes are rarely investigated.…”