The crystal structure of aqua-tris (1,3-diphenylpropane-1,3-dionato-κ2
 O,O′)-lanthanum(III), C45H35LaO7

Hickson, Matthew; Sephton, Abigail; Dugmore, Travis; Hosten, Eric C.; Betz, Richard

doi:10.1515/ncrs-2020-0504

Cited by 2 publications

(8 citation statements)

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“…The shape of the isosurface is triangular rather than circular, meaning that there is no free rotation; this is due to strong interaction with the o1 in the DBM. The preferential positioning of hw in water toward o1 with 1/3 occupancy was revealed for La(III) aqua-tris(dibenzoylmethane) by SC-XRD, and this is in agreement with the shape of the isosurface in Figure . This inconsistency may be caused by arbitrary refinement of the H position by SC-XRD analysis.…”

Section: Force-field Validationsupporting

confidence: 85%

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

et al. 2023

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The seven-coordinate Ho(III) aqua-tris-(dibenzoylmethane)(DBM) complex, referred to as Ho-(DBM) 3 • H 2 O, was first reported in the late 1960s. It has a threefold symmetric structure, with Ho at the center of three dibenzoylmethane ligands and hydrogen-bonded water to ligands. It is considered that the hydrogen bonds between the water molecule and the ligands surrounding Ho play an important role in the formation of its symmetrical structure. In this work, we developed new force-field parameters for classical molecular dynamics (CMD) simulations to theoretically elucidate the structure and dynamics of Ho-(DBM) 3 •H 2 O. To develop the force field, structural optimization and molecular dynamics were performed on the basis of ab initio calculations using the plane-wave pseudopotential method. The force-field parameters for CMD were then optimized to reproduce the data obtained from ab initio calculations. Validation of the developed force field showed good agreement with the experimental crystalline structure and ab initio data. The vibrational properties of water in Ho-(DBM) 3 •H 2 O were investigated by comparison with bulk liquid water. The vibrational motion of water was found to have a characteristic mode originating from stationary rotational motion along the c-axis of Ho(III) aqua-tris(dibenzoylmethane). Contrary to expectations, the hydrogen-bond dynamics of water in Ho-(DBM) 3 •H 2 O were found to be almost equivalent to those of bulk liquid water except for librational motion. This development route for force-field parameters for CMD and the establishment of water dynamics can advance the understanding of water-coordinated metal complexes with high coordination numbers such as Ho-(DBM) 3 •H 2 O.

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Section: Force-field Validationsupporting

confidence: 85%

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

et al. 2023

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show abstract

“…The shape of the isosurface is triangular rather than circular, meaning that there is not free rotation; this is due to strong interaction with the o1= in the DBM. The preferential positioning of hw in water toward o1= with 1/3 occupancy was revealed for La(III) aqua-tris(dibenzoylmethane) by SC-XRD, 3 and this is in agreement with the shape of the isosurface in Fig. 5.…”

Section: Forcefield Validationsupporting

confidence: 83%

“…Unique lanthanide complexes with dibenzoylmethane (DBM) ligands, which are propellershaped molecules, have been studied both for their structural characteristics [1][2][3][4][5] and for application-oriented synthesis. 6 Compounds of lanthanides with +3 oxidation states are important for nuclear-fuel processing 7,8 and magnetic resonance imaging.…”

Section: Introductionmentioning

confidence: 99%

“…12 A seven-coordinate complex structure such as Ho-(DBM) 3 • H 2 O has three-fold symmetry capped with a water molecule, and it exhibits strong luminescence and a very large radiative rate constant. 13,14 Although a considerable number of studies has been conducted regarding synthesis toward applications and single-crystal structural analysis, [1][2][3][4][5] molecular dynamics (MD) simulations of crystalline lanthanide complexes cannot be routinely performed. 15 A wide range of simulation studies has been carried out to understand the structure and dynamics of metal-organic compounds during recent decades (for instance, Refs.…”

Section: Introductionmentioning

confidence: 99%

“…Lattice constants, density in g/cm3 , and mean Ho-o1= and Ho-ow distances in Å. The experimental X-ray results were obtained SC-XRD analysis at 153 K. The PBE and DFT-D3 rows indicate the results of static structural optimization with and without vdW interactions.…”

mentioning

confidence: 99%

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Molecular dynamics studies of Ho(III) aqua-tris(dibenzoylmethane) complex: Role of water dynamics

Ohkubo¹,

Komiyama

Masu

et al. 2023

Preprint

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The seven-coordinate Ho(III) aqua-tris(dibenzoylmethane) complex, referred to as Ho-(DBM)3.H2O, was first reported in the late 1960s. It has a three-fold symmetric structure, with Ho at the center of three {\ligand} ligands and hydrogen bonded to a water molecule. It is considered that the hydrogen bonds between the water molecule and the ligands surrounding Ho play an important role in the formation of its symmetrical structure. In this work, we developed new force-field parameters for classical molecular dynamics (CMD) simulations to theoretically elucidate the structure and dynamics of Ho-(DBM)3.H2O. To develop the force field, structural optimization and molecular dynamics were performed on the basis of ab initio calculations using the plane-wave pseudopotential method. The force-field parameters for CMD were then optimized to reproduce the data obtained from the ab initio calculations. Validation of the developed force field showed good agreement with the experimental crystalline structure and the ab initio data. The vibrational properties of water in Ho-(DBM)3.H2O were investigated by comparison with bulk liquid water. The vibrational motion of water was found to have a characteristic mode originating from stationary rotational motion along the c axis of Ho(III) aqua-tris(dibenzoylmethane). Contrary to expectations, the hydrogen-bond dynamics of water in Ho-(DBM)3.H2O were found to be almost equivalent to those of bulk liquid water except for librational motion. This development route for force-field parameters for CMD and the establishment of water dynamics can advance the understanding of water-coordinated metal complexes with high coordination numbers such as Ho-(DBM)3.H2O.

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The crystal structure of aqua-tris (1,3-diphenylpropane-1,3-dionato-κ² O,O′)-lanthanum(III), C₄₅H₃₅LaO₇

Abstract: C45H35LaO7, trigonal, R3 (no. 146), a = 22.3832(11) Å, c = 6.4522(3) Å, V = 2799.5(3) Å3, Z = 3, Rgt(F) = 0.0192, wRref(F2) = 0.0462, T = 200 K.

Cited by 2 publications

References 15 publications

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

Molecular dynamics studies of Ho(III) aqua-tris(dibenzoylmethane) complex: Role of water dynamics

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The crystal structure of aqua-tris (1,3-diphenylpropane-1,3-dionato-κ2 O,O′)-lanthanum(III), C45H35LaO7

Abstract: C45H35LaO7, trigonal, R3 (no. 146), a = 22.3832(11) Å, c = 6.4522(3) Å, V = 2799.5(3) Å3, Z = 3, Rgt(F) = 0.0192, wRref(F2) = 0.0462, T = 200 K.

Cited by 2 publications

References 15 publications

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

Molecular Dynamics Studies of the Ho(III) Aqua-tris(dibenzoylmethane) Complex: Role of Water Dynamics

Molecular dynamics studies of Ho(III) aqua-tris(dibenzoylmethane) complex: Role of water dynamics

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The crystal structure of aqua-tris (1,3-diphenylpropane-1,3-dionato-κ² O,O′)-lanthanum(III), C₄₅H₃₅LaO₇