TY - JOUR
T1 - Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex
AU - White, Frankie D.
AU - Celis-Barros, Cristian
AU - Rankin, Jillian
AU - Solís-Céspedes, Eduardo
AU - Dan, David
AU - Gaiser, Alyssa N.
AU - Zhou, Yan
AU - Colangelo, Jasmine
AU - Páez-Hernández, Dayán
AU - Arratia-Pérez, Ramiro
AU - Albrecht-Schmitt, Thomas E.
N1 - Funding Information:
This joint work was supported as part of the Center for Actinide Science and Technology (CAST), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0016568 and the Heavy Elements Chemistry Program (HEC) under Award Number DE-FG02-13ER16414. CAST provided the computational aspects of the research while (HEC) provided the experimental research. Part of the computational calculations were provided by Fondecyt 1180017 and Fondecyt 1150629 grants.
PY - 2019/3/4
Y1 - 2019/3/4
N2 -
The reaction of SmI
2
with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu
4
N][BPh
4
], allows for the isolation of [Sm
II
(DB30C10)][BPh
4
]
2
as bright-red crystals in good yield. Exposure of [Sm(DB30C10)]
2+
to solvents containing trace water results in the conversion to the dinuclear Sm
III
complex, Sm
2
(DB30C10)(OH)
2
I
4
. Structural analysis of both complexes shows substantial rearrangement of the crown ether from a folded, Pac-Man form with Sm
II
to a twisted conformation with Sm
III
. The optical properties of [Sm
II
(DB30C10)][BPh
4
]
2
exhibit a strong temperature dependence and change from broad-band absorption features indicative of domination by 5d states to fine features characteristic of 4f 4f transitions at low temperatures. Examination of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) shows that the ground state of Sm
II
in [Sm
II
(DB30C10)]
2+
is a 4f
6
state with low-lying 4f
5
5d
1
states, where the latter states have been lowered in energy by 12 000 cm
-1
with respect to the free ion. The decacoordination of the Sm
II
cation by the crown ether is responsible for this alteration in the energies of the excited state and demonstrates the ability to tune the electronic structure of Sm
II
.
AB -
The reaction of SmI
2
with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu
4
N][BPh
4
], allows for the isolation of [Sm
II
(DB30C10)][BPh
4
]
2
as bright-red crystals in good yield. Exposure of [Sm(DB30C10)]
2+
to solvents containing trace water results in the conversion to the dinuclear Sm
III
complex, Sm
2
(DB30C10)(OH)
2
I
4
. Structural analysis of both complexes shows substantial rearrangement of the crown ether from a folded, Pac-Man form with Sm
II
to a twisted conformation with Sm
III
. The optical properties of [Sm
II
(DB30C10)][BPh
4
]
2
exhibit a strong temperature dependence and change from broad-band absorption features indicative of domination by 5d states to fine features characteristic of 4f 4f transitions at low temperatures. Examination of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) shows that the ground state of Sm
II
in [Sm
II
(DB30C10)]
2+
is a 4f
6
state with low-lying 4f
5
5d
1
states, where the latter states have been lowered in energy by 12 000 cm
-1
with respect to the free ion. The decacoordination of the Sm
II
cation by the crown ether is responsible for this alteration in the energies of the excited state and demonstrates the ability to tune the electronic structure of Sm
II
.
UR - http://www.scopus.com/inward/record.url?scp=85062430138&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b03566
DO - 10.1021/acs.inorgchem.8b03566
M3 - Article
C2 - 30788962
AN - SCOPUS:85062430138
SN - 0020-1669
VL - 58
SP - 3457
EP - 3465
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -