Two novel mononuclear neodymium alkoxides [Nd{OC(C
14
H
11
S
2
)}
3
(thf)
3
]·thf (
9
) and [Nd{OC(C
16
H
13
S)}
3
(thf)
3
]·thf (
10
) have been prepared by the reaction between Nd[N(SiMe
3
)
2
]
3
and the tertiary alcohols HO-C(C
14
H
11
S
2
) (
3
) and HO-C(C
16
H
13
S) (
4
). The geometry around the neodymium metal is almost octahedral with a facial ligand arrangement similar to [Nd{OC(C
8
H
5
S
2
)
3
}
3
(thf)
3
]·4thf (
5
), [Nd{OC(C
4
H
3
S)
3
}
3
(thf)
3
]·thf (
7
) and Er[OC(C
4
H
3
S)
3
]
3
(thf)
3
(
8
) (X-ray diffraction on single crystals). The cyclic voltammograms of a series of neodymium and erbium alkoxides indicate that the electrochemical properties are essentially dominated by the organic ligands. In comparison to the carbinols HO-C(C
8
H
5
S
2
)
3
(
1
), HO-C(C
4
H
3
S)
3
(
2
), HO-C(C
14
H
11
S
2
) (
3
) or HO-C(C
16
H
13
S) (
4
), the oxidation peak potentials of the thienyl units for the neodymium alkoxides [Nd{OC(C
8
H
5
S
2
)
3
}
3
(thf)
3
]·4thf (
5
), [Nd{OC(C
4
H
3
S)
3
}
3
(thf)
3
]·thf (
7
), [Nd{OC(C
14
H
11
S
2
)}
3
(thf)
3
]·thf (
9
) and [Nd{OC(C
16
H
13
S)}
3
(thf)
3
]·thf (
10
) are marginally shifted towards higher values by 0.03-0.10 V, whereas for Er[OC(C
8
H
5
S
2
)
3
]
3
(thf) (
6
) and Er[OC(C
4
H
3
S)
3
]
3
(thf)
3
(
8
) a decrease of these potentials is noticed. Repetitive cyclic voltammetry does not generate polymeric films for
7
–
10
, as found for the free organic ligands
2
–
4
. Contrarily, the mononuclear precursors [Nd{OC(C
8
H
5
S
2
)
3
}
3
(thf)
3
]·4thf (
5
) and Er[OC(C
8
H
5
S
2
)
3
]
3
(thf) (
6
) are electro-oxidized and electro-active polymer films are obtained and characterized. To investigate the positions of the excited states of the ligands, emission spectra of the carbinols
1
–
4
have been recorded. The luminescence studies of the neodymium alkoxides reveal an energy transfer from the ligand to the metal centre with a remarkable Nd emission efficiency upon ligand excitation in the case of
5
.