Loading…
A new heterometallic terbium( iii )–ruthenium( ii ) complex and its terbium( iii )–zinc( ii ) analog: syntheses, characterization, luminescence, and electrochemical properties
Synthesis of a d–f heterometallic trinuclear complex [Tb(NO 3 ) 2 ( L2 ){Ru(ttpy)} 2 ](PF 6 ) 5 ( 6 ) ( L2 = N 1 , N 2 -bis(2-(( Z )-2-(4-(2,2′:6′,2′′)-terpyridin-4′-yl-benzyloxy)benzylideneamino)ethyl)ethane-1,2-diamine; ttpy = 4′-tolyl-2,2′:6′,2′′-terpyridine) and intramolecular energy transfer fr...
Saved in:
| Published in: | New journal of chemistry 2015-01, Vol.39 (6), p.4284-4294 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Article |
| Language: | English |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | Synthesis of a d–f heterometallic trinuclear complex [Tb(NO
3
)
2
(
L2
){Ru(ttpy)}
2
](PF
6
)
5
(
6
) (
L2
=
N
1
,
N
2
-bis(2-((
Z
)-2-(4-(2,2′:6′,2′′)-terpyridin-4′-yl-benzyloxy)benzylideneamino)ethyl)ethane-1,2-diamine; ttpy = 4′-tolyl-2,2′:6′,2′′-terpyridine) and intramolecular energy transfer from terbium(
iii
) to ruthenium(
ii
) at room temperature are reported. 2-(4-(2,2′:6′,2′′)-Terpyridin-4′-yl-benzyloxy)benzaldehyde (
L1
) is characterized by X-ray diffraction: triclinic,
P
1̄. The terbium(
iii
) complex [Tb(NO
3
)
2
(
L2
)]NO
3
·5H
2
O (
2
) is synthesized by Schiff base condensation of triethylenetetraamine with
L1
in the presence of Tb(NO
3
)
3
·5H
2
O as the template as well as by the reaction of the preformed Schiff base
L2
with Tb(NO
3
)
3
·5H
2
O. The dinuclear complex [{Ru(ttpy)}
2
(
L2
)](PF
6
)
4
(
5
) is synthesized by Schiff base condensation of triethylenetetraamine with the mononuclear complex [Ru(
L1
)(ttpy)](PF
6
)
2
(
4
). The terbium(
iii
) complex
2
exhibits a set of seven emission bands at 490, 545, 585, 622, 651, 668, and 684 nm characteristic of the
5
D
4
→
7
F
0–6
transitions of terbium(
iii
). The Tb
III
–Ru
II
d–f heterometallic complex
6
exhibits emission at 687 nm characteristic of the ruthenium(
ii
) tolylterpyridine molecular components. Ruthenium(
ii
) luminescence is sensitized at room temperature by intramolecular intercomponent energy transfer from the luminescent
5
D
4
metal centered excited state of terbium(
iii
) to the
3
MLCT state of ruthenium(
ii
) with a concomitant increase in the ruthenium(
ii
) luminescence lifetime of 1.20 ns. The Tb
III
–Zn
II
heterometallic assembly [Tb(NO
3
)
2
(
L2
){Zn(ttpy)}
2
](PF
6
)
5
(
7
) exhibits emission bands characteristic of the terbium(
iii
) center. The results indicate photoinduced intramolecular energy transfer from the ttpy moieties of the [Zn(ttpy)
2
]
2+
molecular components to the terbium(
iii
) center. This study demonstrates the use of the terpyridine derivative appended terbium(
iii
) complex as a synthon for the construction of heterometallic d–f assemblies. The two ruthenium(
ii
) centers of
6
undergo electrochemical oxidation at the same potential (the
E
1/2
for the Ru(
ii
)/Ru(
iii
) redox couple is 0.93 V) indicating their electrochemical equivalence. |
|---|---|
| ISSN: | 1144-0546 1369-9261 |
| DOI: | 10.1039/C5NJ00082C |