V. Amendola et al., pH-controlled translocation of Ni-II within a ditopic receptor bearing an appended anthracene fragment: a mechanical switch of fluorescence, J CHEM S DA, (2), 2000, pp. 185-189
Citations number
26
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The sexidentate ligand 1 offers two distinct adjacent quadridentate coordin
ating compartments: a compartment B, consisting of two amine nitrogen atoms
and two quinoline nitrogen atoms, and a poorly coordinating compartment AH
(2), consisting of two amine nitrogen atoms and two amide nitrogen atoms, w
hich, on deprotonation of the two amide groups, give the strongly coordinat
ing donor set A(2-). Potentiometric and spectroscopic studies have shown th
at at pH=7.5 the Ni-II ion stays in the B compartment (high-spin state, oct
ahedral stereochemistry) and at pH greater than or equal to 9.5, Ni-II is l
ocated in the adjacent A(2-) compartment, as a low-spin centre, in a square
stereochemistry. Thus, the Ni-II centre can be translocated from one compa
rtment to the other by varying the pH from 7.5 to 9.5 and vice versa. The B
-to-AH(2) translocation (tau=0.25 +/- 0.01 s) is faster than the reverse A(
2-)-to-B process (tau=2.2 +/- 0.1 s). When an anthracene (An) fragment is c
ovalently linked to the AH(2) moiety (system 2), the translocation of the N
i-II ion switches ON/OFF the An fluorescent emission, depending on whether
the metal is positioned in the A(2-) (OFF) or B compartment (ON). Quenching
is due to a Ni-II-to-An* electron transfer process. Owing to steric hindra
nce of the bulky An substituent, both direct (B-to-AH(2), tau=12 +/- 1 s) a
nd reverse (A(2-)-to-B, tau=66 +/- 12 s) processes are distinctly slower th
an observed for system 1.