4 research outputs found
Low-Energy and Long-Lived Emission from Polypyridyl Ruthenium(II) Complexes Having A Stable-Radical Substituent
Novel polypyridyl
rutheniumĀ(II) complexes having a 2,2ā²-bipyridine (bpy) derivative
which possesses a 1,5-dimethyl-6-oxoverdazyl radical (OV) group as
a stable-radical substituent were designed and synthesized. The radicalārutheniumĀ(II)
complexes showed low-energy/intense MLCT absorption and low-energy/long-lived
MLCT emission, and these characteristics of the complexes were explained
by the electron-withdrawing nature of the OV group. Furthermore, the
radical-substituent effects were enhanced by the presence of the electron-donating
methyl groups at the 4- and 4ā²-positions of bpy in the ancillary
ligands. The detailed electrochemical, spectroscopic, and photophysical
properties of the complexes were discussed in terms of the systematic
modification of the second coordination sphere in the main and ancillary
ligands
Anion-Controlled Assembly of Four Manganese Ions: Structural, Magnetic, and Electrochemical Properties of Tetramanganese Complexes Stabilized by Xanthene-Bridged Schiff Base Ligands
The reaction of manganeseĀ(II) acetate with a xanthene-bridged
bisĀ[3-(salicylideneamino)-1-propanol]
ligand, H<sub>4</sub>L, afforded the tetramanganeseĀ(II,II,III,III)
complex [Mn<sub>4</sub>(L)<sub>2</sub>(Ī¼-OAc)<sub>2</sub>],
which has an incomplete double-cubane structure. The corresponding
reaction using manganeseĀ(II) chloride in the presence of a base gave
the tetramanganeseĀ(III,III,III,III) complex [Mn<sub>4</sub>(L)<sub>2</sub>Cl<sub>3</sub>(Ī¼<sub>4</sub>-Cl)Ā(OH<sub>2</sub>)], in
which four Mn ions are bridged by a Cl<sup>ā</sup> ion. A pair
of L ligands has a propensity to incorporate four Mn ions, the arrangement
and oxidation states of which are dependent on the coexistent anions
Anion-Controlled Assembly of Four Manganese Ions: Structural, Magnetic, and Electrochemical Properties of Tetramanganese Complexes Stabilized by Xanthene-Bridged Schiff Base Ligands
The reaction of manganeseĀ(II) acetate with a xanthene-bridged
bisĀ[3-(salicylideneamino)-1-propanol]
ligand, H<sub>4</sub>L, afforded the tetramanganeseĀ(II,II,III,III)
complex [Mn<sub>4</sub>(L)<sub>2</sub>(Ī¼-OAc)<sub>2</sub>],
which has an incomplete double-cubane structure. The corresponding
reaction using manganeseĀ(II) chloride in the presence of a base gave
the tetramanganeseĀ(III,III,III,III) complex [Mn<sub>4</sub>(L)<sub>2</sub>Cl<sub>3</sub>(Ī¼<sub>4</sub>-Cl)Ā(OH<sub>2</sub>)], in
which four Mn ions are bridged by a Cl<sup>ā</sup> ion. A pair
of L ligands has a propensity to incorporate four Mn ions, the arrangement
and oxidation states of which are dependent on the coexistent anions
Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression
Contrary to 4,4ā²-dipyridinium (i.e., archetypal
methyl viologen),
which is reduced by two single-electron transfers (stepwise reduction),
the 4,1ā²-dipyridinium isomer (so-called āhead-to-tailā
isomer) undergoes two electron transfers at apparently the same potential
(single-step reduction). A combined theoretical and experimental study
has been undertaken to establish that the latter electrochemical behavior,
also observed for other polyarylpyridinium electrophores, is due to
potential compression originating in a large structural rearrangement.
Three series of branched expanded pyridiniums (EPs) were prepared: <i>N</i>-aryl-2,4,6-triphenylpyridiniums (Ar-<b>TP</b>), <i>N</i>-aryl-2,3,4,5,6-pentaphenylpyridiniums (Ar-<b>XP</b>), and <i>N</i>-aryl-3,5-dimethyl-2,4,6-triphenylpyridinium
(Ar-<b>DMTP</b>). The intramolecular steric strain was tuned
via <i>N</i>-pyridinio aryl group (Ar) phenyl (Ph), 4-pyridyl
(Py), and 4-pyridylium (qPy) and their bulky 3,5-dimethyl counterparts,
xylyl (Xy), lutidyl (Lu), and lutidylium (qLu), respectively. Ferrocenyl
subunits as internal redox references were covalently appended to
representative electrophores in order to count the electrons involved
in EP-centered reduction processes. Depending on the steric constraint
around the <i>N</i>-pyridinio site, the two-electron reduction
is single-step (Ar = Ph, Py, qPy) or stepwise (Ar = Xy, Lu, qLu).
This steric switching of the potential compression is accurately accounted
for by ab initio modeling (Density Functional Theory, DFT) that proposes
a mechanism for pyramidalization of the N<sub>pyridinio</sub> atom
coupled with reduction. When the hybridization change of this atom
is hindered (Ar = Xy, Lu, qLu), the first reduction is a one-electron
process. Theory also reveals that the single-step two-electron reduction
involves couples of redox isomers (electromers) displaying both the
axial geometry of native EPs and the pyramidalized geometry of doubly
reduced EPs. This picture is confirmed by a combined UVāvisāNIR
spectroelectrochemical and time-dependent DFT study: comparison of
in situ spectroelectrochemical data with the calculated electronic
transitions makes it possible to both evidence the distortion and
identify the predicted electromers, which play decisive roles in the
electron-transfer mechanism. Last, this mechanism is further supported
by in-depth analysis of the electronic structures of electrophores
in their various reduction states (including electromeric forms)