10.1021/ic300872m.s001
André Bessette
André
Bessette
Janaina G. Ferreira
Janaina G.
Ferreira
Martin Giguère
Martin
Giguère
Francis Bélanger
Francis
Bélanger
Denis Désilets
Denis
Désilets
Garry S. Hanan
Garry S.
Hanan
Azadipyrromethene Dye
Derivatives in Coordination
Chemistry: the Structure–Property Relationship in Homoleptic
Metal(II) Complexes
American Chemical Society
2012
BF
1.25 V
pseudoreversible
SCE
compounds 2 b
ADPM
3 b
5 b
homoleptic complexes
DPM
Azadipyrromethene Dye Derivatives
0.80 V
2012-11-19 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Azadipyrromethene_Dye_Derivatives_in_Coordination_Chemistry_the_Structure_Property_Relationship_in_Homoleptic_Metal_II_Complexes/2467612
As a chromophore closely related to dipyrromethene (DPM),
the azadipyrromethene
(ADPM) family has attracted much interest in the life sciences and
optoelectronic fields. A high-yielding microwave-assisted synthesis
is reported for new homoleptic complexes of cobalt(II), nickel(II),
copper(II) and zinc(II) based on the tetrakis(<i>p</i>-methoxyphenyl)azadipyrromethene
ligand <b>1b</b>. These complexes are compared with other homoleptic
complexes of the same metal(II) series based on the tetraphenylazadipyrromethene <b>1a</b> and also with related BF<sub>2</sub><sup>+</sup> chelates
(Aza-BODIPYs <b>6a</b> and <b>6b</b>) for a better understanding
of trends arising from substitution of the chelate and/or the electron-donating
effect of the <i>p</i>-methoxy substituents. The electrochemical
behavior of the new compounds <b>2b</b>, <b>3b</b>, and <b>5b</b> in dichloromethane revealed two pseudoreversible reductions
(<b>2b</b>, −1.09 and −1.25 V vs SCE; <b>3b</b>, −1.05 and −1.29 V; <b>5b</b>, −1.13
and −1.25 V) followed by a third irreversible process (<b>2b</b>, −1.78 V; <b>3b</b>, −1.80 V; <b>5b</b>, −1.77 V) along with two pseudoreversible oxidations
(<b>2b</b>, 0.55 and 0.80 V; <b>3b</b>, 0.56 and 0.80
V; <b>5b</b>, 0.55 and 0.80 V) followed by two closely spaced
irreversible processes (<b>2b</b>, 1.21 and 1.27 V; <b>3b</b>, 1.21 and 1.28 V; <b>5b</b>, 1.22 and 1.25 V). On its side,
copper(II) homoleptic complex <b>4b</b> revealed only one pseudoreversible
reduction at −0.59 V followed by three irreversible processes
at −0.95, −1.54, and −1.74 V, respectively. The
oxidation behavior of this complex exhibited two pseudoreversible
processes (0.55 and 0.82 V) and two irreversible processes (1.19 and
1.25 V). The redox processes are assigned and discussed in relation
to their photophysical properties. X-ray structures for <b>1b</b> and related copper(II) complex <b>2b</b> are also discussed.