Alkyl- and Aryl-Substituted Corroles. 5. Synthesis, Physicochemical
Properties, and X-ray Structural Characterization of Copper Biscorroles
and Porphyrin−Corrole Dyads
Roger Guilard
Claude P. Gros
Jean-Michel Barbe
Enrique Espinosa
François Jérôme
Alain Tabard
Jean-Marc Latour
Jianguo Shao
Zhongping Ou
Karl M. Kadish
10.1021/ic049651c.s005
https://acs.figshare.com/articles/dataset/Alkyl_and_Aryl_Substituted_Corroles_5_Synthesis_Physicochemical_Properties_and_X_ray_Structural_Characterization_of_Copper_Biscorroles_and_Porphyrin_Corrole_Dyads/3315919
The synthesis and characterization of cofacial copper biscorroles and porphyrin−corroles linked by a biphenylenyl or
anthracenyl spacer are described. The investigated compounds are represented as (BCA)Cu<sub>2</sub> and (BCB)Cu<sub>2</sub> in the
case of the biscorrole (BC) derivatives and (PCA)Cu<sub>2</sub> and (PCB)Cu<sub>2</sub> in the case of porphyrin (P)−corrole (C) dyads,
where A and B represent the anthracenyl and biphenylenyl bridges, respectively. A related monomeric corrole
(Me<sub>4</sub>Ph<sub>5</sub>Cor)Cu and monomeric porphyrin (Me<sub>2</sub>Et<sub>6</sub>PhP)Cu that comprise the two halves of the porphyrin−corrole
dyads were also studied. Electron spin resonance (ESR), <sup>1</sup>H NMR, and magnetic measurements data demonstrate
that the copper corrole macrocycle, when linked to another copper corrole or copper(II) porphyrin, can be considered
to be a Cu(III) complex in equilibrium with a Cu(II) radical species, copper(III) corrole being the main oxidation state
of the corrole species at all temperatures. The cofacial orientation of (BCB)Cu<sub>2</sub>, (BCA)Cu<sub>2</sub>, and (PCB)Cu<sub>2</sub> was confirmed
by X-ray crystallography. Structural data: (BCB)Cu<sub>2</sub>(C<sub>110</sub>H<sub>82</sub>N<sub>8</sub>Cu<sub>2</sub>·3CDCl<sub>3</sub>), triclinic, space group <i>P</i>1̄, <i>a</i> = 10.2550(2) Å, <i>b</i> = 16.3890(3) Å, <i>c</i> = 29.7910(8) Å, <i>α</i> = 74.792(1)°, <i>β</i> = 81.681(1)°, <i>γ</i> = 72.504(2)°, <i>Z</i> = 2; (BCA)Cu<sub>2</sub>(C<sub>112</sub>H<sub>84</sub>N<sub>8</sub>Cu<sub>2</sub>·C<sub>7</sub>H<sub>8</sub>·1.5H<sub>2</sub>O), monoclinic, space group <i>P</i> 2<sub>1</sub>/<i>c</i>, <i>a</i> = 16.0870(4) Å, <i>b</i> = 35.109(2) Å, <i>c</i> = 19.1390(8)
Å, <i>β</i> = 95.183(3)°, <i>Z</i> = 4; (PCB)Cu<sub>2</sub>(C<sub>89</sub>H<sub>71</sub>N<sub>8</sub>Cu<sub>2</sub>·CHCl<sub>3</sub>), monoclinic, space group <i>P</i>2<sub>1</sub>/<i>n</i>, <i>a</i> = 16.7071(3) Å, <i>b</i> =
10.6719(2) Å, <i>c</i> = 40.8555(8) Å, <i>β</i> = 100.870(1)°, <i>Z</i> = 4. The two cofacial biscorroles, (BCA)Cu<sub>2</sub> and (BCB)Cu<sub>2</sub>,
both show three electrooxidations under the same solution conditions. The reduction of (BCA)Cu<sub>2</sub> involves a reversible
electron addition to each macrocycle at the same potential of <i>E</i><sub>1/2</sub> = −0.20 V although (BCB)Cu<sub>2</sub> is reversibly reduced
in two steps to give first [(BCB)Cu<sub>2</sub>]<sup>-</sup> and then [(BCB)Cu<sub>2</sub>]<sup>2-</sup>, each of which was characterized by ESR spectroscopy
as containing a Cu(II) center. These latter electrode reactions occur at <i>E</i><sub>1/2</sub> = −0.36 and −0.51 V versus a saturated
calomel reference electrode. The half-reduced and fully reduced (BCB)Cu<sub>2</sub> show similar Cu(II) ESR spectra, and no
evidence of a triplet signal is observed. The two well-separated reductions of (BCB)Cu<sub>2</sub> to give [(BCB)Cu<sub>2</sub>]<sup>2-</sup> can
be attributed to a stronger π−π interaction between the two macrocycles of this dimer as compared to those of
(BCA)Cu<sub>2</sub>. The copper porphyrin−corrole dyads, (PCA)Cu<sub>2</sub> and (PCB)Cu<sub>2</sub>, show five reversible oxidations and two
reversible reductions, and these potentials are compared with corresponding values for electrochemical reactions of
the porphyrin and corrole monomers under the same solution conditions.
2004-11-15 00:00:00
BC
calomel reference electrode
PCB
PCA
copper corrole macrocycle
BCA
BCB
latter electrode reactions
cofacial copper biscorroles
porphyrin
NMR
Cu
solution conditions
ESR