Electrochemical data of ferrocenylsubphthalocyanine dyads.

The data presented in this paper is related to the research article entitled "Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines" [1] where electrochemical redox data and cyclic voltammograms at only a scan rate of 0.10 V s-1 of four ferrocenylsubphthalocyanine dyads Fc(CH2)nCO2BSubPc(H)12 (n = 0, 1 or 3) and FcCO(CH2)2CO2BSubPc(H)12, are presented. This data article provides extensive electrochemical redox data and cyclic voltammograms at various scan rates from 0.05 up to 5.00 V s-1 to illustrate the effect of the different scan rates on the electrochemical behaviour of the four ferrocenylsubphthalocyanine dyads.

Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines.

A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenyl-carboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H)12 via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H)12. A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH2)3CO2BSubPc(H)12 exhibited the lowest first macrocycle-based reduction potential (-1.871 V vs. Fc/Fc+) reported for SubPcs till date. The oxidation and reduction values of Fc(CH2)nCO2BSubPc(H)12 (n = 0-3), FcCO(CH2)2CO2BSubPc(H)12, and Cl-BSubPc(H)12 illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs.

Oxidation and reduction data of four subphthalocyanines with axially coordinated ferrocenylcarboxylic acids.

Redox data obtained from cyclic voltammetry experiments of the FeII/III and ring-based oxidation and reductions of subphthalocyanines containing a ferrocenylcarboxylic acid as axial ligand, is presented in this data in brief article. The FeII/III oxidation of ferrocenylsubphthalocyanines which containing the electron-withdrawing fluorine atoms at the peripheral and non-peripheral positions, are ca. 0.100 V more positive than FeII/III oxidation of ferrocenylsubphthalocyanines containing hydrogens at the peripheral and non-peripheral positions. For more insight into the reported data, see the related research article "Redox and photophysical properties of four subphthalocyanines containing ferrocenylcarboxylic acid as axial ligands" [1].

Redox and Photophysical Properties of Four Subphthalocyanines Containing Ferrocenylcarboxylic Acid as Axial Ligands.

Four new ferrocenylsubphthalocyanines Y-BSubPc, with ferrocenylcarboxylic acid YH = Fc-CH2-CH2-COOH (1) or Fc-CH═CH-COOH (2) in the axial Y position, were synthesized with a 40% yield. The axial ferrocenylcarboxylic acid moiety did not have a significant influence on the position of the Q bands maxima of the UV/vis spectra of the ferrocenylsubphthalocyanines or on the 1H NMR position of the ring proton peaks of Y-BSubPc(H12) or on the 19F NMR position of the ring F peaks of YSubPc(F12), relative to their respective parent compounds Cl-BSubPc(H12) 3 and Cl-BSubPc(F12) 4, containing axial chlorine. Very weak metal-to-ligand-charge-transfer bands (MLCT) in the near-IR region were observed. An electrochemical study utilizing cyclic voltammetry showed that electronic communication exists between ferrocene on the axial ferrocenylcarboxylic acid and the π-electrons of the macrocycle of the ferrocenylsubphthalocyanine (Fc(CH2)2COO)-BSubPc(H)12,5, (Fc(CH)2COO)-BSubPc(H)12, 6, (Fc(CH2)2COO)-BSubPc(F)12, 7, and (Fc(CH)2COO)-BSubPc(F)12, 8. The Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the subphthalocyanine ligand. The fluorine ring substituents in SubPcs 7 and 8 caused the ferrocenyl oxidation to shift more positive by ca. 0.1 V, compared to SubPcs 5 and 6 without fluorine. Density functional theory (DFT) calculations provided further insight into the properties of these novel ferrocenylsubphthalocyanines. The neutral species of SubPcs 5-8 have LUMOs with mainly π-ring character and HOMOs with mainly iron-d character, confirming ring-based reduction, metal-based Fe(II) to Fe(III) oxidation, as well as weak MLCT in the near-IR region. Further DFT optimization of the cation (oxidized) species was essential to verify the second ring-based oxidation.

Redox data of ferrocenylcarboxylic acids in dichloromethane and acetonitrile.

Redox data obtained from cyclic voltammetry experiments of the FeII/III oxidation of six ferrocenyl carboxylic acids is presented in this data in brief article. Data is obtained from the cyclic voltammograms at scan rates of two orders of magnitude (0.05 - 5.00 Vs-1) using (i) acetonitrile as solvent and tetrabutylammonium hexafluorophosphate as supporting electrolyte and (ii) dichloromethane as solvent and tetrabutylammonium tetrakispentafluorophenylborate, as the electrolyte. Data is reported versus the FeII/III redox couple of ferrocene. For more insight in the reported data, see the related research article "Solvent and substituent effect on Electrochemistry of ferrocenylcarboxylic acids", published in Journal of Electroanalytical Chemistry [1].

Oxidation and reduction data of subphthalocyanines.

The data presented in this paper are related to the research article entitled "Electrochemical behaviour of chloro- and hydroxy-subphthalocyanines" [1]. This paper presents detailed oxidation and reduction potential data, obtained from cyclic voltammograms of three subphthalocyanines (SubPcs), in both dichloromethane (DCM) and dichloroethane (DCE) as solvent. The first SubPc is the unsubstituted boron-subphthalocyanine, (ClB)SubPc(H)12, as reference SubPc, the second SubPc is (ClB)SubPc(F)12, containing an electron-poor macro-cycle and (HOB)SubPc(C12H25)6(H)6, containing an electron-rich macro-cycle. The oxidation and reduction potential of (ClB)SubPc(F)12 in DCM is ca. 0.5 V more positive than that of the reference ClBSubPc(H)12, while oxidation and reduction potential of (HOB)SubPc(C12H25)6(H)6 in DCM is ca. 0.45 V more negative than that of the reference (ClB)SubPc(H)12.

Redox behaviour of cymantrene Fischer carbene complexes in designing organometallic multi-tags.

A series of Group 7 Fischer carbene complexes, [Cp(CO)2 Mn(I) =C(OEt)Ar] (Cp=cyclopentadienyl, Ar=Th=thienyl (1 a), Ar=Fu=furyl (2 a), Ar=Fc=ferrocenyl (3 a)) and biscarbene complexes, [Cp(CO)2 MnC(OEt)Ar'(OEt)CMn(CO)2 Cp] (Ar'=Th'=2,5-thienylene (1 b), Ar'=Fu'=2,5-furylene (2 b), Ar'=Fc'=1,1'-ferrocendiyl (3 b)) was synthesized and characterized. Chemical oxidation of [Cp(CO)2 MnC(OEt)Fc] (3 a) and isolation of the oxidised species [3 a][PF6 ] possessing a Mn(II) centre proved possible below -30 °C in dichloromethane solution. The ESR spectrum of the transiently stable radical cation, [3 a][PF6 ], confirmed the presence of a low-spin Mn(II) centre characterized by a rhombic g tensor (gx =1.975, gy =2.007 and gz =2.130) in frozen dichloromethane at 77 K with (55)  Mn hyperfine coupling constants A1 , A2 and A3 of 115, 33 and 43 G, respectively. Electrochemical studies demonstrated the influence of the Ar substituent on the oxidation potential. All complexes showed that the redox potentials of carbene double bond reduction and Mn(I) oxidation were dependent on the type of Ar group, but only 3 b showed resolved oxidations for the two Mn(I) centres. Surprisingly, Mn(I) oxidation occurs at lower potentials than ferrocenyl oxidation. Density functional theory (DFT) calculations were carried out to delineate the nature of the species involved in the oxidation and reduction processes and clearly confirm that oxidation of Mn(I) is favoured over that of ferrocene.

Substituent effects on the electrochemical, spectroscopic, and structural properties of Fischer mono- and biscarbene complexes of chromium(0).

A series of ten ferrocenyl, furyl, and thienyl mono- and biscarbene chromium(0) complexes were synthesized and characterized spectroscopically and electrochemically. The single crystal structure of the biscarbene complex [(CO)5Cr═C(OEt)-Fu'-(OEt)C═Cr(CO)5] (4a) was determined: C20H12Cr2O13; triclinic; P1; a = 6.2838(5), b = 12.6526(9), c = 29.1888(19) Å, α = 89.575(2), ß = 88.030(2), γ = 87.423(2)°; Z = 4. Results from an electrochemical study in CH2Cl2 were mutually consistent with a computational study in showing that the carbene double bond of 1-6 is reduced to an anion radical, (-)Cr-C• at formal reduction potentials < -1.7 V vs FcH/FcH(+). The Cr centers are oxidized in two successive one electron transfer steps to Cr(II) via the Cr(I) intermediate. Only Cr(I) oxidation is electrochemically irreversible. Dicationic Cr(II) species formed upon two consecutive one-electron oxidation processes are characterized by a peculiar bonding situation as they are stabilized by genuine CH···Cr agostic interactions. With respect to aryl substituents, carbene redox processes occurred at the lowest potentials for ferrocene derivatives followed by furan complexes. Redox process in the thiophene derivatives occurred at the highest potentials. This result is mutually consistent with a (13)C NMR study that showed the Cr═C functionality of furyl complexes were more shielded than thienyl complexes. The NHBu carbene substituent resulted in carbene complexes showing redox processes at substantially lower redox potentials than carbenes having OEt substituents.

Electrochemical illumination of thienyl and ferrocenyl chromium(0) Fischer carbene complexes.

A series of ferrocenyl and thienyl mono- and biscarbene chromium(0) complexes 1-6 were synthesised. The complexes were characterised both spectroscopically and electrochemically, and the single crystal X-ray structure of 3 was determined. Electrochemical measurements in CH2Cl2 revealed that the carbene double bond of 1-6 is reduced to an anion radical, (-)Cr-C˙ at formal reduction potentials <-1.7 V vs. FcH/FcH(+). A computational study on 1, 3 and 4 (B3LYP/def2-SVP level) is consistent with electrochemical results in showing that electrochemically generated chromium(I) species may be further electrochemically irreversibly oxidised to chromium(II) at Epa > 0.95 V. The reactivity towards follow-up chemical reactions of the anodically produced Cr(II) species is much higher than the reactivity of the cathodically produced radical anions as the latter was still observably reoxidised to the parent Cr=C species at fast scan rates. The ferrocenyl group is oxidised electrochemically reversibly to ferrocenium at larger potentials than the electrochemically reversible oxidation of the Cr(0) centre to Cr(I). That all redox centres in 1-6 are involved in one-electron transfer steps was confirmed by comparing the ferrocenyl voltammetric wave with those of the other redox centres in linear sweep voltammetric experiments. The ferrocenyl group was electrochemically shown to stabilise the Cr=C centre almost as much as the NHBu, and much more than the ethoxy and thienyl groups.