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.

Specifications Table

Value of the Data

The electrochemical data of four ferrocenylsubphthalocyanine dyads may used by chemical researchers in the development of macrocyclic compounds such as subphthalocyanines, porphyrins and phthalocyanines.

This data article illustrates the effect of different scan rates (up to 5.0 Vs−1) on the experimental cyclic voltammograms and the related electrochemical data of four ferrocenylsubphthalocyanine dyads.

This data illustrates the effect of different axial ligands L = Fc(CH2)nCO2 (n = 0, 1 or 3) or FcCO(CH2)2CO2, on the formal reduction potential of the ferrocenyl oxidation, the first macrocycle based oxidation and the first macrocycle based reduction of subphthalocyanines L-BSubPc(H)12.

This data illustrates the effect of the aromatic macrocycle of the subphthalocyanine L-BSubPc(H)12 and of the alkyl chain length between B and Fc on the FeII/III oxidation potential of the ferrocenyl group of the ferrocenylcarboxylic acid moieties, L = Fc(CH2)nCO2 (n = 0, 1 or 3) or FcCO(CH2)2CO2, for four ferrocenylsubphthalocyanine dyads.

The ferrocenyl group on the axial ligand of a subphthalocyanine, influences the optical and electrochemical properties of the ferrocenylsubphthalocyanine dyads. Data of this article illustrate how different axial ligands change the redox properties of ferrocenylsubphthalocyanine dyads as may be needed for different applications such as for solar energy applications, sensors and photodynamic therapy. Knowledge of detailed redox data of both the FeII/III and macrocycle based oxidation and reduction processes, of as many as possible different ferrocenylsubphthalocyanine dyads can assist in future research in designing ferrocenylsubphthalocyanine dyads with specific electrochemical properties.

Data Description

We previously reported the electrochemical data of two fluoronated ferrocenyl-subphthalocyanines (Fc(CHm)nCOO)-BSubPc(F)12 (m = 1 or 2 and n = 2) and their non-fluoronated analogues [2]. Here we report detailled electrochemical data of four different ferrocenyl-subphthalocyanines Fc(CHm)nCO2BSubPc(H)12 (m = 2 and n = 0, 1 or 3) and FcCO(CH2)2CO2BSubPc(H)12, see Fig. 1. The ferrocenyl-subphthalocyanines of this study contain ferrocenylcarboxylic acids with different alkyl chain lengths as axial ligands to illustrate the influence of the chain length and type on the observed redox behaviour of the complexes. The electrochemical data of the four ferrocenylsubphthalocyanine dyads, FcCO2BSubPc(H)12, FcCH2CO2BSubPc(H)12, Fc(CH2)3CO2BSubPc(H)12 and FcCO(CH2)2CO2BSubPc(H)12, shown in Fig. 1, are reported in Table 1, Table 2, Table 3, Table 4 and the cyclic voltammograms (CVs) at various scan rates shown Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6. The raw current – potential data is available in the supplementary files uploaded. The electrochemical data and CVs at a scan rate of 0.100 V s−1, are provided in the related research article [1]. All CVs show one Fe based and one macrocycle based oxidation and two macrocycle based reductions for the four SubPcs, similar as was observed for the ferrocenylsubphthalocyanine dyads FcCH2OBSubPc(H)12 [3], FcCO2BSubPc(H)12 [3], FcBSubPc(H)12 [4], FcC CBSubPc(H)12 [4], Fc(CH2)2CO2BSubPc(X)12 and Fc(CH)2CO2BSubPc(X)12 with X = H or F [2,5]. The decreasing trend of redox potential of the iron based oxidation, with increasing alkyl chain length n in Fc(CH2)nCO2BSubPc(H)12 (n = 0–3) is similar to the trend of the oxidation of iron in the free ferrocenylcarboxylic acids Fc(CH2)nCO2H [6]. Reported first macrocycle based oxidation of the SubPcs generally exhibits irreversible behaviour [4,7], however, introduction of a ferrocenylcarboxylic acid moiety in the axial position of the subphthalocyanine L-BSubPc(H)12, led to chemically reversible behaviour (peak current ratios of 1) and with peak current voltage separations of ΔE < 0.092 V [1,2,5].

Fig. 1

Ferrocenylsubphthalocyanine dyads of which the electrochemical data is reported in this study.

Table 1

Electrochemical data (potential in V vs Fc/Fc+) in DCM for 5 × 10−4 mol dm−3 of FcCO2BSubPc(H)12 at indicated scan rates (ν in V/s). See Fig. 3 for peak assignments.

ν (V/s)	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc
1st oxidation (Fc)						2nd oxidation (I)
0.050	0.262	0.075	0.224	2.58	0.99	0.710	0.081	0.670	2.39	0.99
0.200	0.262	0.077	0.224	5.05	0.99	0.711	0.083	0.670	4.68	0.99
0.300	0.263	0.078	0.224	5.78	0.99	0.712	0.084	0.670	5.34	0.99
0.400	0.263	0.079	0.224	8.30	0.99	0.712	0.085	0.670	7.68	0.99
0.500	0.264	0.080	0.224	9.03	0.99	0.713	0.086	0.670	8.35	0.99
5.000	0.265	0.082	0.224	16.34	0.99	0.714	0.088	0.670	23.97	0.99
1st reduction (II)						2nd reduction (III)
0.050	-1.642	0.083	-1.601	2.48	0.99	-2.123	-	-	-	-
0.200	-1.643	0.085	-1.601	4.86	0.99	-2.124	-	-	-	-
0.300	-1.644	0.086	-1.601	5.55	0.99	-2.125	-	-	-	-
0.400	-1.644	0.087	-1.601	7.98	0.99	-2.125	-	-	-	-
0.500	-1.645	0.088	-1.601	8.68	0.99	-2.126	-	-	-	-
5.000	-1.646	0.090	-1.601	22.75	0.99	-2.127	-	-	-	-

Ep = peak anodic potential for oxidation (Eox) and peak cathodic potential for reduction (Ered).

ip is the peak anodic current for oxidation (ipa) and peak cathodic current for reduction (ipc).

ip ratio = ipc/ipa (oxidation peak) or ipa/ipc (reduction peak).

Table 2

Data for 5 × 10−4 mol dm−3 of FcCH2CO2BSubPc(H)12. See caption and footnote at Table 1 for details. See Fig. 4 for peak assignments.

ν (V/s)	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc
1st oxidation (Fc)						2nd oxidation (I)
0.050	-0.005	0.075	-0.043	2.58	0.99	0.709	0.079	0.670	2.41	0.99
0.200	-0.004	0.077	-0.043	5.05	0.99	0.710	0.081	0.670	4.73	0.99
0.300	-0.004	0.078	-0.043	5.78	0.99	0.711	0.082	0.670	5.41	0.99
0.400	-0.003	0.079	-0.043	8.30	0.99	0.711	0.083	0.670	7.77	0.99
0.500	-0.003	0.080	-0.043	9.03	0.99	0.712	0.084	0.670	8.45	0.99
5.000	-0.002	0.082	-0.043	16.14	0.99	0.713	0.088	0.670	23.21	0.99
1st reduction (II)						2nd reduction (III)
0.050	-1.642	0.081	-1.674	2.49	0.99	-2.153	-	-	-	-
0.200	-1.643	0.083	-1.674	4.89	0.99	-2.154	-	-	-	-
0.300	-1.644	0.084	-1.674	5.58	0.99	-2.155	-	-	-	-
0.400	-1.644	0.085	-1.674	8.03	0.99	-2.155	-	-	-	-
0.500	-1.645	0.086	-1.674	8.73	0.99	-2.156	-	-	-	-
5.000	-1.646	0.088	-1.674	23.36	0.99	-2.157	-	-	-	-

Table 3

Data for 5 × 10−4 mol dm−3 of Fc(CH2)3CO2BSubPc(H)12. See caption and footnote at Table 1 for details. See Fig. 5 for peak assignments.

ν (V/s)	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc
1st oxidation (Fc)						2nd oxidation (I)
0.050	-0.024	0.075	-0.062	2.56	0.99	0.710	0.081	0.670	2.34	0.99
0.200	-0.023	0.077	-0.062	5.01	0.99	0.711	0.083	0.670	4.58	0.99
0.300	-0.023	0.078	-0.062	5.73	0.99	0.712	0.084	0.670	5.23	0.99
0.400	-0.022	0.079	-0.062	8.23	0.99	0.712	0.085	0.670	7.52	0.99
0.500	-0.022	0.080	-0.062	8.95	0.99	0.713	0.086	0.670	8.18	0.99
5.000	-0.021	0.082	-0.062	16.57	0.99	0.714	0.088	0.670	23.48	0.99
1st reduction (II)						2nd reduction (III)
0.050	-1.870	0.083	-1.829	2.42	0.99	-2.343	-	-	-	-
0.200	-1.871	0.085	-1.829	4.75	0.99	-2.344	-	-	-	-
0.300	-1.872	0.086	-1.829	5.42	0.99	-2.345	-	-	-	-
0.400	-1.872	0.087	-1.829	7.80	0.99	-2.345	-	-	-	-
0.500	-1.873	0.088	-1.829	8.48	0.99	-2.346	-	-	-	-
5.000	-1.874	0.090	-1.829	22.92	0.99	-2.347	-	-	-	-

Table 4

Data for 5 × 10−4 mol dm−3 of FcCO(CH2)2CO2BSubPc(H)12. See caption and footnote at Table 1 for details. See Fig. 6 for peak assignments.

ν (V/s)	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc	Epa / V	ΔEp / V	Eo′ / V	ipb / μA	ip ratioc
1st oxidation (Fc)						2nd oxidation (I)
0.050	0.300	0.075	0.262	2.55	0.99	0.710	0.081	0.670	2.39	0.99
0.200	0.300	0.077	0.262	5.00	0.99	0.711	0.083	0.670	4.69	0.99
0.300	0.301	0.078	0.262	5.71	0.99	0.712	0.084	0.670	5.36	0.99
0.400	0.301	0.079	0.262	8.21	0.99	0.712	0.085	0.670	7.71	0.99
0.500	0.302	0.080	0.262	8.93	0.99	0.713	0.086	0.670	8.38	0.99
5.000	0.303	0.082	0.262	16.73	0.99	0.714	0.087	0.670	23.72	0.99
1st reduction (II)						2nd reduction (III)
0.050	-1.524	0.085	-1.482	2.44	0.99	-2.003	-	-	-	-
0.200	-1.525	0.087	-1.482	4.77	0.99	-2.004	-	-	-	-
0.300	-1.526	0.088	-1.482	5.46	0.99	-2.005	-	-	-	-
0.400	-1.526	0.089	-1.482	7.84	0.99	-2.005	-	-	-	-
0.500	-1.527	0.090	-1.482	8.53	0.99	-2.006	-	-	-	-
5.000	-1.528	0.092	-1.482	23.15	0.99	-2.007	-	-	-	-

Fig. 2

From top to bottom: Cyclic voltammograms (CVs) of 5 × 10−4 mol dm−3 of FcCO(CH2)2CO2-BSubPc(H)12, FcCO2-BSubPc(H)12, FcCH2CO2-BSubPc(H)12 and Fc(CH2)3CO2-BSubPc(H)12 at the indicated scan rates (Vs−1), in dichloromethane as solvent. Supporting electrolyte = 0.1 mol dm−3 [N(nBu)4][B(C6F5)4]. Scans initiated from ca -1 V in a positive direction. E0’ of the internal standard DMFc is indicated with a green dashed line. E0’ of the ferrocenyl oxidation of the indicated ferrocenylsubphthalocyanine dyads (labelled as Fc) is given in V.

Fig. 3

CVs of 5 × 10−4 mol dm−3 of FcCO2BSubPc(H)12 at scan rates of 0.20, 0.30, 0.40 and 0.50 Vs−1, in dichloromethane as solvent and 0.1 mol dm−3 [N(nBu)4][B(C6F5)4] as supporting electrolyte. Scans initiated from ca -1.1 V in a positive direction. E0’ of the internal standard DMFc is indicated with a red dashed line.

Fig. 4

CVs of 5 × 10−4 mol dm−3 of FcCH2CO2BSubPc(H)12 at scan rates of 0.20, 0.30, 0.40 and 0.50 Vs−1, in dichloromethane as solvent and 0.1 mol dm−3 [N(nBu)4][B(C6F5)4] as supporting electrolyte. Scans initiated from ca -1.1 V in a positive direction. E0’ of the internal standard DMFc is indicated with a red dashed line.

Fig. 5

CVs of 5 × 10−4 mol dm−3 of Fc(CH2)3CO2BSubPc(H)12 at scan rates of 0.20, 0.30, 0.40 and 0.50 Vs−1, in dichloromethane as solvent and 0.1 mol dm−3 [N(nBu)4][B(C6F5)4] as supporting electrolyte. Scans initiated from ca -1.1 V in a positive direction. E0’ of the internal standard DMFc is indicated with a red dashed line.

Fig. 6

CVs of 5 × 10−4 mol dm−3 of FcCO(CH2)2CO2BSubPc(H)12 at scan rates of 0.20, 0.30, 0.40 and 0.50 Vs−1, in dichloromethane as solvent and 0.1 mol dm−3 [N(nBu)4][B(C6F5)4] as supporting electrolyte. Scans initiated from ca -1.1 V in a positive direction. E0’ of the internal standard DMFc is indicated with a red dashed line.

Experimental Design, Materials and Methods

The experimental setup is as described earlier [5], namely: All electrochemical measurements (cyclic voltammetry) were obtained at RT (25°C) on 5 × 10−4 mol dm−3 analyte solution in anhydrous dichloromethane with 0.1 mol dm−3 tetrabutylammonium tetrakispentafluorophenylborate, [N(Bu)4][B(C6F5)4] as supporting electrolyte under an Ar atmosphere (H2O and O2 < 10 ppm) in a glove box (MBraun Lab Master SP), utilizing a Princeton Applied Research PARSTAT 2273 potentiostat with the Powersuite software (Version 2.58). A cell containing three electrodes was used to obtain the CVs, namely a working electrode (glassy C), an auxiliary electrode (Pt wire) and a reference electrode (Pt wire). Decamethylferrocene (E°′ = -0.610 V vs. Fc/Fc+) was used as internal reference, with the data reported vs. the ferrocene/ferrocenium redox couple as suggested by IUPAC [8]. Before each scan the glassy C electrode was prepared as follow: (i) polish on a Buhler polishing mat with 1-micron and with ¼-micron diamond paste, (ii) rinsed with distilled water, acetone and dichloromethane, and (iii) dried.

Ethics Statement

This work does not require any ethical statement.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships which have, or could be perceived to have, influenced the work reported in this article.

Subject	Chemistry
Specific subject area	Electrochemistry
Type of data	Cyclic voltammogramTable
How data were acquired	On an electrochemical analyser connected to a desktop computer, as described in the experimental details.
Data format	RawAnalysed
Parameters for data collection	Pure samples as synthesized.
Description of data collection	All electrochemical experiments were done in 2 ml cell containing three electrodes as described in the experimental details, was used to obtain the CVs.
Data source location	Institution: University of the Free StateCity/Town/Region: BloemfonteinCountry: Republic of South Africa
Data accessibility	In the article and supporting data.
Related research article	P.J. Swarts, J. Conradie, Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines, Molecules. 25 (2020) 2575. doi:10.3390/molecules25112575 [1]