Non-peripherally octakis-substituted phthalocyanines (npPc’s), MPc(C12H25)8 with M = 2H (3) or Zn (4), as well as peripherally octakis-substituted phthalocyanines (pPc’s) with M = Zn (6), Mg (7) and 2H (8), were synthesized by cyclotetramerization of 3,6- (2) or 4,5-bis(dodecyl)phthalonitrile (5), template cyclotetramerization of precursor phthalonitriles in the presence of Zn or Mg, metal insertion into metal-free phthalocyanines, and removal of Mg or Zn from the phthalocyaninato coordination cavity. The more effective synthetic route towards pPc 8 was demetalation of 7. npPc’s were more soluble than pPc’s. The Q-band λmax of npPc’s was red-shifted with ca. 18 nm, compared to that of pPc’s. X-ray photoelectron spectroscopy (XPS) differentiated between N–H, Nmeso and Ncore nitrogen atoms for metal-free phthalocyanines. Binding energies were ca. 399.6, 398.2 and 397.7 eV respectively. X-ray photoelectron spectroscopy (XPS) also showed zinc phthalocyanines 4 and 6 have four equivalent Nmeso and four equivalent N–Zn core nitrogens. In contrast, the Mg phthalocyanine 7 has two sets of core N atoms. One set involves two Ncore atoms strongly coordinated to Mg, while the other encompasses the two remaining Ncore atoms that are weakly associated with Mg. pPc’s 6, 7, and 8 have cyclic voltammetry features consistent with dimerization to form [Pc][Pc+] intermediates upon oxidation but npPc’s 3 and 4 do not. Metalation of metal-free pPc’s and npPc’s shifted all redox potentials to lower values.

Ferrocenylbutoxy-bearing dodecylated phthalocyanines, MPc(C 12 H 25 ) x (OC 4 H 8 Fc) y with M = 2H (compound series 6 and 8) or Zn (compound series 5, 7 and 9), x ≤ 8 and y ≤ 4, were synthesized through either metal-free statistical condensation between 3,6-bis(dodecyl)phthalonitrile, 2, and 4-(1), or 3-(4′ferrocenylbutoxy)phthalonitrile, 4, or a zinc template statistical condensation between 4,5-bis(dodecyl)phthalonitrile, 3, and 1 in the presence of anhydrous zinc acetate, or by zinc insertion into metal-free phthalocyanines. Compounds were designed to have eight nonperipheral dodecyl substituents, six nonperipheral dodecyl, either one peripheral or one nonperipheral 4′ferrocenylbutoxy substituent, four nonperipheral dodecyl and two peripheral 4′-ferrocenylbutoxy substituents, or four peripheral 4′ferrocenylbutoxy substituents. The compound having six peripheral dodecyl and one peripheral 4′-ferrocenylbutoxy substituents was also synthesized. Metal-free and zinc complex Q-band maximum absorption wavelengths increased nonlinearly from 704 to 725 nm for the Q y -band of metal-free compounds, or from 676 to 699 nm for the Q-band of zinc complexes in moving from all peripheralsubstituted to all non-peripheral-substituted complexes. A rare case of accidental Q-band degeneracy where only one electronic Qband is observed for asymmetrical zinc complexes NOT having D 4h symmetry, compounds 5, 7b−e, and 9b, is also described. X-ray photoelectron spectroscopy (XPS) differentiated between four types of phthalocyanine nitrogen atoms; binding energies were ca. 399.8 (N−H), 398.1 (N meso ), 397.8 (N core ), and 398.7 eV (N−Zn), respectively. An electrochemical study of these compounds revealed up to five different redox processes in dichloromethane but only three in tetrahydrofuran (THF). The first ring-based oxidation of both metal-free compounds 6a−e and zinc phthalocyanines 7a−e exhibited a near-linear increase in peak anodic potentials, E pa , with the systematic replacement of two nonperipheral dodecyl substituents with one peripheral 4′-ferrocenylbutoxy group. When four 4′-ferrocenylbutoxy groups were substituted on the phthalocyanine macrocycle, aggregation of the first oxidized species was observed. Zinc insertion into metal-free phthalocyanines lowered formal redox potentials. An electrochemical scheme consistent with electrochemical results is provided.