Four　tetra-a-substituted　phthalocyanines,　represented　as　[(OR)　4Pc]M　where　OR　is　2,　2,4-tri-methyl-3-pentoxy　and　M　=　Co(II),　Ni(II),　Cu(II)　or　Zn(II),　were　investigated　as　to　their　electrochemistry,　UV-visible　and　ESR　spectroscopy.　The　electron-donating　groups　on　the　four　α-positions　of　the　phthalocyanine　macrocycles　lead　to　a　40　nm　red-shift　in　the　position　of　the　most　intense　band　in　the　UV-visible　spectrum　as　compared　to　the　unsubstituted　(Pc)M　derivative　with　the　same　central　metal　ion　under　the　same　solution　conditions.　The　cobalt,　nickel　and　copper　complexes　of　[(OR)　4Pc]M　are　soluble　in　nonaqueous　media　and　show　no　evidence　for　aggregation　at　the　millimolar　concentration　levels　needed　for　electrochemical　measurements.　The　Zn(II)　complex　aggregates　in　DMF　at　these　concentrations　but　monomers　are　formed　upon　diluting　the　solution　or　by　adding　a　complexing　axial　ligand　such　as　pyridine.　The　first　reduction　and　first　oxidation　of　[(OR)　4Pc]Co(II)　leads　to　formation　of　a　Co(I)　and　Co(III)　phthalocyanine　and　this　contrasts　with　the　first　reduction　and　first　oxidation　of　the　Ni(II),　Cu(II)　and　Zn(II)　derivatives　where　electron　addition　and　electron　abstraction　occur　at　the　conjugated　macrocycle,　leading　to　π-anion　and　π-cation　radicals,　respectively.　Copyright　©　2008　Society　of　Porphyrins　&　Phthalocyanines.