Crystalline salts of metal phthalocyanine radical anions [M(Pc˙³⁻)]˙⁻ (M = Cu^II, Pb^II, V^IVO, Sn^IVCl₂) with cryptand(Na⁺) cations: structure, optical and magnetic properties

Abstract

Radical anion salts of metal phthalocyanines (M = CuII, PbII, VIVO and SnIVCl2) with the {cryptand(Na+)} cations have been obtained and studied.

Dianionic Titanyl and Vanadyl (Cation+)2[MIVO(Pc4−)]2− Phthalocyanine Salts Containing Pc4− Macrocycles

“…[9] An intense narrow component observed in the centero ft he EPR signal of 3 at 320.16mT ( Figure 6a)w as also attributed to V IV owing to specific parameters (g = 2.0183 and al inewidth (DH)o f4mT); it cannotbea ttributedt oa na dmixtureofPcC 3À (narrow signals with g = 2.0035a nd DH = 0.1-0.3 mT) [11,12] or [V IV O(PcC 3À )]C À radi-cal anions (broad components with g = 1.992-1.995 and DH = 8-24 mT). [9,10,14] Salt 5 also shows HFS with the appearance of eight lines with as plitting of 14.9-15.3 mT splitting,w hichi sc haracteristic of the interaction of the V IV electron spin with 51 Vn uclei (I = 7/ 2). There are also many weakerl ines in the spectrumo f5 positioned in such aw ay that two lines are located in higher and lower magnetic fields from the more intense central line involved in the eight-line HF structure, with as plitting of 4.2-4.8 mT.T he estimated g-factoro ft he EPR signal in 5 is 1.9753.…”

“…Metal phthalocyanines in an oxidized or reduced form provide highly conducting materials and show promising magnetic properties. [1][2][3][4][5][6][7][8][9][10] The oxidation of metal phthalocyanines has been the main focus of studies to date. [1][2][3][4][5][6] The development of the reduction chemistry of metal phthalocyanines (Pcs) in the solids tate has only recently begun.…”

“…[8][9][10] To date, as eries of crystalline metal phthalocyanine [M(PcC 3À )]C À radicala nion salts were obtainedw ithM= H 2 ,C u II ,N i II ,S n II ,P b II , Sn IV Cl 2 ,T i IV O, V IV O, In III Cl, Mg II OH, and someo ther metals. [9][10][11][12][13][14][15][16] Radical trianion PcC 3À macrocycles were also formed in formally neutral radicals [Al III (L) 2 (PcC 3À )]C,w here L = N-methylimidazole (MeIm) and THF, [17,18] [Ga III (MeIm) 2 (PcC 3À )]C , [18] and [Sn IV Ph(PcC 3À )]C [19] in which the negative charge of PcC 3À is compensated by the positive charge of the central metal atom. Further reduction of these metal phthalocyanines to their dianionic states wasr ealized at more negative reduction potentials (from À1.18 to À1.33 Vv s. saturated calomel electrode (SCE) in DMFf or Zn II Pc, Ni II Pc, and Cu II Pc).…”

Salts with titanyl and vanadyl phthalocyanine radical anions. Molecular design and effect of cations on the structure and magnetic and optical properties

“…Probably, for this reason this field has been developed only recently and the number of reduced metal phthalocyanines obtained till now as crystals is still rather limited. [16][17][18][19][20][21][22][23][24][25][26][27][28] Among them there are salts with cobaltIJI) and ironIJI) phthalocyanine anions [16][17][18][19][20] as well as ironIJI) hexadecachlorophthalocyanine anions. 21,22 Their formation is accompanied by the reduction of metal atoms in the phthalocyanines.…”

Salt of Ring‐Reduced Iron(II) Octaethyltetrapyrazinoporphyrazine Containing Trimetallic Dianions with Peripherally Coordinated ZnCl2 Units: {FeII(TPyzPzEt8)4–(ZnCl2)2}2–

“…Potentially reduced metal phthalocyanines can also manifest promising conducting and magnetic properties. Metal macrocycles can be reduced successfully by strong reductants such as Na/Hg, potassium graphite (KC 8 ) , , LiCp * , decamethylchromocene,, and sodium fluorenone ketyl . Zinc dust can also be used as suitable reductant especially to obtain reduced compounds of iron(II) phthalocyanine or hexadecachlorophthalocyanine , …”