SnPhPc phthalocyanines with dianion Pc²⁻ and radical trianion Pc˙³⁻ macrocycles: syntheses, structures, and properties

Abstract

The interaction of Sn(IV)Cl2Pc with an excess of NaBPh4 in the presence of fullerenes C60 and C70 provides complete dissolution of Sn(IV)Cl2Pc and the formation of blue solutions from which the crystals of [SnPhPc(2-)](+)(BPh4)(-)·C6H14 () or [SnPhPc˙(3-)]·C6H4Cl2 () were selectively isolated. According to the optical spectra, salt contains dianionic Pc(2-) macrocycles, whereas macrocycles are reduced to form the Pc˙(3-) radical trianions in . As a result, the phthalocyanine macrocycle is dianionic in , and the positive charge of Sn(IV) is compensated by the Ph(-), Pc(2-), and BPh4(-) anions in this compound. The formally neutral compound contains two anionic species of Ph(-) and Pc˙(3-) and the Sn(IV) ion as the counter cation. Phenyl substituents are linked to the Sn(IV) atoms by the Sn-C(Ph) bonds of 2.098(2) () and 2.105(2) Å () length. The dianionic Pc(2-) macrocycle significantly deviates from planarity in while Pc˙(3-) is planar in . Salt manifests only a weak impurity EPR signal. Compound manifests an intense EPR signal with g = 2.0046 and a linewidth of 0.5 mT at 298 K due to the presence of Pc˙(3-). Spins are weakly antiferromagnetically coupled in the π-stacking [SnPhPc˙(3-)]2 dimers of with a Weiss temperature of -3 K and the estimated magnetic exchange interaction J/kB = -0.23 K.

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren‐9‐olato− Anions and Indium(III) Phthalocyanine Bromide Radical Anions

“…Am etal phthalocyanine (MPc) in the radical cation or radical anion state can show promising magnetic andc onducting properties. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] For example, the electrochemical or chemical oxidation of neutralM II Pcs or the electrochemical oxidation of {M III (CN) 2 Pc} À anions allows the preparation of compounds with metallic conductivity,w hich,i ns ome cases,i ss table down to liquid-heliumt emperatures. [1][2][3] The oxidation of unsubstituted and substituted manganese(II) phthalocyanines by the organic p-acceptor tetracyanoethyleney ields coordination chain compounds with ferrimagnetic ordering of the spins.…”

“…[4,5] The reduction of MPcsh as also been intensively studied. [6][7][8][9][10][11][12][13][14][15][16][17][18] Interest in this field is evoked by the prediction of metallicconductivityo rs uperconductivity in electron-dopedM Pcs [21] and the observation of ferrimagnetico rdering of spins in (Cp* 2 Cr + )[Fe I (Pc 2À )] À ·4C 6 H 4 Cl 2 (Cp* = pentamethylcyclopentadienyl) with chains of alternating iron(I) phthalocyanine anions (Fe I , S = 1/2) and decamethylchromocenium cations (Cr III , S = 3/ 2). [22] Up to now,s everal types of anionic metal phthalocyanines have been obtained as crystalsa nd have been structurally characterized.…”

“…[6][7][8] Reductioni s also centered on the phthalocyanine macrocycle in [(K + ) 2 (DME) 4 ][Mg II (OH À )(PcC 3À )]C À (DME = 1,2-dimethoxyethane), [M III (MeIm) 2 (PcC 3À )]C (M = Al III ,G a III ;M eIm = N-methylimidazole), [Al III (anisole) 2 (PcC 3À )]C,[ Sn IV Ph(PcC 3À )]C,G e IV (pyridine) 2 (Pc 4À ), and K 2 Nb IV O(Pc 4À )·5DME containing radical trianion andt etraanion phthalocyanine macrocycles. [9][10][11][12][13][14] Reduction of iron and cobalt phthalocyanines is centered on the metal atoms, which results in the formation of the [Fe I (Pc 2À )] À ,[ Co I (Pc 2À )] À ,a nd [Fe 0 (Pc 2À )] 2À anions. [15][16][17][18] Iron(II) hexadecachlorophthalocyanine forms salts with effective p-p stacking or al ayered arrangement of the phthalocyanine macrocycles.…”

Bis(N‐methylimidazole)‐Substituted Neutral Phthalocyanines {MIII(MeIm)2(Pc)·3–}0 (M = Al, Ga) Containing Radical Trianionic Phthalocyanine Macrocycles

“…In [Al III (anisole) 2 (Pc) · 3– ] 0[24] and [Ge IV (Py) 2 (Pc) 4– ] 0[25] , radical trianionic and even tetraanionic phthalocyanine macrocycles, respectively, are formed. Another compound of such type is [Sn IV (Ph – )(Pc) · 3– ] 0 . The negative charges of the phenyl substituent bonded to the Sn IV atom and the radical trianionic phthalocyanine (Pc · 3– ) macrocycle are compensated by the +4 charge of the central tin atom.…”

“…The presence of spin on the macrocycle is proved by optical spectra and X‐ray diffraction studies on single crystals. The Pc · 3– spins manifest themselves in the EPR spectrum and show weak antiferromagnetic coupling of spins within the π‐stacking {SnPhPc} 2 dimers . Coordination complex [Ph 5 CpRu(CO) 2 {Sn II (Pc) · 3– }] 0 can also be classified as a formally neutral compound; it also contains the Pc · 3– radical trianion .…”