The effect of introduction of perfluoro alkyl groups into phthalocyanines, as evidenced by the spectroscopic properties of 1,4,8,11,15,18,22,25-octa-fluoro-2,3,9,10,16,17,23,24-octa-perfluoro isopropyl zinc phthalocyanine, ZnF(64)Pc(-2) and its ring-reduced radical anion species, [ZnF(64)Pc(-3)](-), are reported. A combination of UV-visible absorption and magnetic circular dichroism (MCD) spectroscopy, ESI and MALDI-TOF mass spectrometry, cyclic and differential pulse voltammetry, and complete theoretical calculations using INDO/S and DFT techniques reveals that the substitution of all sixteen hydrogen atoms in protio ZnPc(-2) by eight F and eight i-C(3)F(7) groups red shifts the Q and pi --> pi transitions and narrows the HOMO-LUMO gap while simultaneously preventing ring photooxidation and stabilizing the radical anion. The [ZnF(64)Pc(-3)](-) species, which is in equilibrium in solution with the neutral complex when a reducing agent is present, is unusually stable. The above effects are attributed to the strong electron withdrawing properties of the peripheral substituents, which render ZnF(64)Pc extremely electron deficient.

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Direct measurements of the radical reaction products following the electrochemical and photochemical oxidation and reduction of a metallophthalocyanine pi-ring are reported. Electrospray mass spectrometry was used to detect the presence of the anion zinc(II) (1,4,8,11,15,18,22,25-octafluoro, 2,3,9,10,16,17,23,24-octaperfluoroisopropylphthalocyanine chloride, [ZnperF(64)Pc(-2) (Cl)](-), and its pi ring anion radical species, [ZnperF(64)Pc(-3)(Cl)](2-). This paper describes the use of ESI-MS techniques to determine the products of an on-line, photochemical radical oxidation, using CBr(4) as a sacrificial photoinduced oxidizing agent, which oxidized the radical, [ZnperF(64)Pc(-3)(Cl)](2-) species to [ZnperF(64)Pc(-2)(Cl)](-), where the complete reaction was detected directly by the mass spectrometer. This study makes use of electrospray mass spectrometry to detect the presence of an anion radical as the key component in the ring-reduced species and to monitor the immediate products of the important class of photochemical reduction and oxidation reactions in which radicals of the Zn Pc are formed in situ.

The crystal structure of {[Cu(en) 2 ][KCr(CN) 6 ]} ∞ reveals a novel three-dimensional porous framework in which [Cu(en) 2 ] 2+ acts as a template and K + as a connecting unit.

structure structure (solids and liquids) D 2000 -005An Unusual Three-Dimensional Porous Framework Complex {[Cu(en) 2 ][KCr(CN) 6 ]}∞ (en: Ethylenediamine) from a Template Self-Assembly Reaction.-The title compound is prepared through a one-step self-assembly reaction of [Cu(en) 2 ](ClO 4 ) 2 and K 3 Cr(CN) 6 in aqueous solution. The compound is characterized by IR spectroscopy. The structure of the compound (monoclinic space group C2/c, Z = 4) represents a novel three-dimensional porous framework in which the [Cu(en) 2 ] 2+ ion acts both as a template and as guest. The Cr 3+ ion is octahedrally coordinated by six carbon atoms of the cyano groups. The six nitrogen atoms of the cyano groups coordinate to a potassium