The synthesis of novel magnesium, copper, and metal-free porphyrazines, peripherally substituted with dithia-7-crown-2 (MPz(7)), dithia-15-crown-5 (MPz(15)), and dithia-18-crown-6 (MPz(18)) macrocycles is reported. These compounds are prepared starting from dicyanoethylene containing crown ethers 3, 2(1), and 2(2), respectively, which contain sulfur as well as oxygen heteroatoms. The "crowned" porphyrazines bind silver(I) and mercury-(II) perchlorates. UV/vis spectroscopy and electron paramagnetic resonance measurements reveal that addition of the transition-metal ions leads to dimerization of the porphyrazine complexes. In the case of the dithia-18-crown-6-substituted porphyrazines, the dimers break up to form monomeric 6:1 guest-host complexes when more than 2 equiv of the metal ion is added. The single-crystal structures of the crown ether 2(2) and the porphyrazine MgPz (18) . The structure refinement converged to R 1 = 0.0839 and wR2 = 0.2196. The electrical properties of H2PZO8) have been studied by complex impedance spectroscopy. The bulk electrical conductivity of this compound is approximately 1 order of magnitude higher than that of the corresponding 18-crown-6 phthalocyanine. roduction olecular ionics is a rapidly developing area in chemistry, aimed at the development of molecular systems and devices t can handle and store information using ions as the basic ties. 1-3 Crown ethers, which are capable of selectively ding alkali metal ions, are important building blocks for structing such devices because metal complexation can lead specific response, e.g. a change in electrical conductivity, rder to maximize the reliability, the response must be highly linear, which can be achieved by introducing a cooperative ct in the binding process.2*3 hthalocyanines (Pcs), porphyrins (Pps), and porphyrazines ) are compounds of another class receiving great interest omponents in molecular ionics.4 Pps containing pendant n ether macrocycles were first described by Thanabal and Kobayashi.5 O f particular interest are phthalocyanines substituted with four crown ether rings,2,3 which were reported independently by the groups of Bekaroglu, Kobayashi, and Nolte.6 These compounds display solvent and metal ion induced aggregation behavior.7 We have prepared complexes of crown ether Pcs with various alkali metal picrates and studied the electrical properties of these systems.8,9 The ac electrical conductivities of the K +, Rb+, and Cs+ complexes of 18-crown-6 Pc were shown to be 2-3 orders of magnitude higher than those of the free molecules. It was demonstrated that these higher conductivities are due to the fact that in the complexes the phthalocyanines have a cofacially stacked arrangement. With Ba2+, noncofacial aggregates are formed, which show lower conductivities. The most promising application of crown ether phthalocyanines and their complexes is as sensor materials in gas sensors. 10,11 Other crowned Pcs that have been synthesized and studied are Pcs with azacrown ether and thiacrown ether substituents, Chemistry,...