The oxidative dehydrocyclization of the 3 (indolizin 2´ yl) 2 oxoquinoxaline monopodand performed either electrochemically or under the action of molecular iodine affords new redox active heterocyclophane consisting of the redox switchable biindolizine fragment combined with the polyether bridged π deficient quinoxaline systems. The single crystal X ray diffrac tion study showed that the trioxaundecane chain of heterocyclophane adopts an extended conformation, and one of the phenyl substituents of the molecule closes the pseudocavity formed by the spacer from one of the sides. The cyclic voltammetric study of heterocyclophane in MeCN and DMF showed the three step oxidation of the indolizine fragments accompanied by the single electron transfer in each step. The first and third steps are reversible, and the second step is irreversible. The oxidation at potentials of the first peak gives rise to stable radical cations detected by the ESR method (g = 2.0024, a 2N = 0.26 mT).In recent years, the synthesis of macrocyclic com pounds, which can reversibly respond to external actions (thermal, photochemical, electrochemical, pH, etc.) by changing important properties and characteristics (the cavity size, the surface shape, the electronic structure, the complexing ability, etc.) due to the specially introduced functional groups or fragments, has taken a special place in supramolecular chemistry. 1 Such "sensitive" hetero cyclophanes containing redox active biindolizine systems can serve as molecular switches 2 and membrane carriers 3 and are of great interest in the design of new sensors for modern technologies based on molecular processes. Un like redox active compounds (ferrocenes, 4,5 tetrathia fulvalenes, 6,7 and quaternized 4,4´ bipyridines 8,9 ), bi indolizines have found little use as active regions, which make cyclophanes able to respond to external actions, in spite of the fact that biindolizines are quite stable two step redox systems, whose electrochemical behavior has been studied in sufficient detail. 10-15Indolizines are π rich compounds, which are readily oxidized (~0.2-0.3 V relative to Fc 0/+ ) to form radical cations. 10-14 The stability and subsequent transforma tions of radical cations are determined primarily by the presence of hydrogen atoms in the pyrrole ring of the indolizine system. The radical cations and dications of 3,3´ biindolizines, in which all hydrogen atoms in the five membered ring are replaced by alkyl or aryl groups, are quite stable and can be isolated and characterized as perchlorates. 12 The electrochemical behavior of two dia stereomers of macrocyclic biindolizines, in which both heterofragments are linked at positions 3,3´ and, through a bridge, at positions 1,1´, is different. 13 Thus, the diaste reomer having the anti configuration is oxidized to form stable radical cations and dications, whereas the oxida tion of the diastereomer having the syn configuration is followed by the intramolecular cyclization with the in volvement of the C(5) and C(5´) atoms of the pyridine rings of...