{5,5';19,19'-Bi[phthalocyaninato(2-)]}titanium(1v)-l -chloronaphthalene( 1 /1), [TiL]*C,,H,CI, is obtained by the reaction of [Ti(pc)CI,] (pc = phthalocyaninato dianion, [C,H,,N,] 2-) with Na2(pc) in 1 -chloronaphthalene at 190 "C. An X-ray single-crystal structure (monoclinic, space group C2/c, a = 16.327(3), b = 18.568(4), c =19.022(4) A, p = 94.50(1)", Z = 4) indicates for this complex a sandwich-type structure with the titanium atom in the centre of the molecule and the two phthalocyaninato units 'stapled' by two inter-ring C-C 0 bonds [C(11 )-C(l 1 ') 1.556(6) and C(31 )-C(31') 1.575(6) A]. Due to the staggered orientations of the two macrocyclic rings (relative rotation 45") the planes of the two inner N, systems (each of which is slightly distorted from planarity) form a square-antiprism, with an average interplane distance of 2.32 A (much shorter than that found in similar 'unstapled' complexes), and Ti-N bond distances in the range 2.1 7-2.26 A. The complex shows high thermal stability and can be oxidized by nitric acid to give the species [TiL] NO,. The complexes [TiL] and [TiL] NO, show differing solid-state electrical conductivity properties.Metal phthalocyanines have been intensively investigated as molecular electrical conductors or semiconductors.' Among the various species examined, sandwich-like bis(phtha1ocyaninato)metal complexes of formula M(pc), (pc = phthalocyaninato dianion, [C3,H16N8]'-; M = Sn'V,2v3 a lanthanide, or an actinide 4.5) include the well authenticated 'intrinsic semiconductor' Lu(p~),,~ and generally achieve semiconducting properties when doped with electron acceptors or donors." The M(pc), complexes (M = a lanthanide) are also interesting