The preparation and structural characterization of as eries of lanthanide and uranium(IV)p hthalocyanine halide complexes were achieved by reaction of the corresponding metal halide with Li 2 Pc. Ap reliminarys urvey of their reactivity includes ring reduction of Li(THF) 4 [PcUCl 3 ] with KC 8 leading to the first structurally characterized Pc 4À actinide complex, hydrolysis of PcDyCl(DMSO) to PcDyOH(H 2 O) 3 and preparation of au nique trimeric triangular Li(PcDy) 3 (OH) 4 (H 2 O) cluster.Macrocyclic phthalocyanines, porphyrins, andt heir metal complexes are widelyu sed for applications, such as dyes, pigments, [1] catalysts, [2] and photosensitizes for photodynamic cancert herapy with singlet oxygen. [3] The vast majority of metallophthalocyanine (PcM) complexes utilize transition metals,w ith ap articularf ocus on the late first row elements due to their good fit with the Pc-holeand their very high stability. Pc-complexes of fe lements (Ln = lanthanide;A c = actinide), which were first reported in 1965, [4] are much less investigated, with the notable exceptiono fb is-phthalocyanine sandwich complexes of the form [Pc 2 Ln] À and their more elaborate multidecker analogues, such as Pc 3 Ln 2 , [4,5] whicha re favoured due to the large ionic radii andh igh coordination numbers of the f-block elements, anda re of particulari nterest for single-molecule-magnet applications (especially for Ln = Dy,T b, Er). [6,7] However, furtherc hemistry at the metal site is limited in these Pc 2 -based systemsd ue to the steric and electronic saturation of the Ln centre. The less developed mono-PcLnXo rP cAcX 2 systems have mostly focused on oxy-anions as the axial X-group, with afew examples of X = halide; [8,9] however,t here are very few structurally characterizeds ystems, and their reactivity chemistry is ripe for furtherd evelopment. Herein, we report the synthesis, structure, and preliminaryr eactivity survey of PcM halide materials for both 4f and 5f metals, illustrating a Scheme1.Synthesis of PcDyCl(DMSO), PcErCl(THF), and Li(THF) 4 [PcUCl 3 ]. "Solvent" in PcLn-product = DMSO or THF,depending on the recrystallization conditions(seetext).[a] Dr.