Synthesis of face-to-face metallocene polymers

Naphthalene-based oligothiophene-stacked polymers

“…[1][2][3] Recently, a new type of conjugated polymer that exhibits through-space interactions of pelectron systems has been developed. Poly(dibenzofulvene)s, 4-11 7,7-diarylnorbornane-containing conjugated polymers, 12,13 cyclophanecontaining polymers and face-to-face ferrocene polymers [36][37][38] have been synthesized, and their optical and electrochemical properties have been studied in detail. Polymers with layered aromatic rings and p-electron systems have also been investigated; [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] for example, Chen et al 53 recently reported the synthesis and formation of a twodimensional assembly of polymeric ladder phanes containing face-toface p-electron systems.…”

Synthesis of Aromatic-Ring-Layered Polymers

“…The treatment of 1,8-diiodonaphthalene 39 with 1,1'-ferrocenyldizinc chloride 40 by Negishi coupling afforded polymer P18 with a relatively low M n of 3600 (Arnold et al, 1988). The synthetic procedure was modified as follows: the treatment of bis(2-octyl)ferrocene 43 with NaN(SiMe 3 ) 2 and FeCl 2 provided the ferrocene-stacked polymer P19 with an M n of 18400 (Nugent & Rosenblum, 1993;Rosenblum et al, 1995;Hudson et al, 1999). The addition of CoCl 2 and NiBr 2 instead of FeCl 2 yielded the corresponding ferrocene/cobaltocene-stacked and ferrocene/nickelocene-stacked polymers, respectively.…”

Metallocene-containing conjugated polymers

“…Most studies were performed for pure Fc system [424][425][426] 61ac, M_Fe). Later both Cp ligands of Fc complexes in Scheme 61 were substituted by its mono-alkyl derivative, C 5 H 4 -2-octyl, while Cp ligands in complexes with metal M (Fe or Ni) were not modified, so that a pure Fc system with all Cp ligands was replaced by a alternating sequence of complexes with two Cp or two Cp-octyl ligands [426,427] (61b, M = Fe or Ni). A mixed Fe-Co chain as well as a pure nickelocene polymer was also synthesized [428].…”

“…An approach based on a chain of face-to-face metallocene complexes kept together and parallel by naphthalene molecules (see Scheme 61 and related discussion there) was applied to generate such polymers either with an alternating sequence of ferrocene-nickelocene complexes [426,427] or of ferrocene-cobaltocene ones or with purely nickelocene units [426,428].…”