Living ring‐opening metathesis polymerization of norbornenes bay‐functionalized perylene diimides

Abstract

Ring‐opening metathesis polymerization (ROMP)‐derived poly(oxanorbornene imide)s bearing bay‐linked mono‐alkoxy‐M1 and 1,7‐di‐alkoxy M2 functionalized perylene diimides (PDIs) were synthesized using Grubb's third (G3) and Hoveyda‐Grubbs second generation (HG2) ruthenium‐alkylidene metathesis initiators. The mono‐alkoxy‐derived PDI‐based non‐ladderphane polymer polyM1 displayed 67% to 77% of the trans olefin content in the polymer chain depending on the initiator used for the polymerization. When using the symmetrical 1,7‐di‐alkoxy‐derived PDI‐based polymer polyM2 having the ladderphane type‐structure, this displayed a significant amount of cis and trans olefin contents in the polymer chains, irrespective of the type of initiators used for the polymerization. ROMP of both monomers M1 and M2 proceeded in a well‐controlled manner with a linear dependence of molecular weight on the monomer/initiator ratio using G3 as initiator. Optical properties of the ladderphane‐based polyM2 and non‐ladderphane‐based polyM1 were characterized in both solution and the film state. X‐ray diffraction (XRD) analysis for all the polymers showed significant π‐stacking in the thin film state with ordered molecular packing and closer values of d‐spacing for both polyM1 and polyM2. Film morphology examined by AFM elucidated homogenous smooth polymer surface for both polymers in general, but with some irregularities observed for polyM1. In addition, CV analysis revealed both polymers could be good candidates as electron‐accepting materials, with excellent film‐forming ability, and thermal stability.

Molecular strategy towards ROMP-derived hyperbranched poly(olefin)s featuring various π-bridged perylene diimides

“…58 Thus, the intermolecular interactions between the PDIs are unable to impose linear-type polymerization that was observed for poly(oxanorbornene imide)s derived from single bay -linked 1,7-di-alkoxy functionalized perylene diimides. 54…”

“…PDI-bromide A was synthesised as reported in our previous work. 54 Monomer A was reacted in Stille coupling reaction with the corresponding conjugated tin monomers to afford a series of PDI-π-PDI diols B in good yields (62-85%), ESI (Fig. S1-S11 †).…”

“…The design and characterization of highly conjugated PDI incorporated with linear or ladder-type poly(norbornene)s has achieved a great deal of attention for their prominent applications in organic electronics. 53,54 However, to the best of our knowledge, ROMP-derived PDI incorporated hyperbranched building blocks or polymers have not been reported to date.…”

Organic memory devices and synaptic simulation based on indacenodithienothiophene (IDTT) copolymers with improved planarity

“…In the solution and in the solid state, all copolymers exhibited a main p-p* transition with two peaks due to strong intramolecular interactions. [27][28][29] The absorption maxima of the copolymers in solution are at 545 nm for P1, 548 nm for P2 and 610 nm for P3. In comparison, thin film absorption spectra of P1-P3 display a bathochromic red shift of 2, 15 and 22 nm for P1, P2 and P3, respectively.…”

POSS-containing polynorbornene with pendant perylene diimide: from a unique supramolecular structure to tunable luminescence properties

“…[22][23][24] In particular, the polynorbornene backbone has been chosen to prepare PDI side-chain polymers due to its good chemical stability and possibility of obtaining living polymerization. [25][26][27][28] It should be noted that the aforementioned polymers usually possess a close PDI stacking structure, facilitating the pathways for efficient electron transport. However, the fluorescence quantum yields (QYs) usually decrease significantly due to the expansion of p-stacking in a concentrated solution and in the solid state.…”