Synthesis of ladder‐like polynorbornenes with n‐type perylenendiimide derivatives as bridges

Abstract

Polymerizable tetrachloro‐perylenediimdes containing endo/exo‐norbornene groups on both imide sides were designed and synthesized. Endo/Exo‐type soluble ladder‐like polynorbornenes with perylenediimide (PDI) as bridges were prepared by ring‐opening metathesis polymerization (ROMP). XRD characterizations showed that the ladder‐like polynorbornenes had ordered structures similar to the supramolecular precursors assembled from the corresponding monomers. TGA measurements demonstrated great thermal stabilities for the both target P1‐Endo and P2‐Exo with Td of about 320 °C at 5 wt % loss, respectively, which is important for further application in devices. Both polymers have good solubility in common organic solvents and easy to form thin films. Photophysical studies and cyclic voltammetry investigations reveal that polynorbornene films have wide‐range absorption from 400 nm to 600 nm and the HOMO/LUMO energy levels could be matched well with the donor‐PCzTh‐TVDCN. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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

“…The reason for the low molecular weight characteristics of both polymers are not completely understood, however, we attributed this to the insufficient solubility of the polymers in the eluent or significant chain transfer that is happening during the fast ROMP while using the G3 initiator. Never the less the low molecular weight characteristics of both poly M1 and poly M2 are comparable to the ROMP‐derived poly(norbornene)s reported by others 31,33 …”

“…This methodology can generate a wide variety of high molecular weight polymers in a controlled regioregular and stereoregular manner 28,29 . To date, only a few examples have been reported for the synthesis of ROMP‐derived PDI‐grafted poly(cycloolefin)s and most of the building blocks have been functionalized at the imide ‐linkage on the PDI pendant 25,30–36 . In 2012, Li et al reported an example of such imide ‐functionalized PDI‐based ladder‐type poly(norbornene)s and studied their supramolecular behavior 31 .…”

“…To date, only a few examples have been reported for the synthesis of ROMP‐derived PDI‐grafted poly(cycloolefin)s and most of the building blocks have been functionalized at the imide ‐linkage on the PDI pendant 25,30–36 . In 2012, Li et al reported an example of such imide ‐functionalized PDI‐based ladder‐type poly(norbornene)s and studied their supramolecular behavior 31 . Later, Xie and Sun jointly reported the synthesis of bis( imide )‐linked PDI‐based ladderphane copolymers and investigated the dielectrics and self‐assembled nanostructures 32 .…”

“…In general, both mono‐ and bis‐( imide )‐linked PDI‐grafted norbornene monomers and their corresponding poly(norbornene)s have displayed excellent flexibility, photo‐ and chemical‐stabilities 25,34,35 . Other examples containing carboxylate‐ or amide‐functional groups present in the alkyl side‐chain attachment on the imide ‐position of the PDI unit have also been reported and these functional groups have demonstrated a significant role in determining the polymeric materials property 31–33,36 …”

Surface‐Grafted Semiconductor Layer Prepared by Surface Initiated Ring‐Opening Polymerization of L‐Lysine NCA Derivatives

“…But their poor solubilities make them difficult to process even in solution, not to mention on solid substrates. We have reported two ordered ladder‐like polymers based on PBI derivatives to improve the materials’ thermal stability and solubility while retaining their optoelectronic properties in solution and in the bulk state 16d. 17 Herein, we report a facile method to prepare surface‐tethered polymeric semiconductor films using two novel ε‐ N ‐PBI functionalized L ‐lysine N ‐carboxylic anhydride (NCA) derivatives via SI‐ROP on silicon wafers for potential use in molecule electronic devices.…”