Ladder-Type Polymers and Ladder-Type Polyelectrolytes with On-Chain Dibenz[a,h]anthracene Chromophores

Abstract

The alternating copolymerization of fluorene and diethynyl benzene building blocks and postpolymerization electrophilic cyclization result in the generation of well-defined ladder poly(dibenz[a,h]anthracene)s (PLDBAs). PLDBAs combine the specific optical properties of the aromatic building blocks with well-resolved, vibronically structured photoluminescence spectra and a small Stokes shift (5 nm), as typical characteristics of ladder polymers, with an excellent solubility in organic solvents. Success of the ladderization step was confirmed by NMR-and IR-spectroscopies. The presence of syn-and anti-isomeric repeat units along the polymer backbone was proven by an investigation of corresponding model compounds. In addition, this concept was used for the synthesis of the corresponding ladder polyelectrolytes, bearing cationic imidazolium groups in their sidechains. The polyelectrolytes show very similar optical and electronical properties if compared to their noncharged counterparts but are now soluble in protic, polar solvents as methanol.

Spiropyran‐Functionalized Polymer–Carbon Nanotube Hybrids for Dynamic Optical Memory Devices and UV Sensors

“…All chemicals were used as obtained from commercial suppliers. 2‐Bromo‐9,9‐didodecylfluorene, [ 37 ] 2,7‐dibromo‐9,9‐didodecylfluorene, [ 38 ] monomers, and poly(9,9‐didodecyl‐fluorene‐2,7‐diyl) [ 39 ] (PF12, M n = 12.0 kDa, M w = 18.0 kDa) were synthesized using literature procedures. Spiropyran‐functionalized polyfluorene copolymers (SP11, SP25) were synthesized using a method for postpolymerization functionalization of conjugated polymers [ 22 ] and is described in detail in the Supporting Information.…”

Synthesis of Single‐Handed Helical Spiro‐Conjugated Ladder Polymers through Quantitative and Chemoselective Cyclizations**

“…Fluorene‐ (FL‐ b Me and poly‐FL‐ b Me ) and naphthalene‐ (NAP‐ b Me and poly‐NAP‐ b Me ) based π‐conjugated molecules and polymers with exquisite ladder structures could also be readily synthesized from the corresponding cyclization precursors through the quantitative and chemoselective cyclization approach only when the two methyl substituents were introduced at the 2,6‐positions on the 4‐alkoxyphenyl pendants (Figure 5 A and B(iii‐vi)) [16] . Again, the acid‐promoted alkyne benzannulations of FL‐ a H and NAP‐ a H without 2,6‐dimethyl substituents afforded product mixtures (Figure 5 B(i,ii)).…”

Synthesis of Single‐Handed Helical Spiro‐Conjugated Ladder Polymers through Quantitative and Chemoselective Cyclizations**

“…Fluorene-(FL-b Me and poly-FL-b Me ) and naphthalene-(NAP-b Me and poly-NAP-b Me ) based p-conjugated molecules and polymers with exquisite ladder structures could also be readily synthesized from the corresponding cyclization precursors through the quantitative and chemoselective cyclization approach only when the two methyl substituents were introduced at the 2,6-positions on the 4-alkoxyphenyl pendants (Figure 5 A and B(iii-vi)). [16] Again, the acid-promoted alkyne benzannulations of FL-a H and NAP-a H without 2,6dimethyl substituents afforded product mixtures (Figure 5 B-(i,ii)).…”