Oligo-2,6-naphthylenevinylenes – New Building Blocks for the Preparation of Photoluminescent Polymeric Materials

Abstract

Synthetic strategies towards appropriate symmetric and unsymmetric functionalization of the naphthalene ring are presented. By means of Knoevenagel and Wittig condensation reactions new fluorescent, differently functionalized oligo(2,6‐naphthylenevinylene)s have been synthesized, the presence of terminal aldehyde or bromine substitution opening the way to the incorporation of the fluorescent trimers in a variety of polymeric materials. The effect of substituting the phenylene ring by the more bulky dialkoxynaphthalene system in arylenevinylene‐type materials is studied from the structural point of view and the possibility to tune the emission color and the electron affinity through the introduction of naphthylenevinylene and cyano‐substituted naphthylenevinylene units is also investigated.

Synthesis of phenylenevinylene and naphthylenevinylene homopolymers and block copolymers by ring‐opening metathesis polymerization

“…The monomers including tetraoctyloxy‐substituted cyclophanedienes 1 and tetraoctyloxy‐substituted naphthalenophanedienes 2 and the initiator for ROMP such as the third‐generation Grubbs initiator (Fig. ) were prepared by the modification of the previously established synthetic methods …”

Heck reactions of stilbenoid chromophores with alkoxysilyl-substituted styrenes: Synthesis of monomers for luminescent polymers

“…1 H-, 13 C, and 29 Si-NMR-Spectra: in CDCl 3 , Bruker AC 200 and AM 400. Chemical shifts are reported in ppm and referenced to the solvent or TMS as internal standard.…”

“…† Dedicated to Prof. Dr. H. Ringsdorf on the occasion of his 75th birthday In some applications these well-defined chromophores proved to perform superior to their macromolecular homologues [9]. Additionally, the same strategies for the fine tuning of the electrooptical characteristics are suitable [10][11][12][13], but the strong propensity towards crystallisation is a major drawback for their use in devices. Successful strategies to stabilize amorphous films of monodisperse chromophores are the connection of the rigid π -systems with a flexible polymer, as segments in the main chain [14,15] or as side groups [16], the embedding of the electroactive compounds in a polymeric matrix like polysiloxanes [17,18] and also the linking of conjugated units to form globular molecules with a tetrahedral shape [19][20][21].…”

“…IR (neat): 3015, 2960, 2910, 2855, 1589, 1504, 1455, 1407, 1380, 1252, 1200, 1167, 1110, 1078, 962, 852, 821, 791, 769. 1 H-NMR (CDCl 3 ): 0.34 (s, 3 H, Si-CH 3 ), 0.80-1.00 (m, 12 H, CH 3 ), 1.24 (t, J = 6.9 Hz, 6 H, CH 3 ), 1.20-1.60 (m, 16 H, CH 2 ), 1.74 (sept, J = 6.5 Hz, 2 H, β-CH), 2.22 (s, 3 H, CH 3 ), 3.76-3.88 (m, 8 H, OCH 2 ), 6.72 (s, 1 H, 3-H ph ), 7.02 (s, 1 H, 6-H ph ), 7.10 (d, 1 H, vin), 7.12 (AB, 2 H. vin), 7.46 (d, 1 H, vin), 7.49 (s, 4 H, ph)7.52 (d, 2 H, ph ), 7.61 (d, 2 H, ph ) 13. C-NMR (CDCl 3 ): −4.1 (Si-CH 3 ), 11.3, 14.1, 16.5, 18.4 (CH 3 ), 23.1, 24.12, 29.2, 30.8, 30.9 (CH 2 ), 39.7 (CH), 58.6 (Si-OCH 2 ), 71.0, 72.0 (OCH 2 ), 108.8, 115.8 (C-3, C-6 ph ), 124.0, 124.3, 127.1, 127.9, 128.1, 129.1, 134.1, 136.1, 137.9, 139.0 (CH vin, C q ar), 125.9, 126.7, 126.9, 134.5 (CH ph , ph), 150.7, 151.6 (C-O).…”

Synthesis and optical properties of blue luminescent poly(2,6‐naphthalene)s

“…On the contrary, chiral poly(binaphthyl) analogues, a kind of naphthalene homopolymers reported by Habaue et al, 11 are soluble in organic solvents. Several naphthalene molecules and poly(naphthalenevinylene)s have been reported to show intense photoluminescence (PL), [12][13][14][15] which could be utilized for the optical devices such as organic light emitting diodes and organic lasers etc. Recently, we have reported the synthesis and PL properties of new soluble naphthalene homopolymers and copolymers shown in Figure 1.…”