Synthesis and nonlinear optical properties of donor-acceptor substituted triaryl azole derivatives

Moylan, Christopher R.; Miller, Robert D.; Twieg, Robert J.; Betterton, K.; Lee, Victor Y.; Matray, Tracy J.; Nguyen, Cattien V.

doi:10.1021/cm00034a021

Cited by 101 publications

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“…Both steps are described in Scheme 13. (Moylan et al, 1993) In a 1 L, three-necked, round-bottom flask equipped with a reflux condenser, a magnetic stirrer bar, and a nitrogen inlet were placed 6 g (22 mmol) of 4,4'-dimethoxybenzil, 60 ml of acetic acid (HOAc), and 300 ml HBr (68%). The suspension was heated at reflux with stirring for 4 h to become a homogeneous yellow solution which was cooled to room temperature, during which a yellow solid was formed.…”

Section: Synthesis Of the Monomermentioning

confidence: 99%

Synthesis of Thermally Stable Polyesters

Mighani¹

2012

Polyester

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Section: Synthesis Of the Monomermentioning

confidence: 99%

Synthesis of Thermally Stable Polyesters

Mighani¹

2012

Polyester

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“…Owing to synthetic difficulties, most of the NLO imidazoles developed so far, namely, 2,4,5-triaryl(heteroaryl)-imidazoles only possess short conjugation pathways (spacers) such as phenyl, thienyl or thiazolyl. Following our interest in heterocyclic derivatives for optical applications [14][15][16][17][18][19][20][21], we report in this communication the synthesis and characterization of the linear and nonlinear optical properties of NLO chromophores 3, containing a functionalized oligothienyl π conjugated bridge linked to the imidazo-phenanthroline system, which is original and different from other related reports [1][2][3][4][5][6].…”

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confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10]. Phenanthroline derivatives have been extensively used as ligands in both analytical and preparative coordination chemistry [12].…”

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confidence: 99%

“…Oligothienyl-imidazo-phenanthrolines 3 were synthesised with different thiophenic substituents at the 2-position of the imidazo-phenanthroline moiety in order to evaluate the effect of the nature of the π-conjugated bridge on the solvatochromic and nonlinear optical properties of chromophores 3. Therefore, compounds 3 with either thienyl, bithienyl and terthienyl moieties (substituted with H or methoxy groups) linked to the imidazo-phenanthroline system, were synthesized in good to excellent yields (76-92%), by condensation of 5,6-phenanthroline-dione 2 with formyl-thiophene derivatives 1 [14] in the presence of ammonium acetate in refluxing glacial acetic acid [1] for 15 h (Scheme 1). The structures of the new phenanthrolines 3 were unambiguously confirmed by their analytical and spectral data (Table 1).…”

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New Oligothienyl-Imidazo-Phenanthroline Chromophores for NLO Applications

Batista

Costa

Lodeiro

et al. 2008

MSF

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Abstract. A new series of oligothienyl-imidazo-phenanthrolines 3 were synthesised in good to excellent yields by condensation of 5,6-phenantroline-dione 2 with formyl-thiophene derivatives 1 in the presence of ammonium acetate in glacial acetic acid. Furthermore, their solvatochromism and molecular optical nonlinearities were determined and comparatively studied. The experimental results indicate that phenanthrolines 3, due to their moderate solvatochromic properties and good optical nonlinearities, could be used as suitable probes for the determination of solvent polarity and as nonlinear optical materials.Introduction Donor-acceptor π-conjugated organic materials have received much attention as they offer many new possibilities for devices combining unique optical, electrical and mechanical properties. In particular, chromophores bearing low aromaticity heterocycles along the conjugation path have been investigated and are considered as the most suitable for these applications. Heterocyclic imidazole based chromophores have received increasing attention due to their distinctive linear and nonlinear optical properties and also due to their excellent thermal stability in guest-host systems and good miscibility with high performance polymers. The imidazole ring can be easily tailored to accommodate functional groups, which allows the covalent incorporation of the NLO chromophores into polyamides leading to NLO side chain polymers [1][2][3][4][5][6][7][8][9][10]. New material properties can be achieved when new conjugated systems are composed by different heterocyclic nuclei which allow the fine tuning of important physical and/or photophysical properties. Oligothiophenes behave as very efficient electron relays almost comparable to polyenes, because of the lower resonance energy of thiophene compared to that of benzene, and have been shown to give larger contributions to β. Oligophenylenes attain a rapid saturation beyond the terphenyl unit, whereas oligothiophenes have a strong tendency to increase β with increasing number of thiophene units. Aside from the electron transmission efficiency, another merit of oligothiophenes is their inherent stability from which thiophene-based Donor (D) -Acceptor (A) chromophores should benefit [11].

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“…Although organic NLO materials usually have a much higher NLO response than inorganic materials, their optical application is often limited by the strong, conjugation-induced red-shifts of their longest-wavelength electronic absorption bands from the UV to the visible region [13]. Zyss [14], and Moylan et al [15] have indicated that partial interruption of chain conjugation in linearly p-conjugated materials, for instance, by incorporation of an appropriate spacer, might lead to good NLO properties and avoid extension of the electronic absorptions into the visible region. Thus, benzenoid hetero-spacers 1 ) were incorporated into the hybrid oligomers 4 ± 9 in an attempt to reduce the efficiency of the overall linear p-electron Helvetica Chimica Acta ± Vol.…”

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Modulation ofπ-Electron Conjugation in Oligo(triacetylene) Chromophores by Incorporation of a Central Spacer

Martin

Wytko

Diederich

et al. 1999

HCA

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A comprehensive series of trimeric hybrid oligomers 4 – 14 (Fig. 2) was prepared by insertion of different hetero‐spacers between two (E)‐hex‐3‐ene‐1,5‐diyne (=(E)‐1,2‐diethynylethene, DEE) moieties, and the optical and electrochemical properties of the resulting π‐conjugated materials compared to those of the DEE dimer 2 and trimer 3, which formally contains a DEE moiety as homo‐spacer. The hetero‐spacers varied from benzenoid (phenylene, naphthalene, biphenylene, anthracene), to π‐electron‐deficient (pyrazine, pyridine) and π‐electron‐rich (thiophene, furan) aromatic rings, and to an organometallic trans‐Pt(PEt3)2 fragment. The hybrid oligomers were synthesized following a general strategy which relied on the Sonogashira cross‐coupling between mono‐deprotected DEE 15 and the appropriately bis‐functionalized spacer (Scheme and Table 1). UV/VIS Studies revealed that the majority of the hetero‐spacers were less effective than the homo‐spacer DEE in facilitating π‐electron delocalization along the linearly conjugated oligomeric backbone (Table 2 and Fig. 3). With increasing degree of benzenoid aromaticity in the hetero‐spacer, the electronic communication between the terminal DEE moieties in the hybrid oligomers was reduced. As a remarkable exception, a large bathochromic shift of the longest‐wavelength absorption maximum, which is indicative of enhanced π‐electron delocalization, was obtained upon introducing an anthracene‐9,10‐diyl moiety as hetero‐spacer into oligomer 7 (Figs. 3 and 6). Electrochemical investigations by cyclic and steady‐state voltammetry confirmed the limited extent of π‐electron delocalization in the majority of the hybrid oligomers (Table 3). The fluorescence properties of many of the DEE hybrid materials were dramatically enhanced upon incorporation of the hetero‐spacers (Table 2). The heterocyclic derivatives 10 – 12, containing pyridine, pyrazine, or thiophene spacers, respectively, displayed a strong fluorescence emission, which is present to a significant extent neither in DEE homo‐oligomers nor in the individual heteroaromatic spacer components, demonstrating the value of combining different repeat units to modulate oligomeric and polymeric properties. The pyridine derivative 10 provided an interesting example of a molecular system, in which both the electronic absorption (Fig. 4) and emission characteristics (Table 2) can be reversibly switched as a function of pH (Fig. 5).

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Synthesis and nonlinear optical properties of donor-acceptor substituted triaryl azole derivatives

Cited by 101 publications

References 0 publications

Synthesis of Thermally Stable Polyesters

Synthesis of Thermally Stable Polyesters

New Oligothienyl-Imidazo-Phenanthroline Chromophores for NLO Applications

Modulation ofπ-Electron Conjugation in Oligo(triacetylene) Chromophores by Incorporation of a Central Spacer

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