Novel Unsymmetrical Polydiacetylenes as Materials for Second- and Third-Order Nonlinear Optics

Masse, C. E.; Wiede, K. Vander; Kim, W. H.; Jiang, Xin; Kumar, Jyant; Tripathy, Sukant K.

doi:10.1021/cm00053a015

Cited by 15 publications

(8 citation statements)

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“…5 Over the last decade investigations of the non-linear optical properties have there have been extensive studies of the non-linear optical appeared.11,24 Low loss, monomode, channel waveguides have properties of single crystals, solutions and solution cast thin been fabricated with poly-9SMBU and the quadratic electrofilms of polydiacetylenes. [6][7][8][9][10][11][12][13][14][15][16][17][18][19] These have explored the microoptical coefficient measured.20,37 Degradation of solid films of scopic origins of the non-linearity, determined the properties the nBCMU polymers by ozone was investigated by Patel and relevant for application in all optical devices and produced Yee. 38 Photobleaching of poly-4BCMU spin coated films in new polydiacetylenes designed to have enhanced non-linearity.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic investigation of the photodegradation of polydiacetylene solutions

Bloor¹,

Worboys²

1998

J. Mater. Chem.

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Section: Introductionmentioning

confidence: 99%

Spectroscopic investigation of the photodegradation of polydiacetylene solutions

Bloor¹,

Worboys²

1998

J. Mater. Chem.

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“…Among these polymers, the polydiacetylenes ͑PDA's͒ have enjoyed a period of renaissance [1][2][3][4][5][6][7][8][9][10][11][12][13][14] and the synthesis of novel PDA's has enlarged our knowledge on their properties, in particular, on the values of their nonlinear susceptibilities. 15,16 In the last five years we have been interested in the study of a class of attractive PDA's, the polycarbazolyldiacetylenes, 5,[17][18][19][20][21][22] in particular, of poly͓1,6-di ͑ N-carbazolyl͒-2,4-hexadiyne͔͑polyDCHD͒, 5,[19][20][21][22][23][24][25][26] which is, however, insoluble.…”

Section: Introductionmentioning

confidence: 99%

Long-lived photoexcited states in polydiacetylenes with different molecular and supramolecular organization

et al. 1997

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“…Over at least the past decade, there has been considerable interest in the introduction of specific side groups into polydiacetylenes (PDA, 1 ) to control properties such as polymer chemical reactivity, electronic structure, , and spectroscopy, second-order nonlinear optical (NLO) properties, and chromic phenomena . In recent reports from our laboratories, the synthesis, acentric self-assembly, and second-order NLO properties of the PDA of the n -butoxycarbonylmethylurethane (BCMU) of 1-(5-pyrimidyl)-1,3-octadiyn-8-ol (BPOD, 2a ) point to a design paradigm that merits elaboration.…”

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confidence: 99%

Functionalizable Self-Assembling Polydiacetylenes and Their Optical Properties

Sukwattanasinitt

Wang

et al. 1998

Chem. Mater.

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Over at least the past decade, there has been considerable interest in the introduction of specific side groups into polydiacetylenes (PDA, 1) to control properties such as polymer chemical reactivity, 1 electronic structure, 1,2 and spectroscopy, 3 second-order nonlinear optical (NLO) properties, 4 and chromic phenomena. 5 In recent reports from our laboratories, 6 the synthesis, acentric self-assembly, and second-order NLO properties of the PDA of the n-butoxycarbonylmethylurethane (BCMU) of 1-(5-pyrimidyl)-1,3-octadiyn-8-ol (BPOD, 2a) point to a design paradigm that merits elaboration. In particular, we note three design features: (1) a conjugated backbone; (2) one side group as a chromophore; (3) the other side group with both aliphatic and hydrogenbonded urethane groups to promote solubility and processability. The polymer was found to spontaneously self-assemble into an acentric order with significant second-order optical nonlinearity. We now report the synthesis of the alkoxycarbonyl-methyl urethanes of 9-(N-methyl-N-phenylamino)-5,7-nonadiyn-1-ol (2b,c) and their polymerization. We find that the polymers are soluble and processable and that the benzenoid ring group is susceptible to many of the substitution reactions expected for aromatic amines making it a more versatile system for chemical modification than the previously investigated systems. 1 We further describe novel self-assembling and linear and nonlinear optical properties of the modified polymers. These polymers, in addition to possessing the unusual assembly properties of PDA-BPOD, present some unique processing features. The azobenzene-functionalized PDA from 2b, for example, was photofabricated to produce regular surface relief gratings. We conclude that the PDA from 2b,c and their functionalized forms comprise the most versatile PDA system reported to date, in terms of chemical richness and diverse optical properties.The synthesis of 2b,c is illustrated in Scheme 1. Cadiot-Chodkiewicz coupling of N-methyl-N-propargylaniline and 5-bromohexyn-1-ol leads to 9-(N-methyl-N-phenylamino)-5,7-nonadiyn-1-ol (2d) in 74% yield. Reaction of this diacetylene alcohol with the appropriate isocyanate leads to 2b,c; the yield of 2b is 73%.2b,c are viscous yellow oils at ambient temperature and did not polymerize in that phase on exposure to ultraviolet light. Crystallization was achieved as they were frozen in dry ice in evacuated ampules and polymerized in the solid state by exposure to 46 Mrad 60 Co γ radiation at a dose rate of 0.5 Mrad/h. The PDA from 2b,c, obtained in approximately 40% yield after monomer removal, are red-colored solids that are found to be soluble in a manner similar to PDA-BPOD and -BCMU in solvents such as chloroform and N,Ndimethylformamide (DMF) with an absorption maximum at 473 nm (CHCl 3 ). The 13 C NMR and Raman 2a,b spectra of the PDA from 2b,c verify the assignment of the usual enyne backbone structure, and gel permeation chromatography of a chloroform solution of the PDA of 2b reveals (relative to polystyrene) M w 190 000, ...

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Novel Unsymmetrical Polydiacetylenes as Materials for Second- and Third-Order Nonlinear Optics

Cited by 15 publications

References 0 publications

Spectroscopic investigation of the photodegradation of polydiacetylene solutions

Spectroscopic investigation of the photodegradation of polydiacetylene solutions

Long-lived photoexcited states in polydiacetylenes with different molecular and supramolecular organization

Functionalizable Self-Assembling Polydiacetylenes and Their Optical Properties

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