Solid state phase transformation of a diacetylene by solvation. Crystal structure of a moderately reactive monomer form

Patel, G. N.; Duesler, Eileen N.; Curtin, David Y.; Paul, Iain C.

doi:10.1021/ja00522a003

Cited by 47 publications

(23 citation statements)

References 8 publications

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“…After extraction of residual monomer from partially polymerized crystals a red polymer with a broad absorption at ,a, < 540 nm is obtained, as indicated by the diffuse reflectance spectrum shown in figure 2. A similar absorption behaviour of the polymer is observed for compound (la) and has also been reported for other polydiacetylenes [3,16,17].…”

Section: Polymerization Properties Of the Ester Compounds In The Solisupporting

confidence: 86%

Amphiphilic diacetylenes with pyridine and 2,2?-bipyridine headgroups ? polymerization properties in the crystalline state, in LB-multilayers, and in complexes with transition metal salts. Morphology of polymerized multilayers

Tieke

Weiss

1985

Colloid & Polymer Sci

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Synthesis, amphiphilic properties and polymerization behaviour of a variety of single and double chain esters of pyridine-and 2,2'-bipyridine-carboxylic acids containing the diacetylene moiety are described. Conversion versus 6~ dose curves indicate significant differences in solid-state reactivity of the individual compounds. The esters of isonicotinic acid form polymers that are soluble in chloroform. The monomers can be converted into salt derivatives and transition metal complexes, some of which are characterized concerning their solid state reactivity.Esters of isonicotinic acid form stable monolayers if spread onto neutral or acidified aqueous subphases at temperatures < 15 ~ These monolayers can be deposited on substrates by the Langmuir-Blodgett technique and subsequently be UV-polymerized. In addition, attempts are reported to form polymeric mono-and multilayers by spreading the soluble polymeric amphiphiles at the air-water interface and subsequently transferring the films onto substrates.The two types of polymeric films exhibit morphologies that are significantly different. Polarizing micrographs indicate a domain structure of randomly shaped crystallites of only a few micrometers in diameter for LB-monolayers built up as monomers and polymerized on the substrate. On the other hand, polymer films built up as polymers are inhomogeneous and do not actually represent monomolecular films.

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Section: Polymerization Properties Of the Ester Compounds In The Solisupporting

confidence: 86%

Amphiphilic diacetylenes with pyridine and 2,2?-bipyridine headgroups ? polymerization properties in the crystalline state, in LB-multilayers, and in complexes with transition metal salts. Morphology of polymerized multilayers

Tieke

Weiss

1985

Colloid & Polymer Sci

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“…Generally, symmetrically substituted butadiyne derivatives with two urethane groups often give two arrays of intermolecular Solid-state polymerization of hexayne derivatives S Inayama et al hydrogen bonding within a monomer array. 6,[28][29][30] Thus, 2 seems not to be an exception, and the strong intermolecular hydrogen bonding in one direction helps to maintain the regular structure even after forming the ladder-type PDA. Previously, the visible-near-IR spectrum of the polymer from a hexayne compound with substituents of -(CH 2 ) 5 -O-CO-NH-C 6 H 5 , that is, a homolog of 2 with a different methylene number, was studied, and clear broad bands in the near-IR region were not detected, although excitonic bands appeared.…”

Section: Resultsmentioning

confidence: 99%

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Inayama

Tatewaki

Okada

2009

Polym J

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Three hexayne derivatives with different end groups-that is, 10,12,14,16,18,20-triacontahexayne-1,30-diol (1) and its diphenylurethane (2) and diphenylester (3)-were synthesized, and their solid-state polymerization behaviors were investigated. All three monomers were thermally polymerizable. Polymers from 1 and 2 showed an absorption maximum at about 730 nm, indicating that linear polydiacetylenes (PDAs) with octatetraynyl substituents were synthesized. However, broad absorption bands in the near-infrared region were only observed for 2 at 980 and 860 nm, indicating that regular polymerization occurred in 2 to give ladder-type PDA. On the other hand, a polymer from 3 showed a visible absorption increase but no clear absorption maximum. It was estimated that intermolecular hydrogen bonding between hexayne monomers helps to form polymerizable stacks in 1 and 2. In particular, urethane groups are more effective, and 2 showed the highest reactivity in this study with an ordered interlayer structure even after a two-step solid-state polymerization to give ladder-type PDA. Keywords: ladder polymer; polydiacetylene; solid-state polymerization; p-conjugated polymer Some butadiyne compounds are polymerized in the solid state by ultraviolet irradiation or by thermal treatment. This solid-state polymerization was clarified by Wegner 1 as a single-crystal-to-singlecrystal topochemical transition to yield polydiacetylene (PDA), which is classified as a one-dimensional p-conjugated polymer. Since the reaction is topochemically controlled, the reactivity of butadiyne monomers is greatly affected by their packing in crystals. 2 In fact, when the butadiyne monomers in crystals have a stacking distance d of about 5 Å between adjacent molecules in the array and an angle y of about 45 1 between the butadiyne rod and stacking axis, 1,4-addition polymerization occurs. Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic 5-7 and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest. To achieve larger NLO susceptibility (w (3) ) in PDA, it is necessary to increase the density of the p-conjugated polymer backbone and the p-electron number in a repeating unit. In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five...

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“…Par ailleurs, un m~me monom6re peut pr6senter, plusieurs phases de couleurs et d'activit6s diff6rentes: c'est le cas, par exemple, du bis[(m-tolyl)carbamate] de hexadiyne-2,4 diyl-l,6 (HDmTU) qui cristallise sous deux formes, l'une orange mod6r6ment active, l'autre bleue tr+s active (Patel, Duesler, Curtin & Paul, 1980), ou encore du bis(ph6nylcarbamate) de d6cadiyne-4,6 diyl-1,10 (DDPU) (formes rouge et bleue). Selon Patel, cette diversit6 de couleurs, sp6cifique aux ur&hanes, serait corr616e h la plan6it6 et h r&at de contraintes des molecules polym6res form6es au sein du cristal monom+re.…”

Section: (1)--c (2)--c (3)--c (4) C ( 1)--c (6)--c (5)--c (4) C (1)unclassified

Détermination structurale à 163 K du monomère bis[(p-chlorophényl)carbamate] de hexadiyne-2,4 diyl-1,6, C20H14Cl2N2O4

Brouty¹,

Spinat²,

Whuler³

1983

Acta Crystallogr C

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Solid state phase transformation of a diacetylene by solvation. Crystal structure of a moderately reactive monomer form

Cited by 47 publications

References 8 publications

Amphiphilic diacetylenes with pyridine and 2,2?-bipyridine headgroups ? polymerization properties in the crystalline state, in LB-multilayers, and in complexes with transition metal salts. Morphology of polymerized multilayers

Amphiphilic diacetylenes with pyridine and 2,2?-bipyridine headgroups ? polymerization properties in the crystalline state, in LB-multilayers, and in complexes with transition metal salts. Morphology of polymerized multilayers

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Détermination structurale à 163 K du monomère bis[(p-chlorophényl)carbamate] de hexadiyne-2,4 diyl-1,6, C20H14Cl2N2O4

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