&lt;title&gt;Improved third-order nonlinear optical properties of polydiacetylene derivatives&lt;/title&gt;

Okada, Shuji; Nakanishi, Hachiro; Matsuzawa, Hiroshi; Katagi, Hideyuki; Oshikiri, Toshiyuki; Kasai, Hitoshi; Sarkar, Abhijit; Oikawa, Hidetoshi; Rangel-Rojo, R.; Fukuda, Takashi; Matsuda, Hiro

doi:10.1117/12.368302

Cited by 10 publications

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“…In particular, oligoyne derivatives with five or more conjugated acetylenes yielded ladder polymers with p-conjugation between two PDA backbones, as shown in Figure 1. [20][21][22] At first, one of the butadiyne groups in the oligoyne moiety is polymerized to yield a linear PDA structure (reaction I); thereafter, the other side of the butadiyne group is polymerized to produce the ladder-type PDA structure (reaction II). The interesting electron spin behavior caused by this peculiar pconjugation system has been reported.…”

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“…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 or more conjugated acetylenes yielded ladder polymers with p-conjugation between two PDA backbones, as shown in Figure 1.…”

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

Inayama

Tatewaki

Okada

2009

Polym J

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“…Thus, in order to prepare such ladder-type PDAs, monomers with two butadiyne moieties have been synthesized and their solid-state polymerization was studied. [24][25][26] Especially, the monomers, in which two butadiyne moieties are connected by methylene chains with more than four carbons, were found to give fully polymerized ladder polymers. 25 As a similar approach, preparation of a ladder polymer using p-xylylenediammonium disorbate as the bifunctional monomer in crystalline state was also reported recently.…”

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“…The electronic structure of their π-conjugated polymer backbone must be perturbed by conjugation effect from substituents. 13,14 Thus, we have been synthesizing a variety of PDAs having π-conjugation between polymer backbone and side chains, e.g., PDAs with aromatic substituents [15][16][17][18][19] and acetylenic substituents, [20][21][22][23][24] and confirmed enhancement of NLO properties. [16][17][18] The PDAs in the other category contain design to increase π-conjugated backbone density.…”

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Solid-State Polymerization of Monomers Possessing Two Diphenylbutadiyne Moieties with Amido Groups to Form Ladder Polymers

Matsuo

Okada

Nakanishi

et al. 2002

Polym J

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ABSTRACT:Two series of monomers possessing two diphenylbutadiyne moieties connected by a methylene chain via amido groups, i.e., alkanedi{3-[4-(3-nitrophenyl)butadynyl]anilide} (N-n) and alkanedi{3-[4-(3-alkanoylaminophenyl)butadiynyl]anilide} (mA-n), were synthesized, and their solid-state polymerization behaviors and the polymer structures were investigated by various spectroscopic measurements and powder X-Ray diffractions. Although polymerization of N-n only proceeds in one of two diphenylbutadiyne moieties in a monomer to give single-chain polydiacetylenes, mA-n polymerized at both diphenylbutadiyne moieties to give double-chain polydiacetylenes. All the results suggest that two arrays of intermolecular hydrogen bonding formed between two diphenylbutadiyne moieties for N-n are not sufficient to fix the structure, and atomic movements during polymerization influence the polymerizable stack of the other remaining diphenylbutadiyne to disorder into non-polymerizable one. Meanwhile, mA-n can form four arrays of intermolecular hydrogen bonding on both sides of each diphenylbutadiyne moiety to fix it, and polydiactylene-based ladder polymers were successfully prepared from mA-n.

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An Effective Approach to Achieve a Spin Gapless Semiconductor–Half‐Metal–Metal Transition in Zigzag Graphene Nanoribbons: Attaching A Floating Induced Dipole Field via π–π Interactions

Guan

Chen

et al. 2012

Adv Funct Materials

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Under fi rst-principles computations, a simple strategy is identifi ed to modulate the electronic and magnetic properties of zigzag graphene nanoribbons (zGNRs). This strategy takes advantage of the effect of the fl oating dipole fi eld attached to zGNRs via π -π interactions. This dipole fi eld is induced by the acceptor/donor functional groups, which decorate the ladder-structure polydiacetylene derivatives with an excellent delocalized π -conjugated backbone. By tuning the acceptor/donor groups, -C≡C-number, and zGNR width, greatly enriched electronic and magnetic properties, e.g., spin gapless semiconducting, half-metallic, and metallic behaviors, with the antiferromagnetic − ferromagnetic conversion can be achieved in zGNRs with perfect, 57-reconstructed, and partially hydrogenated edge patterns. can produce potential differences between the edges of zGNRs and drive zGNRs into half-metal, even provide other appealing electronic features, e.g., spin gapless semiconductor, by changing the -C≡C-number of the PDA bridges. Note that PDA and its -C≡C-bridged ladder-structure derivatives have been synthesized experimentally, [71][72][73][74][75] and a PDA layer adhered on the graphene surface has been fabricated recently as a bimorph actuator with compelling advantages to the traditional electromechanical actuation technology, [ 76 ] and the electronic couplings of PDA nanowires on graphite have also been experimentally studied. [77][78][79] Moreover, the NO 2 /NH 2 decorated ladder-structure PDA derivatives linked with one -C≡C-bond were predicted to exhibit signifi cantly enhanced nonlinear optical (NLO) responses due to the excellent π -conjugated delocalization of the PDA backbone. [ 80 ] Here, we perform comprehensive density functional theory (DFT) computations to investigate the electronic and magnetic properties of the joint systems of zGNR and the decorated PDA derivatives, emphasizing the effects of different pairs of acceptor/donor groups, number of -C≡C-bonds in the PDA derivatives and the zGNR width, even the existence of edge 57-reconstruction in zGNRs. Our studies revealed that depositing the decorated PDA derivatives on perfect H-terminated zGNRs renders the joint systems the transition of SGS-halfmetal-metal, accompanied by the magnetic conversion from AFM to FM. Even with the existence of 57-reconstruction at the zGNR edges, abundant electronic and magnetic transitions of AFM SGS-FM half-metal-AFM metal-NM metal can also be observed in the joint systems. Moreover, through partially hydrogenating zGNRs at the 57-reconstructed edges, the effect of the edge reconstruction can be eliminated, and more fascinatingly, the electronic and magnetic properties of the joint systems based on edge-reconstructed wide zGNRs can be generally recovered to those of the corresponding joint systems with perfect narrow H-terminated zGNRs representing the remaining pristine zGNRs inside. DOIThese provide immensely valuable insights for facilitating the spintronic applications and effectively modulating the electronic an...

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<title>Improved third-order nonlinear optical properties of polydiacetylene derivatives</title>

Cited by 10 publications

References 0 publications

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

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

Solid-State Polymerization of Monomers Possessing Two Diphenylbutadiyne Moieties with Amido Groups to Form Ladder Polymers

An Effective Approach to Achieve a Spin Gapless Semiconductor–Half‐Metal–Metal Transition in Zigzag Graphene Nanoribbons: Attaching A Floating Induced Dipole Field via π–π Interactions

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