Constructing π-Electron-Conjugated Diarylbutadiyne-Based Polydiacetylene under Molecular Framework Controlled by Hydrogen Bond and Side-Chain Substituent Position

Tanphibal, Pimsai; Tashiro, Kohji; Chirachanchai, Suwabun

doi:10.1002/marc.201500690

Cited by 14 publications

(6 citation statements)

References 32 publications

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“…In our previous investigations of the solid-state packing of [24]-dehydroannulenes, we noted that carbamate groups could be exploited to achieve tight, in-register crystal packing of the internal butadiyne units . While designing monomers to access [8] A GNRs, we anticipated that either amide, carbamate, or urea functionalities would be suitable to promote tight, in-register packing of simple diphenylbutadiynes, as discovered previously. − Our own synthesis and characterization of diynes 3 , 4a , and 4c confirmed their predisposition to undergo topochemical polymerization (Figure and Scheme ). We also synthesized a range of diphenylbutadiynes containing a number of different amide substituents in their meta position and were delighted to find that many of them, including amide 4b , provide crystals that undergo topochemical polymerization.…”

Section: Resultssupporting

confidence: 70%

Synthesis of N = 8 Armchair Graphene Nanoribbons from Four Distinct Polydiacetylenes

Jordan

Lin

et al. 2017

J. Am. Chem. Soc.

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We demonstrate a highly efficient thermal conversion of four differently substituted polydiacetylenes (PDAs 1 and 2a-c) into virtually indistinguishable N = 8 armchair graphene nanoribbons ([8]GNR). PDAs 1 and 2a-c are themselves easily accessed through photochemically initiated topochemical polymerization of diynes 3 and 4a-c in the crystal. The clean, quantitative transformation of PDAs 1 and 2a-c into [8]GNR occurs via a series of Hopf pericyclic reactions, followed by aromatization reactions of the annulated polycyclic aromatic intermediates, as well as homolytic bond fragmentation of the edge functional groups upon heating up to 600 °C under an inert atmosphere. We characterize the different steps of both processes using complementary spectroscopic techniques (CP/MAS C NMR, Raman, FT-IR, and XPS) and high-resolution transmission electron microscopy (HRTEM). This novel approach to GNRs exploits the power of crystal engineering and solid-state reactions by targeting very large organic structures through programmed chemical transformations. It also affords the first reported [8]GNR, which can now be synthesized on a large scale via two operationally simple and discrete solid-state processes.

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Section: Resultssupporting

confidence: 70%

Synthesis of N = 8 Armchair Graphene Nanoribbons from Four Distinct Polydiacetylenes

Jordan

Lin

et al. 2017

J. Am. Chem. Soc.

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“…An apparent color change from pale yellow to yellow was also observed (inserted in Figure S8). Given the low degree of polymerization (or oligomerization) learned from these spectra, the yellow color was supposed to originate from a solvated polydiacetylene in addition to unreacted monomers and oligomers. , In addition to such a spectrometry method, the existence of the corresponding polymer/oligomer can also be figured out by gel permeation chromatography (Figure S9).…”

Section: Resultsmentioning

confidence: 99%

Engineering Rotaxane-Based Nanoarchitectures via Topochemical Photo-Cross-Linking

et al. 2018

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Polymerization of monomers included by macrocyclic hosts has been found as an efficient way to synthesize sophisticated rotaxane-based nanostructures, whereas such a process triggered by photon has received little coverage so far. Herein, a new diphenyldiacetylene (DPDA) derivative (compound 1) comprising viologen as a binding site toward cucurbit[7]uril (CB[7]) macroring, and isophthalate as a bulky stopper, was rationally designed and prepared. After verifying the photo-cross-linking efficiency of compound 1 upon its regular self-assembly, we also achieved a straightforward construction of rotaxane-based nanoarchitecture 2 ⊂ CB[7] through an in situ photoirradiation on the corresponding pseudo[2]rotaxane 1 ⊂ CB[7]. Although the threading of CB[7] changed the self-assembly behavior of the DPDA derivative, the topochemical reaction could be definitely observed to afford the corresponding photo-cross-linked species. Such a process could be facilely indicated by distinctive photoluminescence enhancement on the basis of π-conjugated skeleton change of DPDA toward potential usage of rotaxane-based systems as smart optoelectronic materials. We anticipate this unique strategy will allow new visions for the synthesis and application of novel luminescent host–guest nanoarchitectures.

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“…One obvious approach to making a tubular structure rigid is to connect the component molecules using covalent bonding. In this regard, macrocyclic compounds containing diacetylene (DA) moieties − are very promising because properly aligned DAs can undergo topochemical polymerization − to produce a conjugated polymer called polydiacetylene (PDA). − As schematically represented in Figure , a macrocyclic diacetylene (MCDA) (Figure a) can self-assemble to form a tubular structure (Figure b). Polymerization of the stacked supramolecular MCDA tube should then lead to formation of tubular PDA, poly(MCDA) (Figure c).…”

Section: Introductionmentioning

confidence: 99%

Chromogenic Tubular Polydiacetylenes from Topochemical Polymerization of Self-Assembled Macrocyclic Diacetylenes

Heo¹,

Kim

Han³

et al. 2017

Macromolecules

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Tubular materials formed by self-assembly of small organic molecules find great utility in chemical and material science. Conventional tubular structures often lack stability because noncovalent molecular interactions are responsible for their conformational integrities. Herein we report the development of covalently linked chromogenic organic nanotubes which are prepared by using topochemical polymerization of self-assembled macrocyclic diacetylenes (MCDAs). Crystal structures of five MCDAs having different diameters were elucidated, and four of these substances were transformed to tubular polydiacetylenes (PDA) by UV-induced polymerization. Surprisingly, MCDA-1 was found to self-assemble in stacks with a tilt angle of 62.1°, which significantly deviates from the optimal value for polymerization of 45°. This observation suggests that geometric parameters derived using linear diacetylene (DA) models might not be strictly applicable to polymerization of MCDA systems. Blue-phase PDAs obtained by polymerization of MCDA-1 and MCDA-3 have different thermochromic and solvatochromic properties, which enable them to be utilized for colorimetric differentiation of aromatic solvents including isomeric xylenes. The observations made and information obtained in this study should enhance the understanding and design of stimulus-responsive rigid organic nanotubes.

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Constructing π-Electron-Conjugated Diarylbutadiyne-Based Polydiacetylene under Molecular Framework Controlled by Hydrogen Bond and Side-Chain Substituent Position

Cited by 14 publications

References 32 publications

Synthesis of N = 8 Armchair Graphene Nanoribbons from Four Distinct Polydiacetylenes

Synthesis of N = 8 Armchair Graphene Nanoribbons from Four Distinct Polydiacetylenes

Engineering Rotaxane-Based Nanoarchitectures via Topochemical Photo-Cross-Linking

Chromogenic Tubular Polydiacetylenes from Topochemical Polymerization of Self-Assembled Macrocyclic Diacetylenes

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