Phenyl−Perfluorophenyl Stacking Interactions:  Topochemical [2+2] Photodimerization and Photopolymerization of Olefinic Compounds

Coates, Geoffrey W.; Dunn, Alex R.; Henling, Lawrence M.; Ziller, Joseph W.; Lobkovsky, and Emil B.; Grubbs, Robert H.

doi:10.1021/ja974072a

Cited by 491 publications

(337 citation statements)

References 70 publications

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“…The zigzag-type polymerization hardly occurs for the 1,3-diene monomers, although such a possibility was postulated for the diacetylene and diolefin polymerizations. 71,72 The present polymerization principles for the 1,3-diene monomers seem to have features similar to the empirical rules for the polymerization of diacetylene compounds reported in the literature; 24, 25 d s 5 Å and θ 45 • . However, the former rules are more sensitive to a slight change in the monomer crystal structure.…”

Section: Topochemical Polymerization Principles (The 5 å Rule)supporting

confidence: 80%

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

111

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ABSTRACT:In this review article, polymer structure control and organic material design based on polymer crystal engineering are described. The structures and properties of crystalline materials are designed using pre-organized molecules through various intermolecular interactions such as hydrogen bonds, π · · · π, CH/π, CH/O, and halogen interactions. Here, we describe the features and mechanisms of the topochemical polymerization of 1,3-diene monomers including some ester, ammonium, and amide derivatives of muconic and sorbic acids, which are 1,3-diene di-and monocarboxylic acid derivatives, respectively. We have proposed the topochemical polymerization principles for diene monomers on the basis of the crystallographic data accumulated for various kinds of diene monomers. The combination of several intermolecular interactions is useful for the construction of molecular packing appropriate for 5 Å stacking in order to facilitate the topochemical polymerization in the crystalline state. We refer to the control of polymer chain structure including tacticity, molecular weight, and ladder structure, and also polymer crystal structures, as well as the organic intercalation system using layered polymer crystals obtained by the topochemical polymerization. A totally solvent-free system for the synthesis of layered polymer crystals is also described.KEY WORDS Topochemical Polymerization / Solid-State Reaction / Crystal Engineering / Supramolecular Synthon / Stereoregular Polymer / Controlled Radical Polymerization / X-Ray Single Crystal Structure Analysis / Intercalation / Controlled polymer synthesis, including the control of polymer chain structures such as molecular weight, molecular weight distribution, chain-end structure, branching, regioselectivity, and stereoselectivity, has great potential for the design of macromolecular architecture leading to advanced nano-materials and devices. [1][2][3][4][5][6][7][8][9][10][11] All the features and functions of polymers importantly depend on primary chain structures and the manner of polymer chain assembly in crystalline and non-crystalline solids, or in a condensed state. Therefore, the control of polymer chain structures in polymer synthesis can hardly be overestimated for the architecture of advanced polymeric materials.Especially, the stereochemistry of polymers has received significant attention in both fundamental and applied fields ever since the first discoveries of stereoregular polymers in the 1950s. 12-14 Highly controlled stereospecific polymerization has been well established by coordination polymerization of olefins and diene monomers and by anionic polymerization of certain types of polar monomers. Radical polymerization is the most important and convenient process for the production of various kinds of vinyl and diene polymers due to recent achievements in well-controlled polymerizations in addition to the classical advantages of the radical process. [15][16][17][18][19][20][21][22] There are two fundamentally different ways to control of the chain structu...

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Section: Topochemical Polymerization Principles (The 5 å Rule)supporting

confidence: 80%

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

111

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“…[20b] The strong association between the F···HÀN hydrogen-bonded foldamers and fullerenes may result from cooperative fluorophenyl···p interactions, as proposed by Row et al, [27,28] and solvophobic interactions (Figure 4). The fact that the values for C 70 are consistently significantly larger than those for C 60 implies À5 m, the emission change of 5 at 458 nm as probe) in chloroform at 25 8C.…”

Section: Resultsmentioning

confidence: 91%

Strong Stacking between F⋅⋅⋅HN Hydrogen‐Bonded Foldamers and Fullerenes: Formation of Supramolecular Nano Networks

Zhu

et al. 2007

Chemistry A European J

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The stacking interactions between FH--N hydrogen-bonded foldamers 1-3, bis-foldamer 4, and tris-foldamer 5 and C(60) and C(70) are described. Compound 4 contains two folded units, which are connected by an isophthalamide linker, whereas 5 has a C(3)-symmetrical discotic structure, in which three folded units are connected by a benzene-1,3,5-tricarboxamide unit. UV/Vis, fluorescence, and NMR experiments have revealed that the foldamers or folded units strongly stack with fullerenes in chloroform. The (apparent) association constants of the respective complexes have been determined by a fluorescence titration method. The strong association is tentatively attributed to intermolecular cooperative fluorophenylpi and solvophobic interactions. A similar but weaker interaction has also been observed between an MeOH--N hydrogen-bonded foldamer and fullerenes. AFM studies have revealed that the surfaces of 3 and 4 show fibrous networks, while the surface of 5 shows particles. In sharp contrast, mixtures of 3 and 4 with C(60) have been shown to generate thinner separated fibrils, whereas a mixture of 5 and C(60) produces honeycomb-like nano networks, for which a columnar cooperative stacking pattern is proposed. The results demonstrate the usefulness of FH--N hydrogen-bonded folded structures in the construction of nanoscaled materials.

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“…Whereas p-stacking interactions between arene rings are common, [11][12][13][14] to our knowledge this is the first example of a p-stacking interaction between an arene ring and a carbonyl ligand. Similar p-stacking interactions have been described between one of the pentafluorophenyl rings and the xylyl isocyanide ligand (CNxyl) of…”

mentioning

confidence: 81%

“…[15] The distance between the center of the C18-C23 ring plane ring along its normal and the C17 À O17 bond is 3.15 as compared with interplanar distances of 3.4-4.4 for fluoroarylaryl stacking interactions. [11][12][13][14] The dihedral angle between the cyclopentadienyl rings planes of 3 b is significantly wider than that of 3 a and slightly narrower than that of 2 (Table 2). Thus, increasing the number of ligands in the equatorial wedge causes the cyclopentadienyl rings to tilt back more on the metal.…”

mentioning

confidence: 95%

Ring‐Borylated 15‐Electron and 17‐Electron ansa‐Chromocene Complexes, their Physical Properties and Molecular Structures

Shapiro

Sinnema

Perrotin

et al. 2007

Chemistry A European J

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A detailed study of the thermal decomposition of the zwitterionic, ring-borylated ansa-chromocene hydrido carbonyl complex [Cr(CO)H{Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (2) is described. This complex is formed in the reaction between [Cr(CO){Me(4)C(2)(C(5)H(4))(2)}] (1) and B(C(6)F(5))(3) in toluene at -78 degrees C. Above -25 degrees C, 2 decomposes to a 50:50 mixture of the low-spin, 17e Cr(III) complexes [Cr(CO){Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (3b) and [Cr(CO){Me(4)C(2)(C(5)H(4))(2)}][HB(C(6)F(5))(3)] (4). Carbon monoxide elimination from 3 b generates high-spin, 15 e [Cr{Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (3a), which coordinates two other electron-donating ligands, such as xylyl isocyanide, PMe3, and PPh(2)Me to form the low-spin, 17 e electron complexes 3c, 3d, and 3e, respectively. High-spin, 15 e [Cr{Me(4)C(2)(C(5)H(4))(2)}][HB(C(6)F(5))(3)] (5) is generated by heating 3 b in toluene at 100 degrees C and periodically removing the evolved CO. Efforts to isolate more than a few X-ray quality crystals of 5 were thwarted by its tendency to form an insoluble precipitate (6) with the same molecular formula. Heating the solution of 5 at 120 degrees C results in its partial conversion (ca. 28 %) to 3a, thereby allowing the formation of 3a in yields as high as 74 % from the reaction between 1 and B(C(6)F(5))(3). The X-ray crystal structures of 3 b-e and 5 are described. Cyclic voltammetry measurements on 3 a-e reveal a dramatic reduction in the redox potentials of the complexes relative to their non-borylated analogues. DFT calculations show that this is due primarily to electrostatic stabilization of the oxidized species by the negatively charged borylate group. EPR and 19F NMR spectroscopy allow 3a to be distinguished from its Lewis base adducts 3 b-e and reveal the relative affinities of different Lewis bases for the chromium.

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Phenyl−Perfluorophenyl Stacking Interactions: Topochemical [2+2] Photodimerization and Photopolymerization of Olefinic Compounds

Cited by 491 publications

References 70 publications

Polymer Structure Control Based on Crystal Engineering for Materials Design

Polymer Structure Control Based on Crystal Engineering for Materials Design

Strong Stacking between F⋅⋅⋅HN Hydrogen‐Bonded Foldamers and Fullerenes: Formation of Supramolecular Nano Networks

Ring‐Borylated 15‐Electron and 17‐Electron ansa‐Chromocene Complexes, their Physical Properties and Molecular Structures

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