Building Shape-Persistent Arylene Ethynylene Macrocycles as Scaffolds for 1,4-Diiodobutadiyne.

Two shape-persistent arylene ethynylene macrocycles have been designed and synthesized as scaffolds to bind the nonpolar molecule 1,4-diiodobutadiyne. Binding via halogen bonding interactions between the pyridine moieties of the macrocycle and 1,4-diiodobutadiyne is predicted by density functional theory calculations and has been demonstrated in solution by 13C NMR titrations. The binding constant for the macrocycle-monomer complex (K = 10.5 L mol-1) is much larger than for other comparable halogen bonds, strongly supporting cooperative binding of both ends of the diyne. These results demonstrate a fully inserted geometry of 1,4-diiodobutadiyne in the complex.

Exploiting Unsaturated Carbon-Iodine Compounds for the Preparation of Carbon-Rich Materials.

Conjugated carbon-rich materials have drawn much academic and industrial attention in recent years, due to their intriguing electronic and optical properties and potential applications including organic photovoltaics, flexible and wearable electronics, and chemical and biological sensors. Unsaturated carbon-iodine compounds, mainly the derivatives of iodoalkenes and iodoalkynes, are a class of molecules in which iodine atoms are directly connected to unsaturated carbons. These compounds provide unique advantages in the pursuit of carbon-rich materials, largely due to the Lewis acidity of iodine atoms and the lability of the carbon-iodine bonds. The Lewis acidity and electrophilicity of iodine in unsaturated carbon-iodine compounds make them excellent donors of halogen bonding, which is an attractive interaction between the electrophilic halogen atoms and Lewis basic species. Halogen bonding has emerged as a reliable building block in crystal engineering and supramolecular architectures. In this Account, we illustrate examples of the controlled assembly of diiodopolyynes within host-guest cocrystals that contain oxalamide or urea hosts with appropriate Lewis basic end groups and diiodobutadiyne or diiodohexatriyne guests. Halogen bonding interactions between the host and guest result in an ordered alignment of the diiodopolyynes that allows for a solid-state topochemical polymerization. We have used this approach to prepare poly(diiododiacetylene), PIDA, and poly(iodoethynyliododiacetylene), PIEDA, two conjugated polymers composed only of carbon and iodine. In addition, the polarity of the carbon-iodine bond gives unsaturated carbon-iodine compounds an electron-rich π-system, permitting electrophilic addition reactions with molecular halogens. The halogenated products of these additions can then serve as precursors to other conjugated carbon-rich systems. The lability of the carbon-iodine bond, together with the polarizability of iodine and the higher electronegativity of sp- and sp2-hybridized carbons, open up further possibilities in pursuing novel carbon nanomaterials from unsaturated carbon-iodine compounds. For example, we have developed an iterative method for the synthesis of longer symmetric polyynes from shorter diiodopolyynes, using Stille coupling to the iodine-capped polyynes. The iodination/coupling cycle symmetrically lengthens the polyyne chain by two carbon-carbon triple bonds. This method is particularly helpful for preparing polyynes with an odd number of carbon-carbon triple bonds. In addition, the lability of the carbon-iodine bonds of PIDA leads to facile carbonization by pyrolysis or laser irradiation. More strikingly, diiodoalkenes undergo quantitative elimination of iodine in the presence of Lewis bases. This reaction can be used to eliminate iodine at room temperature from PIDA, in which the carbon-iodine bonds are much more easily broken than in the diiodopolyynes, resulting in graphitic carbon materials.

Synthesis of Phenanthro[9,10-c]thiophenes by 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-Promoted Cyclo-Oxidation.

A new method to prepare phenanthro[9,10-c]thiophenes has been developed. In the presence of triflic acid, 3,4-diaryl thiophenes undergo 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-promoted cyclo-oxidation. NMR and computational studies indicate that protonation of the thiophene plays a key role in this reaction. The reaction can be used to prepare phenanthro[9,10-c]thiophene, as well as derivatives with alkyl, bromo, and methoxy substituents. However, the yields and selectivity of the reaction depend on both the nature and location of the substituents. Bis(3-methoxyphenyl)thiophene reacts under these conditions to give the desired product in 57 % yield, while bis(4-methoxyphenyl)thiophene gives no product. Bis(3-bromophenyl)thiophene did not react, but cyclo-oxidation of bis(4-bromophenyl)thiophene provides the desired product in 34 % yield.

Regioselective Synthesis of Substituted Cyclopenta[l]phenanthrenes.

A simple and efficient synthesis of cyclopenta[l]phenanthrenes from substituted acetophenones provides access to polycyclic aromatics with a variety of substitution patterns. The synthesis requires only three steps from a silyl enol ether: a Mukaiyama aldol reaction followed by McMurry coupling and then Mallory photocyclooxidation to give the target phenanthrenes. Photocyclization conditions have been found that give regioselective formation of 2,7-phenanthrenes from bis(meta-substituted) stilbenes.

Synthesis of the Stable Ordered Conjugated Polymer Poly(dibromodiacetylene) from an Explosive Monomer.

Dibromobutadiyne is an extremely unstable compound that explodes at room temperature, even under inert atmosphere. This instability has limited the studies of dibromobutadiyne almost entirely to spectroscopic characterization. Here we report an approach to control the reactivity of dibromobutadiyne, via topochemical reaction in cocrystals, leading to the ordered polymer poly(dibromodiacetylene), PBDA. At low temperatures (-15 to -18 °C), dibromobutadiyne can form cocrystals with oxalamide host molecules containing either pyridyl or nitrile side groups, in which halogen bonds align the dibromobutadiyne monomers for topochemical polymerization. The cocrystals with the bis(nitrile) oxalamide host undergo complete ordered polymerization to PBDA, demonstrated by solid-state MAS-NMR, Raman, and optical absorption spectroscopy. Once formed, the polymer can be separated from the host; unlike the monomer, PBDA is stable at room temperature.

Room-temperature carbonization of poly(diiododiacetylene) by reaction with Lewis bases.

Poly(diiododiacetylene) (PIDA) is a conjugated polymer containing an all-carbon backbone and only iodine atom substituents. Adding a Lewis base to the blue PIDA suspension at room temperature leads first to rapid disappearance of the absorption peaks attributed to PIDA, followed more slowly by release of free iodine. The resulting solid material gives a Raman scattering spectrum consistent with graphitic carbon, and it has a much higher conductivity than PIDA itself. Further investigation has led to the discovery of a previously unreported transformation, the reaction of a Lewis base such as pyrrolidine with a trans-diiodoalkene to form the corresponding alkyne. The generality of this iodine elimination further suggests that reaction of PIDA with Lewis bases dehalogenates the polymer, presenting a new method to prepare carbon nanomaterials at room temperature under very mild conditions.

Single-crystal-to-single-crystal topochemical polymerizations by design.

The polymerization of simple conjugated dienes has long been of interest: polydienes occur throughout Nature, and polyisoprene and its analogues form the basis of entire industries. In contrast, the polymers of similar small conjugated compounds, diacetylenes, trienes, and triacetylenes, are either unknown or laboratory curiosities. For 40 years, the only viable synthetic method for the 1,4-polymerization of a diacetylene was a topochemical polymerization in a condensed phase. But such an approach is hit or miss: if the diacetylene monomers have a solid-state structure preorganized at distances matching the repeat distance in the final polymer, then thermal or photochemical energy can bring about the polymerization. However, most monomers lack the proper structural parameters and simply do not react. As discussed in this Account, we have developed a supramolecular host-guest strategy that imposes the necessary structural parameters upon a diacetylene monomer that otherwise does not polymerize. We apply this strategy in the synthesis of new types of conjugated polymers made from diacetylenes, triacetylenes, and trienes. To implement the host-guest strategy, we chose a host that would self-assemble into a supramolecular structure with the requisite intermolecular spacing. For diacetylenes, the ideal spacing is 4.9 A, and the oxalamides, which routinely crystallize with a spacing of 5 A, make ideal host molecules. We chose specific oxalamide host substituents that bind to the diacetylene guest molecule, typically through hydrogen bonding. We have focused upon the single-crystal-to-single-crystal polymerizations, allowing us to obtain and characterize the polymers in perfect crystalline form and to define and better understand the reaction trajectories. We have prepared several new classes of polydiacetylenes using this strategy, including the first terminal polydiacetylenes and an aryl-substituted diacetylene. Interestingly, to prepare poly(diiododiacetylene), we used halogen bonds to bind the host and guest. The simplest polydiacetylene known, poly(diiododiacetylene), lacks the side chains that complicate the structures of similar previous polymers. Future studies should provide insights into the role of such side chains in conjugated materials. We further demonstrated the strength of the host-guest strategy by moving from the polydiacetylenes to the polytriacetylenes. Although the structural requirements for a triacetylene polymerization had been stated decades ago, no one had ever found a triacetylene with the requisite spacing of 7.4 A. We designed a series of pyridine-substituted vinylogous amide hosts to achieve this spacing. Cocrystallization of these host molecules with a triacetylene dicarboxylic acid gave us the desired structure. Using thermal annealing, we completed the synthesis of the triacetylene polymer.

Poly(diiododiacetylene): preparation, isolation, and full characterization of a very simple poly(diacetylene).

Poly(diiodiacetylene), or PIDA, is a conjugated polymer containing the poly(diacetylene) (PDA) backbone but with only iodine atom substituents. The monomer diiodobutadiyne (1) can be aligned in the solid state with bis(nitrile) oxalamide hosts by hydrogen bonds between oxalamide groups and weak Lewis acid-base interactions (halogen bonds) between nitriles and iodoalkynes. The resulting cocrystals start out pale blue but turn shiny and copper-colored as the polymerization progresses. The development of a crystallization methodology that greatly improves the yield of PIDA to about 50% now allows the full characterization of the polymer by X-ray diffraction, solid-state (13)C MAS NMR, Raman, and electron absorption spectroscopy. Comparison of a series of hosts reveals an odd-even effect in the topochemical polymerization, based on the alkyl chain length of the host. In the cocrystals formed with bis(pentanenitrile) oxalamide (4) and bis(heptanenitrile) oxalamide (6), the host/guest ratio is 1:2 and the monomer polymerizes spontaneously at room temperature, while in the case of bis(butanenitrile) oxalamide (3) and bis(hexanenitrile) oxalamide (5), where the host and guest form cocrystals in a 1:1 ratio, the polymerization is disfavored and does not go to completion. The topochemical polymerization can also be observed in water suspensions of micrometer-sized 6.1 cocrystals; the size distribution of these microcrystals, and the resulting polymer chains, can be controlled by sonication. Completely polymerized PIDA cocrystals show a highly resolved vibronic progression in their UV/vis absorption spectra. Extensive rinsing of the crystals in organic solvents such as methanol, THF, and chloroform separates the polymer from the soluble host. Once isolated, PIDA forms blue suspensions in a variety of solvents. The UV/vis absorption spectra of these suspensions match the cocrystal spectrum, without the vibronic resolution. However, they also include a new longer-wavelength absorption peak, associated with aggregation of the polymer chains.

Pressure-induced polymerization of diiodobutadiyne in assembled cocrystals.

Diiodobutadiyne forms cocrystals with bis(pyridyl)oxalamides in which the diyne alignment is near the ideal parameters for topochemical polymerization to the ordered conjugated polymer, poly(diiododiacetylene) (PIDA). Nonetheless, previous efforts to induce polymerization in these samples via heat or irradiation were unsuccessful. We report here the successful ordered polymerization of diiodobutadiyne in these cocrystals, by subjecting them to high external pressure (0.3-10 GPa). At the lower end of the pressure range, the samples contain primarily monomer, as demonstrated by X-ray diffraction studies, but some polymerization does occur, leading to a pronounced color change from colorless to blue and to the development of intense Raman peaks at 962, 1394, and 2055 cm-1, corresponding to the poly(diacetylene). At higher pressures, the samples turn black and contain primarily polymer, as determined by solid-state NMR and Raman spectroscopy. Both density functional theory calculations (B3LYP/LanL2DZ) and comparisons to authentic samples of PIDA have confirmed the data analysis.

Preparation of poly(diiododiacetylene), an ordered conjugated polymer of carbon and iodine.

Conjugated organic polymers generally must include large substituents for stability, either contained within or appended to the polymer chain. In polydiacetylenes, the substituents fulfill another important role: During topochemical polymerization, they control the spacing between the diyne monomers to produce an ordered polymer. By using a co-crystal scaffolding, we have prepared poly(diiododiacetylene), or PIDA, a nearly unadorned carbon chain substituted with only single-atom iodine side groups. The monomer, diiodobutadiyne, forms co-crystals with bis(nitrile) oxalamides, aligned by hydrogen bonds between oxalamide groups and weak Lewis acid-base interactions between nitriles and iodoalkynes. In co-crystals with one oxalamide host, the diyne undergoes spontaneous topochemical polymerization to form PIDA. The structure of the dark blue crystals, which look copper-colored under reflected light, has been confirmed by single-crystal x-ray diffraction, ultraviolet-visible absorption spectroscopy, and scanning electron microscopy.

Designed cocrystals based on the pyridine-iodoalkyne halogen bond.

Diiodobutadiyne (1) and diiodohexatriyne (2) form cocrystals with bispyridyl oxalamides and ureas, based on the halogen bond between the alkynyl iodine and pyridine nitrogen. In each cocrystal, the oxalamide or urea host forms one-dimensional hydrogen-bonded networks, aligning the diiodopolyyne for potential topochemical polymerization with a repeat distance matching the host repeat.

Theoretical analysis of the 13C NMR of iodoalkynes upon complexation with Lewis bases.

Recent experiments have demonstrated that the (13)C NMR spectra of iodoalkynes exhibit a strong solvent effect because of complexation with Lewis-basic solvents. This paper describes DFT NMR calculations (B3LYP-GIAO with LanL2DZ or Sadlej pVTZ basis set) of iodoalkynes and their Lewis acid-base complexes, interpreted by using Natural Chemical Shift (NCS) analysis within the framework of the Ramsey formalism for chemical shift. In particular, the paper presents calculations on diiodoethyne and its complexes with one and two ammonia molecules. Examination of the orbital changes upon forming the mono- and bisammonia complexes indicates that mixing of the nitrogen lone pair with the C-I antibonding orbital increases the paramagnetic deshielding at C1. Further increases can be attributed to increased polarization of the iodine lone-pair orbitals onto C1. The haloiodoalkyne series XCCI (X = F, Cl, Br, I) offers additional support for this model of the solvent effect.

Tetrabromobutatriene: completing the perhalocumulene series.

[structure: see text] Tetrabromobutatriene, C(4)Br(4), can be prepared directly from dibromobutadiyne by reaction with Br(2) at -25 degrees C in concentrated hexanes solution. The cumulene precipitates out of the reaction mixture as a yellow powder. Under palladium-catalyzed coupling conditions, C(4)Br(4) can undergo allylic rearrangement, giving a mixture of products, including some with butenyne backbones. However, in furan solution, C(4)Br(4) reacts cleanly at its central double bond to give the furan Diels-Alder adduct. Under Suzuki conditions, this adduct reacts at the furan double bond rather than at bromide.

Experimental studies of the 13C NMR of iodoalkynes in Lewis-basic solvents.

The (13)C NMR spectra of two different iodoalkynes, 1-iodo-1-hexyne (1) and diiodoethyne (2), exhibit a strong solvent dependence. Comparisons of the data with several common empirical models, including Gutmann's Donor numbers, Reichardt's E(N)(T), and Taft and Kamlet's beta and pi, demonstrate that this solvent effect arises from a specific acid-base interaction. Solvent basicity measures such as Donor numbers and beta values correlate well with the alpha-carbon chemical shift of 1, but polarity measures such as E(N)(T) and pi do not correlate. The similarity of the solvent effect for 1 and 2 suggests that carbon-carbon bond polarization may not play a role in the change in chemical shift, as previously hypothesized.

The effect of Lewis bases on the (13)c NMR of iodoalkynes.

In Lewis-basic solvents, alkynyl carbons bonded to iodine have chemical shifts approximately 12-15 ppm higher in frequency than the corresponding shifts in CDCl3. We offer computational evidence that this solvent effect comes directly from polarization of the iodoalkyne triple bond. Hartree-Fock and Density Functional Theory calculations reproduce the change in chemical shift for a gas-phase complex between the iodoalkyne and dimethyl sulfoxide as Lewis base. The amount of spin-orbit coupling from the adjacent iodine does not change appreciably in the complex, according to the calculations.