On-surface synthesis of porous graphene nanoribbons containing nonplanar [14]annulene pores

The precise introduction of nonplanar pores in the backbone of graphene nanoribbon represents a great challenge. Here, we explore a synthetic strategy toward the preparation of nonplanar porous graphene nanoribbon from a predesigned dibromohexabenzotetracene monomer bearing four cove-edges. Successive thermal annealing steps of the monomers indicate that the dehalogenative aryl-aryl homocoupling yields a twisted polymer precursor on a gold surface and the subsequent cyclodehydrogenation leads to a defective porous graphene nanoribbon containing nonplanar [14]annulene pores and five-membered rings as characterized by scanning tunneling microscopy and noncontact atomic force microscopy. Although the C–C bonds producing [14]annulene pores are not achieved with high yield, our results provide new synthetic perspectives for the on-surface growth of nonplanar porous graphene nanoribbons.     

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.     

Porous Carbon Fibers Containing Pores with Sizes Controlled at the Ångstrom Level by the Cavity Size of Pillar[6]arene

We report a new synthesis method of fibrous carbon material with pores sizes that are precisely controlled at the Ångstrom level, by carbonization of two dimensional (2D) porous sheets of pillar[6]arenes. The 2D porous sheets were prepared by 2D supramolecular polymerization induced by oxidation of hydroquinone units of pillar[6]arenes. Owing to the hexagonal structure of pillar[6]arene, the assembly induced by 2D supramolecular polymerization gave hexagonal 2D porous sheets, and the highly ordered structure of the 2D porous sheets formed regular fibrous structures. Then, carbonization of the 2D porous sheets afforded fibrous carbon materials with micropores. The micropore size of the fibrous porous carbon prepared from pillar[6]arene was the same size as that of the starting material pillar[6]arene assembly.     

The Stabilization Energy of [18] Annulene. A thermochemical determination

The thermal rearrangement of [18]annulene in solution gives benzene and 1,2-benzo-1,3,7-cyclooctatriene. This reaction has been investigated using a differential scanning calorimeter and the associated enthalpy change has been measured. The enthalpy of the reaction (in the gase phase at 298°K) is From this value and the enthalpies of formation of the reaction products, the enthalpy of formation of [18]annulene is obtained: The stabilization energy of [18]annulene, defined as the difference between the enthalpy of formation of the hypothetical Kékulé [18]annulene (with single and double bonds of normal lengths) and the heat of formation of the real molecule is then a value close to the corresponding quantity found for benzene. The very large stabilization energy of [18]annulen (100 ± 6 kcal mol^?1) previously reported in the literature, based on measurements of the heat of combustion, is not correct since the annulene is certainly oxidized in the bomb prior to combustion. The isodynamic conformational mobility of [18]annulene is not incompatible with a stabilization energy of 37 kcal mol^?1; the activation enthalpy observed for this process (ΔH^≠ = 16.1 kcal mol^?1) indicates that the stabilization is not completely destroyed in the transition state. The mechanism of the thermolysis of [18]annulen, investigated by kinetic measurements and by analysis of the shape of the thermograms, is discussed.     

[18]Annulene

The geometry of [18]annulene has been fully optimized within the D_6h point group (la) utilizing ab initio MO theory at the STO-3G level to give carbon-carbon bond lengths of 1.391 and 1.400 Å. This structure is found to be 35.7 kcal/mol less stable than a D_3h structure (1b) with alternating bond lengths of 1.330 and 1.479 Å. The ionization potentials are calculated to be in the ranges. 6.2–7.1 (1a) and 7.4–8.1 eV (1b)     

Concerning the Structure of [18]Annulene

A recent computational study of Schleyer and co‐workers [1] is reviewed, which led these authors to the firm conclusion that [18]annulene has a localized structure with alternating single and double C,C bonds, contrary to earlier crystallographic analyses of X‐ray‐diffraction data favoring a delocalized non‐alternating form. It is pointed out i) that deceptive orientational disorder phenomena in the crystal might be subject to experimental resolution in this case, and ii) that, in contrast to gas and solution phases, [18]annulene might possibly assume the non‐alternating structure in the crystalline solid state.     

Die Bildungsenthalpie 1,6-überbrückter [10] Annulene

The enthalpies of formation of 1.6-methano-[10] annulene (IV) (ΔHf₂₉₈ (IV, g) = 75.2 ± 0.6 kcal mol^?1), 1.6-imino-[10] annulene (V) (ΔHf₂₉₈(V, g) = 87.8 ± 0.7 kcal mol^?1) and of 1.6-oxido-[10] annulene (VI) (ΔHf₂₉₈(VI, g) = 47.8 ± 1.2 kcal mol^?1) have been determined by combustion calorimetry. The difficulties connected with an attempt to derive meaningfull «resonance energies» are discussed.     

Expanded Porphyrin Contraction: From [22]Triphyrin(6.6.0) to [22]Triphyrin(6.5.0)

An expanded triphyrin containing a bipyrrole moiety and annulene links, namely tetraphenyl-[22]triphyrin(6.5.0), 2 , has been synthesized. The synthesis proceeded by a postsynthetic transformation of tetraphenyl-[22]triphyrin(6.6.0), 1 , in a metal-free unexpected and unprecedented ring contraction during column chromatography on alumina. The observed transformation, located at the hydrocarbon chain linking the pyrrole units, formally corresponds to a subtraction of one carbon atom from an annulene circuit. In contrast to the flexible substrate 1 , the product 2 is conformationally rigid, and capable of chloride anion binding in its protonated form.     

The Photoelectron Spectrum of [18]Annulene

The PE. spectrum of [18]annulene has been measured and correlated with MO-calculations. The experimental ionization energies can only be explained by computing the electronic states of the cation, that is by taking into account the electron correlation and reorganization in the ionic states. The results allow a discussion of the structure of the neutral molecule; they are consistent with a D_6hpoint group of symmetry.     

Computation of the ESR. Coupling Constants of the [16]Annulene Radical Anion; Theoretical and Experimental Reinvestigation of the Excited States of [16]Annulene and its Mono- and Dinegative Ions

The problem of assigning the two small ESR. coupling constants of the [16]annulene radical anion to the two sets of four equivalent outer and inner ring protons is treated by three different semiempirical MO methods. All three methods indicate that the smaller coupling constant (0.743 Gauss) should be assigned to the inner protons, and the larger one (0.963 Gauss) to the outer ones. The electronic spectra of [16]annulene, its radical anion, and its dianion have been remeasured. Especially interesting was the detection of a symmetry-forbidden band of the radical anion at 1473 nm (6789 cm^?1, logε 2.57). The spectra are discussed in terms of different MO models.     

12]Annulene radical anions revisited: evaluation of structure assignments based on computed energetic and electron spin resonance data

We report density functional and coupled cluster calculations on numerous monocyclic and bicyclic (CH)12(*-) isomers. At the RCCSD(T)/cc-pVDZ//UB3LYP/6-31+G* level, a nearly planar, bond-equalized radical anion of 1,7-di-trans-[12]annulene (4a(*-)) is lowest in energy; several other isomers and conformations lie within 3 kcal/mol of 4a(*-). RCCSD(T)/AUG-cc-pVDZ//UB3LYP/6-31+G* results place the all-cis isomer 3(*-) slightly below 4a(*-) in energy. Validation studies on the heptalene radical anion, [16]annulene radical anion, and tri-trans-[12]annulene radical anion indicate that electron spin resonance (ESR) hyperfine coupling constants (aH values) computed at the BLYP/EPR-III level on DFT geometries give much better agreement with experimental values than those computed using B3LYP/6-31G*. We were unable to locate any C12H12(*-) isomer that could account for the ESR spectrum previously attributed to a highly twisted structure for the 1,7-di-trans-[12]annulene radical anion. Our computed energetic and ESR data for [12]annulene radical anions and their valence isomers suggest that 4a(*-) may have been made, yet its ESR spectrum was incorrectly assigned to the bicyclic isomer 6b(*-). Finally, the computed (1)H NMR shift values of the dianion of 4 reveal a distinct diatropic ring current that should aid in its characterization.     

Synthesis and properties of trefoil-shaped tris(hexadehydrotribenzo[12]annulene) and tris(tetradehydrotribenzo[12]annulene)

[reaction: see text] Trefoil-shaped tris(hexadehydrotribenzo[12]annulene) possessing a substructure of the ultimate two-dimensional C(sp)-C(sp(2)) network, graphyne, and the related tris(tetradehydrotribenzo[12]annulene) were synthesized, and their ground- and excited-state properties were investigated.     

Trisdehydro[14]annuleno[16]annulene

Trisdehydro[14]annuleno[16]annulene consisting of an aromatic bisdehydro[14]annulene and an antiaromatic bisdehydro[16]annulene has been synthesized. The strong paratropicity was observed in the [16]annulene moiety being comparable with that of extremely unstable parent bisdehydro[16]annulene.     

Subphthalocyanine-dehydro[18]annulenes

A subphthalocyanine trimer built around a dehydro[18]annulene core was prepared. The synthesis was achieved through direct homocoupling of an ortho-diethynyl-functionalized subphthalocyanine, obtained by palladium-catalyzed cross-coupling of the corresponding diiodo-subphthalocyanine with an ethynyl derivative. The lower analogue dehydro[12]annulene did not form in these homocoupling conditions. The trimers were fully characterized and their electrochemical properties investigated.     

The Low-Temperature UV/VIS Absorption Spectrum of [14]Annulene

The UV/VIS absorption spectrum of [14]annulene was measured in 3-methylpentane at room and liquid-N₂ temperatures and interpreted by the CNDO/S-CI method. This comparison between experiment and theory supports a structure with π-bond delocalization for this molecule.     

Donors and acceptors based on triangular dehydrobenzo[12]annulenes: formation of a triple-layered rosette structure by a charge-transfer complex

We present here the results of studies of the synthesis and properties of donors and acceptors based on triangular dehydrobenzo[12]annulene ([12]DBA) system as a pi core. These studies were aimed at controlling the supramolecular crystal structure. Toward this end, the tricyano[12]DBA 2 and dodecafluoro[12]DBA ( 3) were synthesized as acceptors (A) and the tris(dialkylamino)[12]DBAs 4a-d as donors (D), and their electronic properties were determined by electronic absorption spectroscopy and electrochemical measurements. The main focus, though, was the formation of supramolecular structures in crystals. These compounds form distinct packing patterns as a result of the different intermolecular interactions. Tricyano[12]DBA 2 forms a two-dimensional (2D) sheet structure via hydrogen-bonding interactions, whereas a tilted-stack structure was found for 3 because of the lack of significant intermolecular interactions. Tris(dibutylamino)[12]DBA 4b exhibits a ladder-type 2D structure, probably because of van der Waals interactions between the butyl groups. The most significant finding is that charge-transfer interactions between donor 4a and acceptor 3 combined with their triangular molecular shapes and lateral CH...F hydrogen bonding result in the formation of a 2D rosette structure consisting of two different trimeric (DAD- and ADA-type) sandwich structures with 1:2 and 2:1 A/D ratios, respectively.     

New tetraaza[14]annulene receptors derived from 2,3-diaminonaphthalene: synthesis and crystal structures

The first synthesis of the bis(2-hydroxybenzoyl)dinaphthotetraaza[14]annulene ligand and its O,O-bis-alkylated derivatives containing a decanedioxy bridging moiety, pendant bis-alkoxy groups as well as dicationic butoxypyridinium substituents is reported. The synthetic procedures, full analytical and spectroscopic characterisation (NMR, MS and IR) and crystal structures of the new products are described. The crystal structures show that naphthylene moieties incorporated into the investigated derivatives provide additional opportunities for non-covalent interactions between the molecules.     

An ultrasound assisted cyclocondensation reaction for the efficient synthesis of [1]benzopyranopyrido[d]pyrimidines using porous graphene/MoO3

In this paper, we report a feasible protocol for the preparation of [1]benzopyranopyrido[d]pyrimidines via expeditious sonochemical route. The reaction efficiency was evaluated by influence of several parameters including sonication power, sonication time, different solvents, and using porous graphene/MoO₃ nanocomposite as catalyst, for the first time. The effect of the ultrasonication comparing with the conventional heating on the synthesis of the titled compounds shows that the ultrasonic irradiation is required to rich the cyclized products. The structural properties of porous graphene/MoO₃ nanocomposite were determined by Fourier transform infrared spectroscopy (FT‐IR), powder X‐ray diffractometry (XRD), scanning electron microscope (SEM), Raman spectroscopy, and also by TGA analysis. Confirmation of the structures of compounds 4a – 4h were also established with IR, ¹H NMR, and ¹³C NMR spectroscopic data and also by elemental analyses.     

The second cyclopropannulene: cycloprop-[8]annulene

Reacting (at 0 degrees C) a mixture of CH2Cl2 and monobromo[8]annulene (C8H7Br) with potassium tert-butoxide in hexamethylphosphoramide (HMPA) and following with exposure to potassium metal led to the formation of the anion radical of an HMPA-[6.1.0]bicyclononatetraene condensation product, in which two HMPA fragments are geminal and attached to the number 9 carbon. When the reaction sequence is carried out in THF, the dianion of cycloprop[8]annulene is predominantly formed. Neutral cycloprop[8]annulene can be isolated via the I2 oxidation of the THF solution. The NMR analysis reveals that the eight-membered ring is nearly planar, and the three-membered ring is more like a dimethylenecyclopropane than it is like a cyclopropene. Further, the chemical shifts due to the protons on the eight-membered ring are nearly 2 ppm further upfield than are those for [8]annulene itself, suggesting a paratropic ring current.     

Anion radicals of di-trans-[12]annulene and heptalene in a one-pot synthesis from a common fire retardant

[reaction: see text] Low temperature (-100 degrees C) dehydrohalogenation of 1,2,5,6,9,10-hexabromocyclododecane (a common fire retardant) with potassium tert-butoxide in THF followed by one-electron reduction yields the anion radical of the di-trans form of [12]annulene. This system yields a well-resolved EPR signal that reveals that most of the spin density resides on one side (the planar side) of the anion radical. Five of the carbons in this [12]annulene system are twisted from the plane of the remaining seven carbons, and the rate of rearrangement between the degenerate conformations is on the EPR time scale (k = 10(6)-10(7) s(-1)). Warming of the solution results in the formation of a sigma-bond between the two internal carbons, loss of molecular hydrogen, and consequent generation of the anion radical of heptalene. Tractable quantities of neutral heptalene can be obtained via the reoxidation of this anion radical with iodine.