Metal Ion and Guest-Mediated Spontaneous Resolution and Solvent-Induced Chiral Symmetry Breaking in Guanine-Based Metallosupramolecular Networks.

Two-dimensional (2D) chirality has been actively studied in view of numerous applications of chiral surfaces such as in chiral resolutions and enantioselective catalysis. Here, we report on the expression and amplification of chirality in hybrid 2D metallosupramolecular networks formed by a nucleobase derivative. Self-assembly of a guanine derivative appended with a pyridyl node was studied at the solution-graphite interface in the presence and absence of coordinating metal ions. In the absence of coordinating metal ions, a monolayer that is representative of a racemic compound was obtained. This system underwent spontaneous resolution upon addition of a coordinating ion and led to the formation of a racemic conglomerate. The spontaneous resolution could also be achieved upon addition of a suitable guest molecule. The mirror symmetry observed in the formation of the metallosupramolecular networks could be broken via the use of an enantiopure solvent, which led to the formation of a globally homochiral surface.

Selective gas adsorption by calixarene-based porous octahedral M32 coordination cages.

Giant octahedral M32 coordination cages were prepared via self-assembly of sulfonylcalix[4]arene-supported tetranuclear M(II) clusters (M = Co, Ni) with hybrid linker based on tris(dipyrrinato)cobalt(III) complexes appended with peripherical carboxylic groups. Due to intrinsic and extrinsic porosity, the obtained solid-state supramolecular architectures demonstrated good performance as adsorbents for the separation of industrially important gases mixtures.

Photocycloadditions of Arenes Derived from Lignin.

Intramolecular photocycloaddition reactions of 3,4-alkoxybenzonitriles derived from vanillin with alkenes have been investigated. In contrast to previous reports on photochemical reactions with these compounds, mainly [2 + 3] cycloaddition has been observed. A competing [2 + 2] photocycloaddition plays a minor role. Most probably, these additions occur at the singlet state S1. In the case of a triplet reaction, a different regioselectivity of the [2 + 2] cycloaddition would be observed. Linear and angular [2 + 3] cycloadducts are formed as major products. The first isomer is transformed in the second one by a photochemical vinyl-cyclopropane rearrangement, which increases the selectivity of the reaction. The influence of the substitution pattern on the reactivity and the selectivity has also been investigated.

Structural Transformation of Surface-Confined Porphyrin Networks by Addition of Co Atoms.

The self-assembly of a nickel-porphyrin derivative (Ni-DPPyP) containing two pyridyl coordinating sites and two pentyl chains at trans meso positions was studied with scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) on Au(111). Deposition of Ni-DPPyP onto Au(111) gave rise to a close-packed network for coverages smaller or equal to one monolayer as revealed by STM and LEED. The molecular arrangement of this two-dimensional network is stabilized via hydrogen bonds formed between the pyridyl's nitrogen and hydrogen atoms from the pyrrole groups of neighboring molecules. Subsequent deposition of cobalt atoms onto the close-packed network and post-deposition annealing at 423 K led to the formation of a Co-coordinated hexagonal porous network. As confirmed by XPS measurements, the porous network is stabilized by metal-ligand interactions between one cobalt atom and three pyridyl ligands, each pyridyl ligand coming from a different Ni-DPPyP molecule.

Photochemically Induced Intramolecular Radical Cyclization Reactions with Imines.

The photochemically induced intramolecular hydrogen abstraction or hydrogen atom transfer in cyclic imines 8a,b followed by a cyclization is investigated. Two types of products are observed, one resulting from the formation of a C-C bond, the other from the formation of a C-N bond. A computational study reveals that hydrogen is exclusively transferred to the imine nitrogen leading to a triplet diradical intermediate. After intersystem crossing, the resulting zwitterionic intermediate undergoes cyclization leading to the final product.

Tuning photochemical properties of phosphorus(v) porphyrin photosensitizers.

Photosensitizing and emission properties of P(v) porphyrins were studied. The nature of the axial ligands, occupying the apical position on the P centre adopting an octahedral coordination geometry, strongly influences singlet oxygen generation and charge transfer and allows switching between the two processes.

Phosphorus(V) Porphyrin-Based Molecular Turnstiles.

A new cationic molecular turnstile based on a P(V) porphyrin backbone bearing two pyridyl interaction sites, one at the meso position of the porphyrin and the other on the handle connected to the porphyrin through P-O bonds, was designed and synthesized. The dynamic behavior of the turnstile 2, investigated by 1D and 2D 1H NMR techniques, showed that in the absence of an effector, the turnstile is in its open state and undergoes a free rotation of the rotor (the handle) around the stator (the porphyrin backbone). In the presence of an external effector such as Ag+ cation or H+, the turnstile is switched to its closed states 2-Ag+ and 2-H+, respectively. The locking/unlocking process is reversible and may be achieved by precipitation of AgBr upon addition of Et4NBr in the case of the silver-locked turnstile or by addition of Et3N in the case of the proton-locked turnstile.

Nanopatterning of Surfaces with Monometallic and Heterobimetallic 1D Coordination Polymers: A Molecular Tectonics Approach at the Solid/Liquid Interface.

The self-assembly of multiple molecular components into complex supramolecular architectures is ubiquitous in nature and constitutes one of the most powerful strategies to fabricate multifunctional nanomaterials making use of the bottom-up approach. When spatial confinement in two dimensions on a solid substrate is employed, this approach can be exploited to generate periodically ordered structures from suitably designed molecular tectons. In this study we demonstrate that physisorbed directional periodic arrays of monometallic or heterobimetallic coordination polymers can be generated on a highly oriented pyrolitic graphite surface by combinations of a suitably designed directional organic tecton or metallatecton based on a porphyrin or nickel(II) metalloporphyrin backbone bearing both a pyridyl unit and a terpyridyl unit acting as coordinating sites for CoCl2. The periodic architectures were visualized at the solid/liquid interface with a submolecular resolution by scanning tunneling microscopy and corroborated by combined density functional and time-dependent density functional theory calculations. The capacity to nanopattern the surface for the first time with two distinct metallic centers exhibiting different electronic and optical properties is a key step toward the bottom-up construction of robust multicomponent and, thus, multifunctional molecular nanostructures and nanodevices.

Molecular tectonics based nanopatterning of interfaces with 2D metal-organic frameworks (MOFs).

The nanostructuring of the graphite surface with 2D coordination networks, based on a combination of an acentric porphyrin tecton bearing two divergently oriented monodentate pyridyl units and a CoCl2 metallatecton, behaving as a four connecting node, was achieved at the solid-liquid interface and characterized by scanning tunnelling microscopy.

Sensitisation of the near-infrared emission of Nd(III) from the singlet state of porphyrins bearing four 8-hydroxyquinolinylamide chelates.

The α(4) atropoisomer of a tetraaryl porphyrin and its Pd(II) complex, both bearing four hydroxyquinolinyl chelating units pre-organised on the same face of the porphyrin backbone, bind a Nd(III) centre thus affording either a mononuclear or a heterobinuclear anionic species, respectively. The near-infrared emission of the lanthanide centred at 1064 nm is observed upon excitation of the Soret band at 425 nm. Sensitisation proceeds mainly from the singlet state of the porphyrin.

Stereoselective triplet-sensitised radical reactions of furanone derivatives.

The stereo- and regioselectivity of triplet-sensitised radical reactions of furanone derivatives have been investigated. Furanones 7a,b were excited to the (3)pipi* state by triplet energy transfer from acetone. Intramolecular hydrogen abstraction then occurred such that hydrogen was transferred from the tetrahydropyran to the beta position of the furanone moiety. Radical combination of the tetrahydropyranyl and the oxoallyl radicals led to the final products 8a,b. In the intramolecular reaction, overall, a pyranyl group adds to the alpha position of the furanone. The effect of conformation was first investigated with compounds 9a,b carrying an additional substituent on the tether between the furanone and pyranyl moiety. Further information on the effect of conformation and the relative configuration at the pyranyl anomeric centre and the furanone moiety was obtained from the transformations of the glucose derivatives 12, 14, 17 and 18. Radical abstraction occurred at the anomeric centre and at the 5'-position of the glucosyl moiety. Computational studies of the hydrogen-abstraction step were carried out with model structures. The activation barriers of this step for different stereoisomers and the abstraction at the anomeric centre and at the 6'-position of the tetrahydropyranyl moiety were calculated. The results of this investigation are in accordance with experimental observations. Furthermore, they reveal that the reactivity and regioselectivity are mainly determined in the hydrogen-abstraction step. Intramolecular hydrogen abstraction (almost simultaneous electron and proton transfer) in (3)pipi* excited furanones only takes place under restricted structural conditions in a limited number of conformations that are defined by the relative configuration of the substrates. It is observed that in the biradical intermediate, back-hydrogen transfer occurs leading to the starting compound. In the case of glucose derivatives, this reaction led to epimerisation at the anomeric centre.

Sensitization of the NIR emission of Nd(III) by the alpha4 atropoisomer of a meso-tetraphenyl porphyrin bearing four 8-hydroxyquinolinylamide chelates.

The alpha4 atropoisomer of the meso tetrakis 8-hydroxyquinolinylamide porphyrin and its Pd complex binds Nd(iii) and sensitizes efficiently its near infrared (NIR) emission when excited in the visible domain.

Molecular tectonics: control of pore size and polarity in 3-D hexagonal coordination networks based on porphyrins and a zinc cation.

In the crystalline phase, porphyrin derivatives based on two 4-pyridyl units at the 5 and 15 meso positions and two 4-aryl moieties bearing various groups (CN, OMe, OH and CF(3)) at the 10 and 20 meso positions lead, in the presence of a zinc dication, to the formation of robust 3-D networks presenting hexagonal channels: both the size and the polarity of the pores were tuned by the nature of the substituents attached to the two aryl groups.

Reversible single-crystal-to-single-crystal guest exchange in a 3-D coordination network based on a zinc porphyrin.

A self-complementary tecton based on a zinc porphyrin core bearing two pyridines at the opposite meso positions leads to the formation of a 3-D coordination network in the crystalline phase which offers channels which are filled with solvent molecules; reversible exchange of the guest molecules has been proven to take place in a single-crystal-to-single-crystal type transformation demonstrating the robustness of the coordination framework.

Molecular tectonics: design of luminescent H-bonded molecular networks.

Using bis-amidinium dications as tetra H-bond donor tectons and Au(CN)(2)(-) anion, neutral 1-D networks based on a bis monohapto mode of H-bonding are obtained. Owing to the short metal-metal distance within the network, luminescent crystals are obtained. The emission phenomena may be tuned by the nature of the spacer connecting the two cyclic amidinium groups.

Origin of chiral induction in radical reactions with the diastereoisomers (5R)- and (5S)-5-l-menthyloxyfuran-2[5H]-one.

Acetalization of 5-hydroxyfuran-2[5H]-one with l-menthol yields (5R)- (1) and (5S)-5-l-menthyloxyfuran-2[5H]-one (2) in equal amounts. The diastereomer 1 crystallizes preferentially. For the first time, the isolation of pure diastereoisomer 2 is reported. Different diastereoselectivities were observed in the radical tandem reaction of 1 and 2 with N,N-dimethylaniline. The privileged conformations in solution of the substrates and the products of the radical reaction were then determined, and X-ray crystal structure analyses were carried out on the reaction products. The different stereoselectivities in both cases are explained by different orientations of the menthyloxy substituent.

Molecular tectonics: from enantiomerically pure sugars to enantiomerically pure triple stranded helical coordination network.

The self-assembly between a bis-monodentate tecton based on two pyridine units connected to an enantiomerically pure isomannide stereoisomer and HgCl2 leads to the formation of an enantiomerically pure triple stranded helical infinite coordination network which was structurally characterised by X-ray diffraction on single crystal.

Four-Coordinate, Low-Spin (S = 0) and Six-Coordinate, High-Spin (S = 1) Nickel(II) Complexes of Tetraphenylporphyrins with beta-Pyrrole Electron-Withdrawing Substituents: Porphyrin-Core Expansion and Conformation.

To examine the porphyrin-core expansion and the conformational variations induced by a change in the coordination sphere of nickel(II) from four-coordinate, low-spin (S = 0) to six-coordinate, high-spin (S = 1), several nickel(II) derivatives of tetraphenylporphyrins, substituted in their beta-pyrrole positions with electron-withdrawing groups, were isolated and studied by X-ray crystallography. The four-coordinate nickel(II) complex studied, Ni(TPP(Br)(4)(CN)(4)) (1), is a derivative of the antipodal beta-pyrrole brominated and cyanated macrocycle, 2,3,12,13-tetrabromo-7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrin. One of the six-coordinate species is the bis-pyridine nickel(II) adduct, Ni(TPP(Br)(4)(CN)(4))(py)(2) (2), of this antipodal beta-pyrrole brominated and cyanated ring, whereas the second six-coordinate complex is the bis-1-methylimidazole nickel(II) adduct, Ni(TPP(CN)(4))(1-MeIm)(2) (3), of the antipodal tetracyanated macrocycle, 7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrin. This study confirms that, upon conversion of a four-coordinate, low-spin nickel(II) derivative of a beta-pyrrole-substituted tetraphenylporphyrin into a six-coordinate, high-spin complex, a radial expansion of the porphyrin core also takes place. This radial expansion flattens the porphyrin core, inducing more planarity in the conformations of the six-coordinate nickel(II) porphyrin species. The X-ray structure of 1 reveals an average Ni-N(p) bond distance of 1.920(2) Å, similar to that present in tetragonal Ni(OEP) [(Ni-N(p))(av) = 1.929(3) Å], the ruffled low-spin nickel(II) (S = 0) porphyrin derivative, and many other low-spin nickel(II) complexes of distorted porphyrins. The conformation of the macrocycle present in 1 is severely saddle-shaped with a small ruffling and a minor doming. The structures of 2 and 3 indicate a clear expansion of the porphyrin cores with two sets of (Ni-N(p))(av) bond lengths of 2.040(2) and 2.073(2) Å in 2 and 2.037(2) and 2.068(2) Å in 3, which differ significantly from the average Ni-N(p) distance occurring in 1. Relative to the conformation of the porphyrin ring present in 1, the high-spin complex 2 is less saddle-shaped, but more ruffled. In 3, in which only two opposite pyrrole rings of the porphyrin are substituted by cyano groups, the macrocycle adopts a slightly waved conformation. Crystal data: Ni(TPP(Br)(4)(CN)(4)).2.5(1,2-Cl(2)C(2)H(4)), [1.2.5(1,2-Cl(2)C(2)H(4))], triclinic, space group P&onemacr;, a = 13.741(1) Å, b = 14.029(2) Å, c = 15.201(2) Å, alpha = 89.037(9) degrees, beta = 70.829(8) degrees, gamma = 67.607(8) degrees, V = 2539.4(5) Å(3), T = 20 degrees C, Z = 2, R(F)() = 0.047 and R(wF) = 0.067 based on 5341 reflections with I > 3sigma(I); Ni(TPP(Br)(4)(CN)(4))(py)(2).2.5(1,2-Cl(2)C(2)H(4)), [2.2.5(1,2-Cl(2)C(2)H(4))], triclinic, space group P&onemacr;, a = 11.9472(9) Å, b = 14.3651(7) Å, c = 19.556(1) Å, alpha = 87.049(5) degrees, beta = 73.181(6) degrees, gamma = 70.613(5) degrees, V = 3026.8(4) Å(3), T = 173 K, Z = 2, R(F)() = 0.036, R(wF) = 0.041 based on 6846 reflections with I > 3sigma(I); Ni(TPP(CN)(4))(1-MeIm)(2).2CH(2)Cl(2), [3.2(CH(2)Cl(2))], monoclinic, space group C2/c, a = 26.804(8) Å, b = 10.948(3) Å, c = 19.453(5) Å, beta = 113.13(2) degrees, V = 5251.5 Å(3), T = 20 degrees C, Z = 4, R(F)() = 0.047, R(wF) = 0.067 based on 4384 reflections with I > 3sigma(I).