Isomeric 2,6-pyridino-cryptands based on dibenzo-24-crown-8

Cryptands 4 and 5 were synthesized from cis- and trans-bis(hydroxymethylbenzo)-24-crown-8 by reaction with pyridine-2,6-dicarboxylic acid chloride in 42 and 48% yields, respectively. The new cryptands form pseudorotaxanes with the paraquat derivative N,N'-bis(beta-hydroxyethyl)-4,4'-bipyridinium bis(hexafluorophosphate) ("paraquat diol", 6): Ka=1.0x10(4) and 1.4x10(4) M-1, respectively. The cryptands also form complexes with ammonium hexafluorophosphate. Formation of the paraquat/cryptand-based pseudorotaxanes can be switched off and on in a controllable manner on the basis of the cryptands' abilities to complex KPF6 strongly, providing a new mechanism for control of molecular shuttles. K+ displaces paraquat diol from the cryptands, converting yellow-orange solutions to colorless; however, addition of 18-crown-6 binds the KPF6 and allows the colored cryptand-paraquat complex to reform. Crystal structures are reported for both cryptands, both paraquat diol-based pseudorotaxanes, both NH4PF6 complexes, and both KPF6 complexes.     

Paraquat substituent effect on complexation with a dibenzo-24-crown-8-based cryptand

Dibenzo-24-crown-8-based cryptand 4 forms 1:1 inclusion complexes with three paraquat derivatives, P1, P2, and P3, as demonstrated by proton NMR spectroscopy and X-ray analysis. However, it was found that methyl-substituted paraquat derivatives, P2 and P3, can bind cryptand 4 more strongly than non-methyl-substituted paraquat derivative P1. The association constants (Ka) were determined in acetone by using a UV-vis titration method to be 5.0 x 10(3) M(-1) for 4.P1, 1.0 x 10(5) M(-1) for 4.P2, and 1.2 x 10(5) M(-1) for 4.P3, respectively. In the solid state, 4.P2 and 4.P3 have similar T-type inclusion complexation conformations, which are very different from the pseudorotaxane-type complexation conformation of 4.P1. Theoretical calculations were done to explain these experimental results.     

Three-step synthesis of end-substituted pentacenes

A concise, three-step synthesis of 1,4,8,11-substituted 2,3,9,10-tetrakis(methoxycarbonyl)pentacenes from commercially available 1,2,4,5-tetrakis(bromomethyl)benzene was established. Efficient alkynylation, followed by formation of four fused rings via a zirconacyclopentadiene intermediate, and then oxidation with DDQ gave pentacenes 1a-c. The process was compatible with methyl, phenyl, and trimethylsilyl substituents, which have good solubility in various organic solvents.     

Differentiable McCormick relaxations

McCormick’s classical relaxation technique constructs closed-form convex and concave relaxations of compositions of simple intrinsic functions. These relaxations have several properties which make them useful for lower bounding problems in global optimization: they can be evaluated automatically, accurately, and computationally inexpensively, and they converge rapidly to the relaxed function as the underlying domain is reduced in size. They may also be adapted to yield relaxations of certain implicit functions and differential equation solutions. However, McCormick’s relaxations may be nonsmooth, and this nonsmoothness can create theoretical and computational obstacles when relaxations are to be deployed. This article presents a continuously differentiable variant of McCormick’s original relaxations in the multivariate McCormick framework of Tsoukalas and Mitsos. Gradients of the new differentiable relaxations may be computed efficiently using the standard forward or reverse modes of automatic differentiation. Extensions to differentiable relaxations of implicit functions and solutions of parametric ordinary differential equations are discussed. A C++ implementation based on the library MC++ is described and applied to a case study in nonsmooth nonconvex optimization.     

Electrochemistry in ionic liquids: Case study of a manganese corrole

Voltammetry of [5,10,15-tris(pentafluorophenylcorrole)]Mn(III) was investigated in four different ionic liquids (ILs): 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI); 1-ethyl-3-methylimidazolium ethylsulfate (EMIm-EtOSO3); 1-ethyl-3-methylimidazolium triflate (EMIm-OTf); and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIm-TCB). We found that MnIV/III E _1/2 values depend on IL counter anion: OTf–< EtOSO₃ ^? < TFSI^? < TCB^?. In EMIm-TCB and BMIm- TFSI, reversible, diffusion-controlled Mn^IV/III reactions occurred, as evidenced in each case by the ratio of anodic to cathodic diffusion coefficients over a range of scan rates. Axial coordination was evidenced by a cathodic to anodic diffusion coefficient ratio greater than one, an increasing cathodic to anodic peak current ratio with increasing scan rate, and a split Soret band in the UV-vis spectrum of the complex.     

Anthracene as a sensitiser for near-infrared luminescence in complexes of Nd(III), Er(III) and Yb(III): an unexpected sensitisation mechanism based on electron transfer

The ligand L(1), which contains a chelating 2-(2-pyridyl)benzimidazole (PB) unit with a pendant anthacenyl group An connected via a methylene spacer, (L(1) = PB-An), was used to prepare the 8-coordinate lanthanide(III) complexes [Ln(hfac)(3)(L(1))] (Ln = Nd, Gd, Er, Yb) which have been structurally characterised and all have a square antiprismatic N(2)O(6) coordination geometry. Whereas free L(1) displays typical anthracene-based fluorescence, this fluorescence is completely quenched in its complexes. The An group in L(1) acts as an antenna unit: in the complexes [Ln(hfac)(3)(L(1))] (Ln = Nd, Er, Yb) selective excitation of the anthracene results in sensitised near-infrared luminescence from the lanthanide centres with concomitant quenching of An fluorescence. Surprisingly, the anthracene fluorescence is also quenched even in the Gd(III) complex and in its Zn(II) adduct in which quenching via energy transfer to the metal centre is not possible. It is proposed that the quenching of anthracene fluorescence in coordinated L(1) arises due to intra-ligand photoinduced electron-transfer from the excited anthracene chromophore (1)An* to the coordinated PB unit generating a short-lived charge-separated state [An(.+)-PB(.-)] which collapses by back electron-transfer to give (3)An*. This electron-transfer step is only possible upon coordination of L(1) to the metal centre, which strongly increases the electron acceptor capability of the PB unit, such that (1)An* --> PB PET is endoergonic in free L(1) but exergonic in its complexes. Thus, rather than a conventional set of steps ((1)An* -->(3)An* --> Ln), the sensitization mechanism now includes (1)An* --> PB photoinduced electron transfer to generate charge-separated [An(.+)-PB(.-)], then back electron-transfer to generate (3)An* which finally sensitises the Ln(III) centre via energy transfer. The presence of (3)An* in L(1) and its complexes is confirmed by nanosecond transient absorption studies, which have also shown that the (3)An* lifetime in the Nd(III) complex matches the rise time of Nd-centred near-infrared emission, confirming that the final step of the sequence is (3)An* --> Ln(III) energy-transfer.     

(Eta-C5H4R)Fe(CO)2X], X = Cl, Br, I, NO3, CO2Me and [(eta-C5H4R)Fe(CO)3]+, R = (CH2)nCO2Me (n = 0-2), and CO2CH2CH2OH: a new group of CO-releasing molecules

A new group of CO-releasing molecules, CO-RMs, based on cyclopentadienyl iron carbonyls have been identified. X-Ray structures have been determined for [(eta-C(5)H(4)CO(2)Me)Fe(CO)(2)X], X = Cl, Br, I, NO(3), CO(2)Me, [(eta-C(5)H(4)CO(2)Me)Fe(CO)(2)](2), [(eta-C(5)H(4)CO(2)CH(2)CH(2)OH)Fe(CO)(2)](2) and [(eta-C(5)H(4)CO(2)Me)Fe(CO)(3)][FeCl(4)]. Half-lives for CO release, (1)H, (13)C, and (17)OC NMR and IR spectra have been determined along with some biological data for these compounds, [(eta-C(5)H(4)CO(2)CH(2)CH(2)OH)Fe(CO)(3)](+) and [[eta-C(5)H(4)(CH(2))(n)CO(2)Me]Fe(CO)(3)](+), n = 1, 2. More specifically, cytotoxicity assays and inhibition of nitrite formation in stimulated RAW264.7 macrophages are reported for most of the compounds analyzed. [(eta-C(5)H(5))Fe(CO)(2)X], X = Cl, Br, I, were also examined for comparison. Correlations between the half-lives for CO release and spectroscopic parameters are found within each group of compounds, but not between the groups.     

Probing heme coordination states of inducible nitric oxide synthase with a ReI(imidazole-alkyl-nitroarginine) sensitizer-wire

Mammalian inducible nitric oxide synthase (iNOS) catalyzes the production of l-citrulline and nitric oxide (NO) from L-arginine and O2. The Soret peak in the spectrum of the iNOS heme domain (iNOSoxy) shifts from 423 to 390 nm upon addition of a sensitizer-wire, [ReI-imidazole-(CH2)8-nitroarginine]+, or [ReC8argNO2]+, owing to partial displacement of the water ligand in the active site. From analysis of competitive binding experiments with imidazole, the dissociation constant (Kd) for [ReC8argNO2]+-iNOSoxy was determined to be 3.0+/-0.1 microM, confirming that the sensitizer-wire binds with higher affinity than both L-arginine (Kd=22+/-5 microM) and imidazole (Kd=14+/-3 microM). Laser excitation (355 nm) of [ReC8argNO2]+-iNOSoxy triggers electron transfer to the active site of the enzyme, producing a ferroheme in less than approximately 1 micros.     

A cyclodextrin-insulated anthracene rotaxane with enhanced fluorescence and photostability

A beta-cyclodextrin anthracene rotaxane was synthesized and found to be significantly more resistant to fluorescence quenching and photobleaching than the uninsulated anthracene derivative.     

Insulated molecular wires

An astonishing assortment of structures have been described as "insulated molecular wires" (IMWs), thus illustrating the diversity of approaches to molecular-scale insulation. These systems demonstrate the scope of encapsulation in the molecular engineering of optoelectronic materials and organic semiconductors. This Review surveys the synthesis and structural characterization of IMWs, and highlights emerging structure-property relationships to determine how insulation can enhance the behavior of a molecular wire. We focus mainly on three IMW architectures: polyrotaxanes, polymer-wrapped pi systems, and dendronized polymers, and compare the properties of these systems with those of conjugated polymers threaded through mesoporous frameworks and zeolites. Encapsulation of molecular wires can enhance properties as diverse as luminescence, electrical transport, and chemical stability, which points to applications in electroluminescent displays, sensors, and the photochemical generation of hydrogen.