The interaction of calixpyrrole with several chloride salts has been studied in the solid state by X-ray crystallography as well as in solution by isothermal titration calorimetry (ITC) and (1)H NMR spectroscopic titrations. The titration results in dimethylsulfoxide, acetonitrile, nitromethane, 1,2-dichloroethane, and dichloromethane, carried out using various chloride salts, specifically tetraethylammonium (TEA), tetrapropylammonium (TPA), tetrabutylammonium (TBA), tetraethylphosphonium (TEP), tetrabutylphosphonium (TBP), and tetraphenylphosphonium (TPhP), showed no dependence on method of measurement. The resulting affinity constants (K(a)), on the other hand, were found to be highly dependent on the choice of solvent with K(a)'s ranging from 10(2)-10(5) M(-1) being recorded in the test solvents used for this study. In dichloromethane, a strong dependence on the countercation was also seen, with the K(a)'s for the interaction with chloride ranging from 10(2)-10(4) M(-1). In the case of TPA, TBA, and TBP, the ITC data could not be fit to a 1:1 binding profile.

Three calix[4]pyrroles bearing m-orcinol-derived diether straps of different lengths on one side of the tetrapyrrolic core have been synthesized and characterized. Structural information for an analogous diester bridged strapped system reported previously (Yoon, D. W.; Hwang, H.; Lee, C. H. Angew. Chem., Int. Ed. Engl. 2002, 41, 1757-1759) is also provided as are bromide and chloride anion affinities for all four systems determined by Isothermal Titration Calorimetry (ITC) in acetonitrile. Although both sets of the strapped calix[4]pyrroles displayed enhanced affinities for chloride and bromide anion, differences were seen among the various receptors that support the conclusion that the anion binding ability of calixpyrrole-type systems can be effectively tuned by modifying the length and nature of the bridging straps. In the specific case of the diether systems, the largest chloride affinity was seen with the shortest strap, whereas the largest affinity for bromide anion was recorded in the case of the longest strap. On the basis of these findings, as well as supporting (1)H NMR spectroscopic studies, it is postulated that not only cavity size per se, but also the ability of the aryl portion of the strap to serve as a CH hydrogen bond donor site are important in regulating the observed anion affinities.

A calix[4]pyrrole incorporating four appended tetrathiafulvalene (TTF) units has been synthesized, and its receptor abilities toward neutral electron-deficient guests, such as 1,3,5-trinitrobenzene, tetrafluoro-p-benzoquinone, and tetrachloro-p-benzoquinone, have been studied in solution by UV-vis and 1H NMR spectroscopies as well as in the solid-state by X-ray crystallography. In its 1,3-alternate conformation a 1:2 sandwich-like complex-stabilized by charge transfer and hydrogen bonding interactions-is formed between the tetra-TTF calix[4]pyrrole and the guest molecules. However, upon addition of chloride ions to the complex the 1,3-alternate conformation is changed in favor of a cone conformation which serves to effect a release of the guests from the tetra-TTF calix[4]pyrrole.

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meso-Aryl substituted rubyrin ([26]hexaphyrin(1.1.0.1.1.0)) 2 and a series of rubyrin-type large expanded porphyrins were obtained from a facile one-pot oxidative coupling reaction of meso-pentafluorophenyl substituted tripyrrane 1. The structures of two of the resulting products were determined by single-crystal X-ray diffraction analysis. Whereas [52]dodecaphyrin(1.1.0.1.1.0.1.1.0.1.1.0) 4 takes a symmetric helical conformation, the larger species, [62]pentadecaphyrin(1.1.0.1.1.0.1.1.0.1.1.0.1.1.0) 5, adopts a nonsymmetric distorted conformation in the solid state that contains an intramolecular helical structure. The ability of rubyrin 2 to act as an anion receptor in its diprotonated form (2(.)2H(+)) was demonstrated in methanolic solutions. Oxidation of 2 with MnO(2) gave [24]rubyrin 6, a species that displays antiaromatic characteristics. [26]Rubyrin 2 and [24]rubyrin 6 both underwent metallation when reacted with Zn(OAc)(2) to give the corresponding bis-zinc(II) complexes 7 and 8 quantitatively without engendering a change in the oxidation state of the ligands. As a result, complexes 7 and 8 exhibit aromatic and antiaromatic character, respectively. NICS calculation on these compounds also supported aromaticity of 2 and 7, and antiaromaticity of 6 and 8.

Reported here is the synthesis and characterization of a new class of macrocycle that represents a hybrid between texaphyrin and calixpyrrole. These polypyrrolic macrocycles were prepared in one step by the acid-catalyzed condensation between diformyl dipyrromethanes and ophenylenediamines in high yields. The X-ray crystal structure of one of these new "chimeras" was solved. It reveals that the diprotonated Schiff-base macrocycle has a V-shape in which one chloride anion is bound. Isothermal titration calorimetry (ITC) studies served to confirm the ability of the hybrid macrocycles to bind chloride anion in acetonitrile solution. These compounds may be useful as easy-to-make anion receptors.

The anion binding properties of fluorinated calix[n]pyrroles (n = 4-6) in aprotic solvents (acetonitrile and DMSO) and modified reaction conditions allowing for the synthesis and isolation of the hitherto missing dodecafluorocalix[6]pyrrole from the condensation of 3,4-difluoro-1H-pyrrole and acetone are described. In acetonitrile solution containing 2% water, the association constants for the 1:1 binding interaction between octafluorocalix[4]pyrrole and chloride anion obtained with isothermal titration calorimetry (ITC) and (1)H NMR titration methods were found to match reasonably well. As compared to its nonfluorinated congener, octafluorocalix[4]pyrrole was found to display enhanced binding affinities for several representative anions in pure acetonitrile as judged from ITC analyses. Similar analyses of the fluorinated calix[n]pyrroles revealed an increase in the relative affinity for bromide over chloride with increasing macrocycle size, as manifest in a decrease in the binding ratio K(a(Cl))/K(a(Br)). Anion binding studies in the solid state, involving single-crystal X-ray diffraction analyses of the chloride and acetate anion complexes of octafluorocalix[4]pyrrole and decafluorocalix[5]pyrrole, respectively, confirmed the expected hydrogen bond interactions between the pyrrolic NH protons and the bound anions.

The chemically synthesized suppressor and leveler are added together with bis(3-sulfopropyl)disulfide (SPS) to galvanostatically fill up the trenches with the similar dimensions to those of the through silicon vias. In our previous study, the deposition of the coarse-grained Cu was indicated as a drawback of the synthesized additives, i.e., polyoxy polymer with amine terminal groups and pyridine derivatives containing additional amine groups. In this study, the modified chemistry of organic additives is used, enabling the bottom-up filling of trenches and improving the microstructure of the deposited Cu. The conversion of the functional groups from amine to hydroxyl groups in both the suppressor and leveler, and the uniform adsorption of modified suppressor improved the microstructure of the deposited Cu. The void-free trench filling is induced by the selective adsorption and accumulation of SPS at the bottom and negligible deposition on the top and side-walls of the trenches. Based on the filling mechanism, the trenches with 9 μm width and 50 μm depth are galvanostatically filled in ≤20 min. Intensive researches have been focused on the fabrication of 3-dimensional (3D) interconnection among electronic devices to achieve a high-density integration and multifunctional single device.1-3 The metallization of through silicon vias (TSVs), one of a promising technology for the 3D packaging, is expected to enhance the operation speed and performance of the microelectronic devices.4-8 A void-free filling of the TSVs by Cu electrodeposition with proper organic additives chemistry has been actively investigated to reduce processing time. 9-11A concentration gradient of suppressing agent, high at the via top while decreasing gradually toward the via bottom, typically induces a bottom-up via filling. The Cu deposit according to the filling time typically reveals a V-shaped profile reflecting the gradient of additive coverage. [12][13][14] Recently, an extreme bottom-up filling of the vias was achieved using one component of additive, suppressor, resulting in a clearly flat filling profile rather than the V-shape. 15,16 Based on the previous results, L. Yang et al. reported that the difference in the adsorption density of suppressing agents between the via top and bottom was required for a void-free bottom-up filling. 17Moreover, the accumulation of accelerator at the bottom of the via was also highlighted in understanding the filling mechanism. In the case of recessed features with submicrometer dimensions, accelerators including bis(3-sulfopropyl)disulfide (SPS) promoted copper deposition, enabling the superconformal filling in the combination with suppressors, based on a curvature-enhanced-accelerator coverage (CEAC) mechanism.18-26 However, the same additive composition or deposition method used in the CEAC model itself mostly failed in the void-free filling of the TSVs. Therefore, additional steps including the selective deactivation of the adsorbed SPS on the top of the vias were introduced to improve the filling perf...