The Chemical Record

Cover image for Vol. 16 Issue 2

April 2016

Volume 16, Issue 2

Pages 581–1016

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Personal Account
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      Cover Picture (page 581)

      Version of Record online: 22 APR 2016 | DOI: 10.1002/tcr.201690001

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  2. Personal Account

    1. Top of page
    2. Cover Picture
    3. Personal Account
    1. Combination of Metal Coordination Tetrahedra and Asymmetric Coordination Geometries of Sb(III) in the Organically Directed Chalcogenidometalates: Structural Diversity and Ion-exchange Properties (pages 582–600)

      Mei-Ling Feng, Kai-Yao Wang and Xiao-Ying Huang

      Version of Record online: 26 JAN 2016 | DOI: 10.1002/tcr.201500243

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      The synthetic strategy of the combination of metal tetrahedra and asymmetric coordination polyhedra of Sb(III) in the presence of various organic species under solvothermal conditions leads to new chalcogenidometalates with diverse structures and ion-exchange properties.

    2. Single-molecule Spectroscopy: Exploring Heterogeneity in Chemical and Biological Systems (pages 601–613)

      Shirsendu Ghosh and Kankan Bhattacharyya

      Version of Record online: 27 JAN 2016 | DOI: 10.1002/tcr.201500214

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      Single-molecule spectroscopy: understanding microheterogeneity, structure, and function of chemical and biological systems utilizing single-molecule spectroscopy.

    3. Prospects of Graphene as a Potential Carrier-Transport Material in Third-Generation Solar Cells (pages 614–632)

      Towhid H. Chowdhury, Ashraful Islam, A. K. Mahmud Hasan, M. Asri Mat Terdi, M. Arunakumari, Surya Prakash Singh, Md. Khorshed Alam, Idriss M. Bedja, Mohd Hafidz Ruslan, Kamaruzzaman Sopian, Nowshad Amin and Md. Akhtaruzzaman

      Version of Record online: 27 JAN 2016 | DOI: 10.1002/tcr.201500206

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      The application of graphene in third-generation solar cells offers the potential to overcome the limitations of existing solar cell technologies. The use of graphene in organic photovoltaics, dye-sensitized solar cells, and third-generation inorganic–organic hybrid perovskite solar cells is reviewed.

    4. Recent Advances in Layered Metal Chalcogenides as Superconductors and Thermoelectric Materials: Fe-Based and Bi-Based Chalcogenides (pages 633–651)

      Yoshikazu Mizuguchi

      Version of Record online: 29 JAN 2016 | DOI: 10.1002/tcr.201500263

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      Layered metal chalcogenides can be multifunctional materials due to their flexibility of crystal structure and physical properties. In this article, I review the discovery of Fe-based and Bi-based superconductors and thermoelectric materials. In particular, I discuss the importance of chemical and physical pressure effects on the material design and the enhancement of functionalities.

    5. Biomimetic Assembly Lines Producing Natural Product Analogs: Strategies from a Versatile Manifold to Skeletally Diverse Scaffolds (pages 652–666)

      Hiroki Oguri

      Version of Record online: 1 FEB 2016 | DOI: 10.1002/tcr.201500213

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      Biomimetic assembly lines gaining concise and programmable access to skeletally and stereochemically diverse natural product analogs have been developed. This account illustrates synthetic strategies exploiting versatile manifolds that allow modular assembly of building blocks and subsequent divergent cyclizations to produce densely functionalized scaffolds bearing three-dimensional structural variations and biological relevance. Successful discovery of several lead candidates for chemotherapy of African sleeping sickness provides the proof-of-concept of this synthetic approach.

    6. Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C–F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol (pages 667–687)

      Cuibo Liu and Bin Zhang

      Version of Record online: 1 FEB 2016 | DOI: 10.1002/tcr.201500248

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      Cleavage of C–F bonds in polyfluoroarenes is an important and powerful tool in synthetic chemistry. The transition-metal-free nucleophilic aromatic substitution (SNAr) is simple, mild, economical, and environmentally benign, and its application toward C–F bond functionalization is reviewed here. The use of the SNAr strategy for the creation of C–C, C–N, C–O, C–S, and C–H bonds in pharmaceutical building blocks and materials molecules is discussed, alongside its mechanistic pathways and limitations and perspectives on the future development of this chemistry.

    7. Umpolung Reactions of α-Imino Esters: Useful Methods for the Preparation of α-Amino Acid Frameworks (pages 688–702)

      Isao Mizota and Makoto Shimizu

      Version of Record online: 2 FEB 2016 | DOI: 10.1002/tcr.201500267

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      Our recent efforts toward the development of tandem reactions utilizing umpolung reactions of α-imino esters are summarized. Various efficient methods such as diastereoselective Mannich reactions, application to flow systems, regioselective syntheses of alkynyl amino esters and allenyl esters, vinylogous aldol reactions, four-component coupling reactions, N,N,C-trialkylations, and enamine syntheses are described.

    8. Computational Methods for MOF/Polymer Membranes (pages 703–718)

      Ilknur Erucar and Seda Keskin

      Version of Record online: 4 FEB 2016 | DOI: 10.1002/tcr.201500275

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      Metal–organic framework (MOF)/polymer mixed matrix membranes (MMMs) combine the excellent gas permeability and selectivity of MOFs with the easy processability of polymers. There has been a large demand for computational studies that can accurately predict the gas separation performance of MOF/polymer MMMs prior to experiments. In this Personal Account, we review the current computational approaches for modeling MOF-based MMMs and discuss the strategies to identify the most promising MOF/polymer pairs for specific gas separations.

    9. The Structure-property Relationships of D-π-A BODIPY Dyes for Dye-sensitized Solar Cells (pages 719–733)

      Mao Mao and Qin-Hua Song

      Version of Record online: 5 FEB 2016 | DOI: 10.1002/tcr.201500251

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      The structure-property relationships of D-π-A BODIPY dyes for dye-sensitized solar cells: developments in the field of D-A BODIPY dye sensitizers for DSSCs with liquid electrolytes in the last decade are discussed, and various molecular design strategies for these sensitizers, as well as their photophysical and electrochemical behaviors and their device performance, are described.

    10. Photoinduced Electron Transfer in Organic Solar Cells (pages 734–753)

      Peng Song, Yuanzuo Li, Fengcai Ma, Tõnu Pullerits and Mengtao Sun

      Version of Record online: 8 FEB 2016 | DOI: 10.1002/tcr.201500244

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      Photoinduced electron transfer in organic solar cells: Electron transfer (ET) is the key process in light-driven charge separation reactions in organic solar cells. The current review summarizes the progress in the theoretical modelling of ET in OSCs, while there is still much to be understood on the role and influence of external circumstances on power conversion efficiencies of OPV materials.

    11. Ruthenium-Amine Conjugated Organometallic Materials for Multistate Near-IR Electrochromism and Information Storage (pages 754–767)

      Jian-Hong Tang, Chang-Jiang Yao, Bin-Bin Cui and Yu-Wu Zhong

      Version of Record online: 8 FEB 2016 | DOI: 10.1002/tcr.201500252

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      Monometallic or dimetallic complexes with the ruthenium-amine conjugated structural unit display consecutive redox waves with low potentials and intense near-infrared absorptions. Thin films of these complexes show multistate near-infrared electrochromism with good contrast ratios and long optical retention times. Flip-flop and flip-flap-flop memories have been demonstrated on the basis of these thin films.

    12. Development of C3-Symmetric Tris-Urea Low-Molecular-Weight Gelators (pages 768–782)

      Masamichi Yamanaka

      Version of Record online: 25 FEB 2016 | DOI: 10.1002/tcr.201500282

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      Coming together as one: Diverse supramolecular gels of organic solvents and aqueous solutions are developed from structurally related C3-symmetric tris-urea frameworks. Supramolecular hydrogels obtained from amphiphilic tris-ureas can be used in the electrophoresis of proteins.

    13. Three-Dimensional Tissue Models Constructed by Cells with Nanometer- or Micrometer-Sized Films on the Surfaces (pages 783–796)

      Chun-Yen Liu, Michiya Matsusaki and Mitsuru Akashi

      Version of Record online: 29 FEB 2016 | DOI: 10.1002/tcr.201500272

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      Put a coat on: Various thicknesses of 3D tissues are easily constructed by nano- and microcoating technologies on cell surfaces. A summary of the effects of both coating methods on tissue thicknesses, cell–cell distances, cell location, and even functionalized tissue models are presented.

    14. Recent Progress in Synthesis and Application of Thiophene Oligomers Based on Bithiophene Dicarbanions (pages 797–809)

      Lu Li, Chunmei Zhao and Hua Wang

      Version of Record online: 29 FEB 2016 | DOI: 10.1002/tcr.201500270

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      Back in the saddle: Synthetic work on full thiophene oligomers with novel molecular structures, such as helical, double-helical, and saddle-shaped configurations, is described. Most of these novel thiophene oligomers are derived from three bithiophenes, bi(dithienothiophene), and their dicarbanions.

    15. Detection of Contaminants of High Environmental Impact by Means of Fluorogenic Probes (pages 810–824)

      José García-Calvo, Patricia Calvo-Gredilla, Marcos Ibáñez-Llorente, Teresa Rodríguez and Tomás Torroba

      Version of Record online: 29 FEB 2016 | DOI: 10.1002/tcr.201500253

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      Detection of contaminants of high environmental impact by means of fluorogenic probes: Selective fluorogenic probes for contaminants of high environmental impact, which were able to show large differences in their fluorescence in the presence of selected analytes, were used in the preparation of fluorogenic probes for the detection of contaminants of high environmental impact which currently have no good solutions: phosphorylating agents, such as chemical weapons; methyl mercury(II); the cyanide anion; amino-acid metabolites, such as doping substances; and biogenic amine mimics, such as drugs of abuse and recreational drugs.

    16. Molecular Design for Cryogenic Magnetic Coolants (pages 825–834)

      Jun-Liang Liu, Yan-Cong Chen and Ming-Liang Tong

      Version of Record online: 1 MAR 2016 | DOI: 10.1002/tcr.201500278

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      Four explicit strategies for improving the magnetocaloric effect, which were proposed from the theoretical viewpoint, are described. Through the application of these strategies, a series of magnetic coolants have been discovered by our research group.

    17. Transition Metal-Catalyzed Carbonylative C[BOND]H Bond Functionalization of Arenes and C(sp3)[BOND]H Bond of Alkanes (pages 835–856)

      Sandip T. Gadge, Prashant Gautam and Bhalchandra M. Bhanage

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500280

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      Carbonylative C[BOND]H bond functionalization of alkanes and arenes assisted by directing groups and in the absence of directing groups is discussed. The C[BOND]H bond functionalization can be carried out in the presence of gaseous CO, as well as CO surrogates. This methodology thus comes as an atom-economical and step-economical way of synthesizing molecules.

    18. Synthetic Reactions Using Low-valent Titanium Reagents Derived from Ti(OR)4 or CpTiX3 (X = O-i-Pr or Cl) in the Presence of Me3SiCl and Mg (pages 857–872)

      Sentaro Okamoto

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500277

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      A specific low-valent titanium (LVT) species generated from Me3SiCl, Ti(OR)4 or CpTiX3 (X = O-i-Pr or Cl), Me3SiCl, and Mg mediates several synthetic reactions, such as C–O bond-cleaving reactions of allyl and propargyl ethers, esters, and carbamates, N–S bond cleavage of sulfonamides, intra- and inter-molecular alkyne or alkyne/nitrile cycloaddition, radical reduction of epoxides and oxetanes, and McMurry coupling of aryl aldehydes.

    19. Synthesis and Applications of π-Extended Naphthalene Diimides (pages 873–885)

      Cheng Li, Zhi Lin, Yan Li and Zhaohui Wang

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500246

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      Synthesis and applications of π-extended naphthalene diimides: the synthesis strategies, structure-property relationships, and applications of π-extended naphthalene diimides, including acene diimides and heterocyclic acene diimides, are described.

    20. Transition-metal-catalyzed Chelation-assisted C–H Functionalization of Aromatic Substrates (pages 886–896)

      Binlin Zhao, Zhuangzhi Shi and Yu Yuan

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500241

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      Transition-metal-catalyzed chelation-assisted C–H activation provides atom- and step-economical approaches for the construction of functional compounds. In this account, a more detailed discussion is directed towards our recent studies of the transition-metal-catalyzed chelation-assisted C–H/C–H functionalization of aromatic substrates bearing directing functional groups.

    21. Applications of Chiral Squaramides: From Asymmetric Organocatalysis to Biologically Active Compounds (pages 897–906)

      Xin Han, Hai-Bing Zhou and Chune Dong

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500266

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      This review seeks to provide coverage on the recent advances in chiral squaramide-catalyzed asymmetric transformations and their application in the synthesis of a variety of chiral biologically active compounds. It aims to give an overview highlighting the new reaction types and enantioenriched medicinal scaffolds developed in the last few years.

    22. Synthesis of Organofluoro Compounds Using Methyl Perfluoroalk-2-ynoates as Building Blocks (pages 907–923)

      Xuechun Sun, Jing Han, Jie Chen, Hui Zhang and Weiguo Cao

      Version of Record online: 10 MAR 2016 | DOI: 10.1002/tcr.201500258

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      Synthetic applications of methyl perfluoroalk-2-ynoates, leading to the convenient preparation of a wide range of perfluoroalkylated compounds, are reviewed.

    23. Titanium Salan/Salalen Complexes: The Twofaced Janus of Asymmetric Oxidation Catalysis (pages 924–939)

      Evgenii P. Talsi, Anna A. Bryliakova and Konstantin P. Bryliakov

      Version of Record online: 15 MAR 2016 | DOI: 10.1002/tcr.201500273

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      The versatile titanium(IV) salan and salalen catalysts conduct the asymmetric epoxidation of olefins and oxidation of thioethers with H2O2 with good to excellent enantioselectivities. The catalytic properties of these complexes, the available structure-reactivity relationships, and the data on the mechanisms of their action are summarized.

    24. Catalytic Water Oxidation by Ruthenium Complexes Containing Negatively Charged Ligand Frameworks (pages 940–963)

      Markus D. Kärkäs and Björn Åkermark

      Version of Record online: 15 MAR 2016 | DOI: 10.1002/tcr.201500254

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      Light harvesting for the production of solar fuels has been extensively investigated as an attractive approach to clean and carbon-neutral energy. In this context, an essential component is a catalyst that is able to oxidize water to dioxygen. This account describes our group's efforts in designing Ru-based water oxidation catalysts containing negatively charged ligand scaffolds. The benefits of incorporating these anionic ligands are presented, along with mechanistic details.

    25. Optically Active Hybrid Materials Constructed from Helically Substituted Polyacetylenes (pages 964–976)

      Huanyu Zhang, Biao Zhao and Jianping Deng

      Version of Record online: 17 MAR 2016 | DOI: 10.1002/tcr.201500298

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      Adding twists: An overview on optically active hybrid materials constructed from helically substituted polyacetylenes (HSPAs) is provided with an emphasis on preparation and applications. The hybrid materials are classified into three main groups: HSPA/silica; HSPA/graphene, and HSPA/Fe3O4 magnetic nanoparticles (NPs). This article is expected to inspire more interest in advanced chiral hybrid materials.

    26. Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate (pages 977–986)

      Yan-Na Ma and Shang-Dong Yang

      Version of Record online: 17 MAR 2016 | DOI: 10.1002/tcr.201500242

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      Asymmetric synthesis of chiral atropisomeric bis-aryl organophosphorus from menthyl H-phosphinate: new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C–H functionalization are described.

    27. The Frontier of Molecular Spintronics Based on Multiple-Decker Phthalocyaninato TbIII Single-Molecule Magnets (pages 987–1016)

      Keiichi Katoh, Tadahiro Komeda and Masahiro Yamashita

      Version of Record online: 16 MAR 2016 | DOI: 10.1002/tcr.201500290

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      A single-molecule magnet (SMM) of a multi-decker TbIII phthalocyaninato complex; synthesis and characterization of its film using scanning tunneling microscopy (STM), which reveals the morphology of the molecule and spin-state by detecting Kondo resonance.