Dominik Lungerich

Odd-bods have much in common: Odd–even effects are well-known for n-alkanes in the solid state, but they are not expected in the liquid state. Quasi-elastic neutron scattering uncovered a surprising odd–even effect in the dynamic properties of liquid n-alkanes (see graph) that violates the Kauzmann–Eyring prediction. The result demands reexamination and extension of the classical theories of molecular viscous flow.

[Communication]
Ke Yang, Zhikun Cai, Abhishek Jaiswal, Madhusudan Tyagi, Jeffrey S. Moore, Yang Zhang
Angew. Chem. Int. Ed., October 12, 2016, DOI: 10.1002/anie.201607316. Read article

Marcin A. Majewski, Yongseok Hong, Prof. Tadeusz Lis, Dr. Janusz Gregoliński, Prof. Piotr J. Chmielewski, Dr. Joanna Cybińska, Prof. Dongho Kim and Prof. Marcin Stępień

A non-Euclidean belt: Octulene, the largest coronoid ring reported to date, features a saddle-shaped aromatic hydrocarbon ring that fits on a hyperbolic surface. The large central cavity, in spite of its low electrostatic potential, acts as an anion receptor in nonpolar media, with a particularly good affinity for the chloride anion.

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Mix and go: Presented herein is a mild, operationally simple, mix-and-go procedure for the synthesis of acyclic trisubstituted Z-enediynes from readily available terminal alkynes in good yields. This method stems from a serendipitous discovery, and makes use of cooperative palladium/copper bimetallic catalysis and air as an oxidant to effect an intriguing alkyne trimerization to yield the valuable Z-enediyne moiety.

[Communication]
Jin Tu Danence Lee, Yu Zhao
Angew. Chem. Int. Ed., October 07, 2016, DOI: 10.1002/anie.201608192. Read article

Abstract

Nature Chemistry. doi:10.1038/nchem.2612

Authors: Hai Qian, Morgan E. Cousins, Erik H. Horak, Audrey Wakefield, Matthew D. Liptak & Ivan Aprahamian

A family of fluorescent molecular rotors has been developed and their mechanism for emission understood. It has been observed that, although most fluorescent molecules emit from their lowest energy excited state, S1 (in accordance with Kasha's rule), BODIHY dyes do not. Furthermore, their fluorescence is enhanced through restricted rotor rotation, which suppresses internal conversion to the dark S1 state.

A convenient leap into the red: Two synthetic steps provide access to a new family of highly fluorescent fluorophores termed BOIMPYs. Two BF₂ units enable the efficient exploitation of the meso position and lead to absorption at λ≈600 nm. Owing to the structural similarity to well-studied BODIPY dyes, common modes of post-functionalization can be easily transferred to the new motif.

[Communication]
Lukas J. Patalag, Peter G. Jones, Daniel B. Werz
Angew. Chem. Int. Ed., September 20, 2016, DOI: 10.1002/anie.201606883. Read article

Like a hand in a glove: When decorated with electron-donating thiol groups, trithiasumanenes assembled with fullerenes both in solution and in the solid state. The supramolecular complexes were unambiguously characterized by X-ray diffraction, which revealed their concave–convex supramolecular recognition (see picture). The crystals of the supramolecular complexes showed remarkable thermal stability and high photoconductivity.

[Communication]
Yu-Min Liu, Dan Xia, Bo-Wei Li, Qian-Yan Zhang, Tsuneaki Sakurai, Yuan-Zhi Tan, Shu Seki, Su-Yuan Xie, Lan-Sun Zheng
Angew. Chem. Int. Ed., September 21, 2016, DOI: 10.1002/anie.201606383. Read article

Squeezing cross-coupling products: Complex cis-[Pd(C₆F₅)₂(THF)₂] was used as a meter to quantify directly the efficiency of ligands to promote reductive elimination in carbon–carbon bond formation. The ligand could be ranked and compared to others. The complex is a good precatalyst for palladium(0) catalytic species PdL_n.

[Communication]
Estefanía Gioria, Juan del Pozo, Jesús M. Martínez-Ilarduya, Pablo Espinet
Angew. Chem. Int. Ed., September 16, 2016, DOI: 10.1002/anie.201607089. Read article

Fusion porphyrins: Quinoline-fused porphyrins were obtained by a Suzuki–Miyaura coupling of β-borylated porphyrins with 2-iodoaniline and subsequent Pictet–Spengler cyclization. This method also allowed the synthesis of phenanthroline-fused porphyrin dimers through a β-to-β 1,4-(2,3-diamino)phenylene-bridged Ni^II/porphyrin dimer. The phenanthroline site of the dimer coordinated to either a Ni^II or Zn^II cation, causing electronic and steric perturbations.

[Communication]
Ke Gao, Norihito Fukui, Seok II Jung, Hideki Yorimitsu, Dongho Kim, Atsuhiro Osuka
Angew. Chem. Int. Ed., September 16, 2016, DOI: 10.1002/anie.201606293. Read article

A phosphole-fused porphyrin dimer as a representative of a new class of phosphorus-containing porphyrins was synthesized. This structure exhibits remarkably broadened absorption as well as unique optoelectronic properties and is a good electron acceptor owing to the unique phosphole-fused structure.

[Communication]
Tomohiro Higashino, Tomoki Yamada, Tsuneaki Sakurai, Shu Seki, Hiroshi Imahori
Angew. Chem. Int. Ed., September 09, 2016, DOI: 10.1002/anie.201607417. Read article

“… To what extent is reproducibility a significant issue in chemical research? How can problems involving irreproducibility be minimized? … Researchers should be aware of the dangers of unconscious investigator bias, all papers should provide adequate experimental detail, and Reviewers have a responsibility to carefully examine papers for adequacy of experimental detail and support for the conclusions …” Read more in the Editorial by Robert G. Bergman and Rick L. Danheiser.

[Editorial]
Robert G. Bergman, Rick L. Danheiser
Angew. Chem. Int. Ed., August 25, 2016, DOI: 10.1002/anie.201606591. Read article

Abstract

Abstract

A new approach to fused helicenes is reported, in which varied substituents are readily incorporated in the extended aromatic frame. From an alkynyl precursor, the final helical compounds are obtained in a two-step process, in which the final C−C bond is photochemically forged by coupling cyclization and dehydroiodination. The distortion of the π-system from planarity leads to unusual packing in the solid state.

[Communication]
Rana K. Mohamed, Sayantan Mondal, Joseph V. Guerrera, Teresa M. Eaton, Thomas E. Albrecht-Schmitt, Michael Shatruk, Igor V. Alabugin
Angew. Chem. Int. Ed., August 18, 2016, DOI: 10.1002/anie.201606330. Read article

A reactive cyclopentadiene ring in 21-carba-23-thiaporphyrin enables the formation of a dimer with a direct covalent bond between internal carbon atoms and a unique parallel-displaced arrangement of the two macrocyclic π planes. The dimer shows exceptional reactivity towards acids which cause its cleavage and formation of the asymmetric carbathiaporphyrin–carbatichlorin dyad or 2,3-dihalo-21-carba-23-thiachlorin depending on the acid used.

[Communication]
Anna Berlicka, Michał J. Białek, Lechosław Latos-Grażyński
Angew. Chem. Int. Ed., August 17, 2016, DOI: 10.1002/anie.201606298. Read article

2C; confusion and cyclization: Circularly orientated BODIPY-based macrocycles were synthesized based on multiply N-confused calix[n]phyrin (n=4, 6, 8) derivatives. These novel BODIPYmers exhibit unique size-dependent photophysical properties.

[Communication]
Masatoshi Ishida, Toshihiro Omagari, Ryuji Hirosawa, Keisuke Jono, Young Mo Sung, Yuhsuke Yasutake, Hidemitsu Uno, Motoki Toganoh, Hajime Nakanotani, Susumu Fukatsu, Dongho Kim, Hiroyuki Furuta
Angew. Chem. Int. Ed., August 17, 2016, DOI: 10.1002/anie.201606246. Read article

Very stable suspensions of high-quality single- or few-layer antimonene were obtained by liquid-phase exfoliation under sonication without the need for a surfactant. The Raman spectrum of antimonene was found to strongly depend on its thickness, which was also rationalized by quantum-mechanical calculations.

[Communication]
Carlos Gibaja, David Rodriguez-San-Miguel, Pablo Ares, Julio Gómez-Herrero, Maria Varela, Roland Gillen, Janina Maultzsch, Frank Hauke, Andreas Hirsch, Gonzalo Abellán, Félix Zamora
Angew. Chem. Int. Ed., August 16, 2016, DOI: 10.1002/anie.201605298. Read article