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We report a facile desymmetrization of 1,4‐diethynylbicyclo[2.2.2]octane. One of the acetylene termini was protected by TMS and the desired product was purified by sublimation. It is stable but reactive, as shown by the synthesis of a complex pyridine‐terminated molecular rod containing both a bicyclo[1.1.1]pentane and a bicyclo[2.2.2]octane cage. Six crystal structures of key intermediates are presented. Facile desymmetrization of 1,4‐diethynylbicyclo[2.2.2]octane based on TMS protection of one of the acetylene termini followed by sublimation of the desired product is presented. The reactivity of this derivative was demonstrated in the synthesis of a complex pyridine‐terminated molecular rod containing both a bicyclo[1.1.1]pentane and a bicyclo[2.2.2]octane cage. [ABSTRACT FROM AUTHOR]

We report on the structures of three dibromothiophene compounds (4, 5, and 12) and the analysis of the patterns of self-assembly in the solid state by C-- Br--Br--C halogen bonds of a selected set of 16 di- or poly-bromine-- (poly)thiophene monomers sorted according to the dimensionality of their halogen-bonded, extended frameworks thereby identifying syn- or anti-strings and layers. We conclude that in 1, 2, 9, and 10, the antiparallel orientation of successive C-- Br--Br--C halogen-bonded dibromothiophene units along extended anti-strings is linked to the occurrence of solid-state polymerization. [ABSTRACT FROM AUTHOR]

We report on the structures of three dibromothiophene compounds (4, 5, and 12) and the analysis of the patterns of self-assembly in the solid state by C-- Br--Br--C halogen bonds of a selected set of 16 di- or poly-bromine-- (poly)thiophene monomers sorted according to the dimensionality of their halogen-bonded, extended frameworks thereby identifying syn- or anti-strings and layers. We conclude that in 1, 2, 9, and 10, the antiparallel orientation of successive C-- Br--Br--C halogen-bonded dibromothiophene units along extended anti-strings is linked to the occurrence of solid-state polymerization. [ABSTRACT FROM AUTHOR]

We report on the synthesis and application of a 2 nm long, curved ditopic biscarboxylic ligand with a 1,4-bis(ethynyl)bicyclo[2.2.2]octane rotator core and an helical twist to the construction of an extended single-crystalline framework solid with paddlewheel hinges, [CuII]2[1,4-bis(carboxyphenyl ethynyl)bicyclo[2.2.2]octane]2(H2O)2 or [CuII]2(bbcbco)2(H2O)2. The interconnection of interpenetrated square lattices involves short rotor-rotor H ···H interactions (1.9 to 2.4 Å) such that the moving parts are expected to rub onto each other in the lattice in a Brownian rotational motion with a calculated rotational barrier of 3.7 kcal ·mol-1. Variable-temperature 1H spin-lattice relaxation ( T1) experiments carried out on a static crystalline sample did not provide however a value of this rotational barrier because the relaxation proved to be dominated by the coupling of the moving protons to the electronic spins of the CuII dimers. Remarkably, we reveal how the singlet-triplet spin dynamics of non-interacting CuII dimers is elegantly characterized by solid state NMR spectroscopic experiments yielding an exchange coupling constant, Jexp = -365 K = -254 cm-1, in good agreement with theoretical estimations and experimental data on related CuII dimer systems. [ABSTRACT FROM AUTHOR]

We report on a series of amino acid derivatives of tetrathiafulvalene as well as on the structure-directing abilities of their peptide residues in the crystalline solid state to stabilize patterns of interactions such as β strands and sheet motifs. Characteristic hydrogen-bonding motifs are indeed identified within ethylenedithiotetrathiafulvalene (EDT-TTF) and dimethyltetrathiafulvalene (Me2-TTF) based compounds 1- 5. Esters 1- 3 contain hydrogen-bond acceptors, namely carbonyl groups, as well as one strong (NH) and one weak (C [ABSTRACT FROM AUTHOR]

Studies the crystal structures of bis(tetraphenylphosphonium) bis[cis-1,2-bis(methoxycarbonyl)ethlene-dithiolato-Kappa[sup 2]S,S' nickelate(II) and bis(tetraphenylphosphonium) bis[cis-1,2-bis(methoxycarbonyl)ethylene-dithiolato-Kappa[sup 2]nickelate(III) iodide. Location of the nickel atoms; Paramagnetic complexes.

Two‐dimensional (2D) van der Waals materials with in‐plane anisotropy are of great interest for directional transport of charge and energy, as exemplified by recent studies on black phosphorus and α‐phase molybdenum trioxide (α‐MO3). Here, a layered van der Waals semiconductor with in‐plane anisotropy built upon the superatomic units of Mo6S3Br6 is reported. This material possesses robust 2D characteristics with a direct gap of 1.64 eV, as determined by scanning tunneling spectroscopy and first‐principles calculations. Polarization‐dependent Raman spectroscopy measurement and density functional theory calculation reveal strong in‐plane anisotropy. These results suggest an effective strategy to explore anisotropic 2D electronic and optoelectronic properties from superatomic building blocks with multifunctionality, emergent properties, and hierarchical control. [ABSTRACT FROM AUTHOR]

In the title compound, (C10H9NOS6)K[Hg(SCN)4] or (EDT–TTF–CONHMe)K[Hg(SCN)4)], fully oxidized organic (EDT–TTF–CONHMe)+· radical cations form quasi-one-dimensional stacks running along the monoclinic 21 axis and alternating along the crystallographic [101] direction with inorganic anion stacks made from mixed K+–[Hg(SCN)4]2− ribbons. For each anion, three essentially collinear SCN ligands inter­act with the K+ ions via short N⋯K contacts, while the terminal N atom of the fourth SCN group is engaged in a number of hydrogen-bond contacts with the –CH, –NH and –CH2 hydrogen-bond donors of the amide function. Radical cations are dimerized along the stacks and the crystal conductivity is activated. [ABSTRACT FROM AUTHOR]

In the title compound, (C(10)H(9)NOS(6))K[Hg(SCN)(4)] or (EDT-TTF-CONHMe)K[Hg(SCN)(4))], fully oxidized organic (EDT-TTF-CONHMe)(+.) radical cations form quasi-one-dimensional stacks running along the monoclinic 2(1) axis and alternating along the crystallographic [101] direction with inorganic anion stacks made from mixed K(+)-[Hg(SCN)(4)](2-) ribbons. For each anion, three essentially collinear SCN ligands interact with the K(+) ions via short N...K contacts, while the terminal N atom of the fourth SCN group is engaged in a number of hydrogen-bond contacts with the -CH, -NH and -CH(2) hydrogen-bond donors of the amide function. Radical cations are dimerized along the stacks and the crystal conductivity is activated.