A series of new charge-transfer cocrystals of F2TCNQ with anthracene, tetracene, and chrysene was prepared and characterized. The donor and acceptor molecules are arranged in alternating D–A–D–A stacks. The linear acenes in combination with F2TCNQ form layered structures due to in-plane lateral donor–acceptor and acceptor–acceptor interactions via multiple C–H···N and C–H···F hydrogen bonds, which govern the crystal structure and significantly alter face-to-face π–π interactions. In the cocrystal of F2TCNQ with chrysene no interactions between acceptor molecules are observed, and the π–π interactions prevail. Thus, the donor–acceptor interplanar distance is the smallest in the chrysene complex despite its lower energy level of the HOMO and weaker donor ability, as determined through electrochemical oxidation potentials in this series of PAHs. The charge-transfer values estimated through empirical correlations and QTAIM analysis also do not manifest a direct dependence on the donor ability of PAHs. Thus, though face-to-face π–π interactions dictate the formation of cocrystals, the lateral noncovalent interactions are as important for the supramolecular arrangement and charge transfer. UV/vis spectroscopy and electronic structure quantum chemical calculations show that these cocrystals may be classified as small-gap semiconductors with energy gaps of 0.7–1.3 eV.

Reaction between aryl substituted sodium 1,2,3-triphospholides or bis-1,2,3-triphospholide and [Fe(η6-(C6H5CH3)Cp]+[PF6]- in boiling diglyme results in pure 1,2,3-triphosphaferrocenes 1-3 or bis-(1,2,3-triphosphaferrocene) 4, respectively, with good yields. The structure of all obtained...

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The key intermediate palladacycles (mono-, bi-, and tetranuclear) with phosphonate, acetate, and other counterions in C­(sp2)–H phosphonation are analyzed in terms of their redox properties, mutual transitions, reactivity, and reaction pathways for the selective production of the desired products. It was found that, in the presence of pyridine, the reaction proceeds through a mononuclear palladacycle, which at a relatively high electrolysis potential gives the product of ortho-phosphonation of the arene with a C–P bond in good yield. Under acidic conditions, the process involves the tetrapalladium intermediate and leads to a product with a C–O–P bond. Phosphorous acid gives inorganic phosphoric derivatives of 2-phenylpyridine. The electrochemical data on the redox properties of key palladacycles 4 and 5 and their potentials and energy gaps are confirmed by DFT calculations.

The reaction of triferrocenylthiophosphite with elemental sulfur leads to triferrocenyltetrathiophosphate. The molecule of tetrathiophosphate adopts propeller-like all synclinal-conformation of the ferrocenyl fragments respective to the P=S bond. All ferrocenyl groups have nearly ideal eclipsed conformation of the cyclopentadienyl fragments. The Fc3S3P (1), Fc3S3P=O, (2) and Fc3S3P=S (3) demonstrate three reversible and well-separated ferrocenyl-based redox events. The electronic structures of 1–3 have been studied quantum-chemically; the energies and composition of frontier orbitals have been calculated.

Aryl-substituted sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienides Na(C3R3P2) (R = Ph, 4-Me-C6H4, 4-Cl-C6H4, 1a-c) react with [FeCp(η6-C6H5CH3)][PF6] to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferrocenes [FeCp(η5-P2C3R3)] (2a-c) in 71-78% yield. The structures of 2a-c were confirmed by NMR,...

Thiacalix[4]arene-functionalized polydiacetylene (PDA) vesicles showed selective colorimetric response toward several lanthanide ions. This approach can be a good basis for lanthanide express analysis.

High-quality single crystals of the charge transfer compound tetracene−F 4 TCNQ (1:1) were grown by physical vapor transport and characterized by IR and UV/vis spectroscopy as well as by accurate single-crystal X-ray diffraction in combination with a topological analysis of electron density distribution. The cocrystal is assembled via weak noncovalent π•••π interactions. Experimental static deformation density maps demonstrate the regions of charge accumulation directed toward the areas of electron density depletion within the stacks composed of alternating donor and acceptor molecules; the energy of these interactions is estimated to be 11.3 kcal/mol per acceptor molecule. The cumulative energy of multiple side-on F•••H and N•••H intermolecular attractive interactions is approximately the same as the value for face-to-face interactions. The estimation of the charge transfer degree by various methods gives a value in the range 0.10−0.20 e.