Search results for "ta116"
showing 10 items of 942 documents
Halogen-bonded solvates of tetrahaloethynyl cavitands
2017
The formation and structures of halogen-bonded solvates of three different tetrahaloethynyl cavitands with acetone, chloroform, acetonitrile, DMF and DMSO were prepared and investigated. The inclusion and host–guest behaviour of the resorcinarene cavitands was found to be highly dependent on the flexibility of the ethylene-bridging unit.
Unveiling Electronic Transitions in Three Novel Chiral Azo-Compounds Using Linear and Nonlinear Circular Dichroism: A Theoretical−Experimental Study
2011
Herein, we report on the experimental and theoretically study of the linear absorption, electronic circular dichroism (ECD) spectra, as well as the two-photon absorption circular-linear dichroism measurements of three different chiral azo derivatives in dimethylsulfoxide solution. Using potential energy surfaces and frontier orbital analysis, we established the most stable conformation for each molecule and elucidated their different electronic transitions. Our theoretical calculations allowed us to unambiguously identify the spectral position of such transitions and correlate them with the spectral profiles observed in the two-photon absorption spectra. To further elucidate the characteris…
Chiral self-sorting behaviour of [2.2]paracyclophane-based bis(pyridine) ligands
2019
Two constitutionally isomeric chiral bis(pyridine) ligands based on planar chiral 4,15-difunctionalized [2.2]paracyclophanes were synthesized, the respective enantiomers were separated via HPLC on a chiral stationary phase, and their self-assembly behaviour upon coordination to palladium(ii) ions was studied with regard to chiral self-sorting effects. As proven by NMR spectroscopy, mass spectrometry, CD spectroscopy, UV-Vis spectroscopy and X-ray crystallography both ligands form the expected dinuclear complexes upon coordination to cis-protected di- or tetravalent palladium(ii) ions, respectively, however, with distinct differences concerning their chiral self-sorting ability. peerReviewed
Formation of a novel ferromagnetic end-to-end cyanate bridged homochiral helical copper(ii) Schiff base complex via spontaneous symmetry breaking
2014
A homochiral helical coordination polymer of copper(II) has been synthesized using achiral precursors via spontaneous symmetry breaking and has been confirmed by single crystal X-ray diffraction and solid-state CD spectroscopy. The variable temperature magnetic measurements indicate the presence of weak ferromagnetic exchange interactions mediated by end-to-end cyanate bridges (J = +0.12 cm(-1)).
Enantiomerically pure trinuclear helicates via diastereoselective self-assembly and characterization of their redox chemistry.
2014
A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2, 2′-dihydroxy-1, 1′-binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereoselective self-assembly into D2-symmeteric double-stranded trinuclear helicates upon coordination to copper(I) and silver(I) ions and to D3-symmetric triple-stranded trinuclear helicates upon coordination to copper(II), zinc(II), and iron(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly …
Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.
2013
Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Ta…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters
2018
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good corre…
Cytotoxicities of Polysubstituted Chlorodicarbonyl(cyclopentadienyl) and (Indenyl)ruthenium Complexes
2013
Polysubstituted cyclopentadienyl and indenyl complexes of ruthenium were synthesized and investigated to elucidate their potential cytotoxic activities. In particular, substituted (indenyl)ruthenium complexes inhibited the proliferation of a panel of human adherent cancer cells with comparable activity to reference agent cisplatin. One of the active compounds exerted a concentration dependent inhibition of cell cycle at G1–S transiton as evidenced by flow cytometry.
Patterning and tuning of electrical and optical properties of graphene by laser induced two-photon oxidation
2015
Graphene, being an ultrathin, durable, flexible, transparent material with superior conductivity and unusual optical properties, promises many novel applications in electronics, photonics and optoelectronics. For applications in electronics, patterning and modification of electrical properties is very desirable since pristine graphene has no band gap. Here we demonstrate a simple all-optical patterning method for graphene, based on laser induced two-photon oxidation. By tuning the intensity of irradiation and the number of pulses the level of oxidation can be controlled to high precision and, therefore, a band gap can be introduced and electrical and optical properties can be continuously t…
Ab initiolattice dynamical studies of silicon clathrate frameworks and their negative thermal expansion
2014
The thermal and lattice dynamical properties of seven silicon clathrate framework structures are investigated with ab initio density functional methods (frameworks I, II, IV, V, VII, VIII, and H). The negative thermal expansion (NTE) phenomenon is investigated by means of quasiharmonic approximation and applying it to equal time displacement correlation functions. The thermal properties of the studied clathrate frameworks, excluding the VII framework, resemble those of the crystalline silicon diamond structure. The clathrate framework VII was found to have anomalous NTE temperature range up to 300 K and it is suitable for further studies of the mechanisms of NTE. Investigation of the displa…