Darstellung, Konformationen und chiroptische Eigenschaften der zehngliedrigen planarchiralen Naphthalinophane 4, 5 (heterocyclisch) und 6 -8 (carbocyclisch) werden beschrieben. Die Enantiomereii von 4 und 6 werden mitteldruckchromatographisch an (-)-a-(2,4,5,7-Tetranitro-9-fluoreny1idenaminooxy)propionsaure (TAPA) angereichert und polarimetrisch und circulardichrographisch untersucht. 'H-NMR-Spektren belegen die anti-Konformationen fur 4 und 6 -8, wlhrend sie fur 5 eine konformativ flexible syn-Konformation nahelegen. New Planarchiral[2.2]PhanesSyntheses, Structures, and Chiroptical PropertiesPreparation, conformations and chiroptical properties of the ten-membered, planarchiral naphthalinophanes 4, 5 (heterocyclic) and 6 -8 (carbocyclic) are described. 4 and 6 are chromalographically enriched using (-)-a-(2,4,5,7-tetranitro-9-fluorenylideneaminooxy)propionic acid (TAPA), Optical rotations and circular dichroisms of 4 and 6 are determined. The anticonformations are ascertained for 4 and 6 -8 by 'H NMR spectroscopy, whereas a conformational flexible syn conformation is supposed for 5 . Geeignete carbo-1) and h e t e r o c y~l i s c h e 2~~

No abstract

We have synthesized a dendrimer (1) consisting of a 1,4,8,11-tetraazacyclotetradecane (cyclam) core, appended with four benzyl substituents that carry, in the 3- and 5-positions, a dansyl amide derivative (of type 2), in which the amide hydrogen is replaced by a benzyl unit that carries an oligoethylene glycol chain in the 3- and 5-positions. All together, the dendrimer contains 16 potentially luminescent moieties (eight dansyl- and eight dimethoxybenzene-type units) and three distinct types of multivalent sites that, in principle, can be protonated or coordinated to metal ions (the cyclam nitrogen atoms, the amine moieties of the eight dansyl units, and the 16 oligoethylene glycol chains). We have studied the absorption and luminescence properties of 1, 2, and 3 in acetonitrile and the changes taking place upon titration with acid and a variety of divalent (Co2+, Ni2+, Cu2+, Zn2+), and trivalent (Nd3+, Eu3+, Gd3+) metal ions as triflate and/or nitrate salts. The results obtained show that: 1) double protonation of the cyclam ring takes place before protonation of the dansyl units; 2) the oligoethylene glycol chains do not interfere with protonation of the cyclam core and the dansyl units in the ground state, but affect the luminescence of the protonated dansyl units; 3) the first equivalent of metal ion is coordinated by the cyclam core; 4) the interaction of the resulting cyclam complex with the appended dansyl units depends on the nature of the metal ion; 5) coordination of metal ions by the dansyl units follows at high metal-ion concentrations; 6) the effect of the metal ion depends on the nature of the counterion. This example demonstrates that dendrimers may exhibit complete functionality resulting from the integration of the specific properties of their component units.

SummaryA series of dithienophenazines with different lengths of the oligomeric thiophene units (quaterthiophenes and sexithiophenes) was synthesized. The thiophene and phenazine units act as electron donors and acceptors, respectively, resulting in characteristic absorption spectra. The optical spectra were calculated using time-dependent density functional theory at the B3LYP/TZVP level and verify the experimental data. Adsorption of the dithienophenazines on highly ordered pyrolytic graphite (HOPG) was investigated by scanning tunneling microscopy, showing that one of the compounds forms highly organized self-assembled monolayers.

No abstract