The synthesis and properties of a new polycyclic aromatic hydrocarbon containing eight annulated rings and based on the anthanthrene core is described. An unexpected, nucleophile-dependent Michael addition to a dibenzanthanthrene-1,7-dione is found, giving a product with three triisopropylsilylacetylene units and a remarkable solid-state structure (as determined by X-ray crystallography).

The synthesis of structurally relevant compounds that model the chemical behavior and supramolecular aggregation of the asphaltenes, the most polar and metal-rich fraction of heavy petroleum, has been extended to include fusions of important petroleum biomarkers. The synthetic protocol features a multicomponent reaction to form a dyad composed of a fused steroidal naphthoquinoline, followed by a pyrrole cyclocondensation reaction to incorporate the dyad into a chiral triad containing a Ni^II-porphyrin substituent. This synthetic protocol has been used to prepare large molecules that represent both “continental” and “archipelago” models of asphaltene composition. The steroid–naphthoquinoline–porphyrin triads have been studied by UV/Vis and circular dichroism (CD) spectroscopies, and the results suggest that the naphthoquinoline core, a tetrahydro[4]helicene, adopts a helical conformation, producing a CD signal electronically related to the characteristic Soret absorption band of the porphyrin subunit. Finally, supramolecular aspects of asphaltene aggregation have been examined on a molecular level through analysis of axial coordination of pyridine to the Ni-porphyrin. The relative affinity of pyridine for binding to the Ni center of the porphyrin is evaluated by comparing binding propensities in a series of sterically differentiated substituted porphyrins.

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO_x) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO_x NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO₂ NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

Die Stabilisierung langer [n]Cumulene wird üblicherweise erreicht, indem sterisch anspruchsvolle “Schutzgruppen” an den Enden angebracht werden, welche die reaktive Kohlenstoffkette abschirmen. Wir stellen hier eine alternative Strategie vor: Stabilisierung durch Einfädeln der sp-Kohlenstoffkette in einen Phenanthrolin-basierten Makrocyclus. Dies führt zu stabilen [9]Cumulen-Rotaxanen, die es uns erlaubten, die Eigenschaften von [n]Cumulenen in Abhängigkeit von ihrer Länge in bis dato unerreichtem Detail zu untersuchen. Dabei nutzten wir quantitative UV/Vis-Spektroskopie, Cyclovoltammetrie und dynamische Differenzkalorimetrie. Die experimentellen Befunde können durch DFT-Rechnungen reproduziert und verstanden werden.

The stabilization of long [n]cumulenes has traditionally been achieved by placing sterically bulky “protecting groups” at the termini, which shield the reactive carbon chain from unwanted reactions. Herein, we present an alternative strategy: stabilization through threading the sp-hybridized carbon chain through a phenanthroline-based macrocycle. The result is stable [9]cumulene rotaxanes that enable the study of properties as a function of length for [n]cumulenes in unprecedented detail, including by quantitative UV/Vis spectroscopy, cyclic voltammetry, and differential scanning calorimetry. The experimental results are supported by DFT calculations.

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO_x) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO_x NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO₂ NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

For the last 60+ years, the synthesis and study of cumulenes and polyynes have been the focus of a small, but dedicated, group of researchers. Many of the remarkable electronic, optical, and structural properties of cumulenes and polyynes had already been identified in the earliest reports. The molecular lengths achievable by the initial syntheses were, unfortunately, somewhat limited by synthetic methods available. For the past 15 years, we have worked toward expanding on the synthesis of cumulenes and polyynes through the development of new methods and stabilization motifs. As new compounds have become available, homologous series of cumulenes and polyynes have then been examined as a function of molecular length. While we are not yet there, we would like to eventually provide a general description of the sp-carbon allotrope carbyne, and this account presents some of our efforts toward this goal.

Conformational changes in the conjugated backbone of poly- and oligodiacetylenes (PDAs and ODAs) play an important role in determining the electronic properties of these compounds. At the same time, conformational changes can also result in a folded structure that shows helical chirality. Using D-camphor as a chiral building block, we have designed a high-yielding, iterative synthesis of monodisperse, optically pure cis-oligodiacetylenes (ODAs). cis-ODAs up to the tridecamer have been formed, which is the longest monodisperse cis-ODA reported to date. UV/Vis spectroscopy suggests a large effective conjugation length in THF, likely the result of a linear, planar conformation in this solvent. High-resolution STM/AFM measurements of the nonamer cast from THF onto HOPG show a linear structure. In iPrOH, circular dichroism (CD) spectra suggest the formation of chiral aggregates for ODAs with at least nine D-camphor units, based on a strong CD response.

The use of cumulenes in synthetic transformations offers the possibility to form structurally interesting and potentially useful conjugated molecules. The cycloaddition reaction of a tetraaryl[5]cumulene with the electron-deficient olefin tetracyanoethylene affords unusual products, including functionalized dendralenes and alkylidene cyclobutanes, as well as a symmetric [4]radialene that shows unique solvatochromism, with λ_max values approaching the near-IR region. These carbon-rich products have been investigated spectroscopically and by X-ray crystallographic analysis (five structures). The cycloaddition reaction sequence has also been explored by mechanistic and theoretical studies. The obtained results clearly demonstrate the potential of [5]cumulenes to serve as precursors for unprecedented conjugated structures.

Konformationsänderungen des konjugierten Rückgrats von Poly- und Oligodiacetylenen (PDAs und ODAs) spielen bei der Bestimmung der elektronischen Eigenschaften dieser Verbindungen eine wichtige Rolle. Gleichzeitig können Konformationsänderungen auch zu gefalteten Strukturen führen, die helikale Chiralität aufweisen. Durch Verwendung von D-Campher als chiraler Baustein konnten monodisperse, optisch reine cis-Oligodiacetylene (ODAs) in hoher Ausbeute erhalten werden. cis-ODAs bis zur Länge des Tridecamers wurden synthetisiert, was dem längsten bisher bekannten monodispersen cis-ODA entspricht. UV/Vis-Spektroskopie deutet auf eine hohe effektive Konjugationslänge in THF hin, vermutlich aufgrund einer linearen planaren Konformation in diesem Lösungsmittel. Hochauflösende STM/AFM-Messungen von Filmen des Nonamers, abgeschieden aus einer THF-Lösung auf HOPG, zeigen eine lineare Struktur. In iPrOH gemessene Zirkulardichroismus(CD)-Spektren legen die Bildung chiraler Aggregate der ODAs mit mindestens neun D-Campher-Einheiten nahe. Die CD-Resonanz ist konzentrations- und temperaturabhängig.

Die Verwendung von Cumulenen in chemischen Umsetzungen eröffnet die Möglichkeit, strukturell interessante und potenziell nützliche konjugierte Moleküle herzustellen. Die Cycloadditionsreaktion eines Tetraaryl[5]cumulens mit dem elektronenarmen Olefin Tetracyanoethylen liefert außergewöhnliche Produkte, darunter funktionalisierte Dendralene und Alkylidencyclobutane sowie ein symmetrisches [4]Radialen mit einer besonderen Solvatochromie, dessen λ_max-Werte sich dem Nah-IR-Bereich nähern. Diese kohlenstoffreichen Produkte wurden spektroskopisch und röntgenographisch (für fünf der Verbindungen) untersucht. Auch ein möglicher Ablauf der Cycloadditionsreaktion wurde mithilfe mechanistischer und theoretischer Untersuchungen ermittelt. Die Ergebnisse unterstreichen das Potenzial von [5]Cumulenen, als Vorstufen für neuartige konjugierte Systeme zu dienen.

Versatile, iterative synthetic protocols to form expanded [n]radialenes have been developed (n=3 and 4), which allow for a variety of groups to be placed around the periphery of the macrocyclic framework. The successful use of the Sonogashira cross-coupling reaction to complete the final ring closure demonstrates the ability of this reaction to tolerate significant ring strain while producing moderate to excellent product yields. The resulting radialenes show good stability under normal laboratory conditions in spite of their strained, cyclic structures. The physical and electronic characteristics of the macrocycles have been documented by UV-visible spectroscopy, electrochemical methods, and X-ray crystallography (four derivatives), and these studies provide insight into the properties of these compounds as a function of pendent substitution in terms of conjugation and donor/acceptor functionalization.