Cumulene rotaxanes: stabilization and study of [9]cumulenes.
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.
Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski.
Michael
M
Franz
Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski.
Johanna A
JA
Januszewski
Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski.
Dominik
D
Wendinger
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (Germany).
Christian
C
Neiss
Department of Chemistry, University of Oxford (UK).
Levon D
LD
Movsisyan
Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski.
Frank
F
Hampel
Department of Chemistry, University of Oxford (UK).
Harry L
HL
Anderson
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (Germany).
Andreas
A
Görling
Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski. rik.tykwinski@fau.de.
Rik R
RR
Tykwinski
carbynes; cumulenes; dispersion forces; electrochemistry; rotaxanes