96468-23-4Relevant academic research and scientific papers
Photoinduced Pedalo-Type Motion in an Azodicarboxamide-Based Molecular Switch
Amirjalayer, Saeed,Martinez-Cuezva, Alberto,Berna, Jose,Woutersen, Sander,Buma, Wybren Jan
, p. 1792 - 1796 (2018)
Well-defined structural changes of molecular units that can be triggered by light are crucial for the development of photoactive functional materials. Herein, we report on a novel switch that has azodicarboxamide as its photo-triggerable element. Time-resolved UV-pump/IR probe spectroscopy in combination with quantum-chemical calculations shows that the azodicarboxamide functionality, in contrast to other azo-based chromophores, does not undergo trans–cis photoisomerization. Instead, a photoinduced pedalo-type motion occurs, which because of its volume-conserving properties enables the design of functional molecular systems with controllable motion in a confined space.
Azodicarboxamides as template binding motifs for the building of hydrogen-bonded molecular shuttles
Berna, Jose,Alajarin, Mateo,Orenes, Raul-Angel
supporting information; experimental part, p. 10741 - 10747 (2010/09/16)
Azodicarboxamides (R2NCON-NCONR2) are shown to act as new templates for the assembly of unprecedented azo-functionalized hydrogen-bond-assembled [2]rotaxanes. Moreover, these binding sites can be reversibly and efficiently interconverted with their hydrazo forms through a hydrogenation-dehydrogenation strategy of the nitrogen-nitrogen bond. This novel chemically switchable control element has been implemented in stimuli-responsive molecular shuttles that work through a reversible azo/hydrazo interconversion, producing large amplitude net positional changes with a good discrimination between the binding sites of the macrocycle in both states of the shuttle. These molecular shuttles are able to operate by two different mechanisms: in a discrete mode through two reversible and independent chemical events and, importantly, in a continuous regime through a catalyzed ester bond formation reaction in which the shuttle acts as an organocatalyst. In this latter, the incorporation of both states of the shuttle into this simple chemical reaction network promotes a dynamic translocation of the macrocycle between two nitrogen and carbon-based stations of the thread allowing an energetically uphill esterification process to take place.
