The nonheme iron(IV)-oxido complex trans-N3-[(L1)FeIV=O(Cl)]+, where L1 is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, has an S = 1 electronic ground state and is the most reactive nonheme iron...
You can′t separate this couple: One of the azo‐substituted tripycenes synthesized in this work is highlighted in front of its UV‐Vis absorption spectrum. Even though the azobenzenes are separated by a sp3 center, they experience excitonic coupling, as illustrated by the lightning. More information can be found in the Research Article by H. A. Wegner and co‐workers (DOI: 10.1002/chem.202200972). Design by Felix Bernt.
Herein, we report a series of azobenzene-substituted triptycenes. In their design, these switching units were placed in close proximity, but electronically separated by a sp 3 center. The azobenzene switches were prepared by Baeyer-Mills coupling as key step. The isomerization behavior was investigated by 1 H NMR spectroscopy, UV/Vis spectroscopy, and HPLC. It was shown that all azobenzene moieties are efficiently switchable. Despite the geometric decoupling of the chromophores, computational studies revealed exci-tonic coupling effects between the individual azobenzene units depending on the connectivity pattern due to the different transition dipole moments of the π!π* excitations. Transition probabilities for those excitations are slightly altered, which is also revealed in their absorption spectra. These insights provide new design parameters for combining multiple photoswitches in one molecule, which have high potential as energy or information storage systems, or, among others, in molecular machines and supramolecular chemistry.
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