Influence of Rotator Design on the Speed of Self-Assembled
Four-Component Nanorotors: Coordinative Versus Dispersive Interactions
Pronay Kumar Biswas
Suchismita Saha
Yerramsetti Nanaji
Anup Rana
Michael Schmittel
10.1021/acs.inorgchem.7b00740.s001
https://acs.figshare.com/articles/journal_contribution/Influence_of_Rotator_Design_on_the_Speed_of_Self-Assembled_Four-Component_Nanorotors_Coordinative_Versus_Dispersive_Interactions/5011985
Four-component nanorotors
are prepared by the self-assembly of stator [Cu<sub>4</sub>(<b>4</b>)]<sup>4+</sup> with its four copper(I)-loaded phenanthroline
stations and various rotators carrying one, two, or three pyridine
terminals. The fourth component, 1,4-diazabicyclo[2.2.2]octane, serves
as
a connecting axle between rotator and stator. Capitalizing on the
heteroleptic pyridyl and phenanthroline metal complexes concept, the
rotator’s pyridine terminals are connected to the copper(I)-loaded
phenanthroline stations (N<sub>py</sub> → [Cu(phen)]<sup>+</sup>) in the STOP state and disconnected in the transition state of rotation.
As the barrier of the thermally activated rotation, measured by variable-temperature <sup>1</sup>H NMR, is mainly governed by attractive forces between stator
stations and rotator terminals, it increases along the series <i>E</i><sub>a</sub> (monopyridine rotator) < <i>E</i><sub>a</sub> (dipyridine rotator) < <i>E</i><sub>a</sub> (tripyridine rotator). However, there are even distinct differences
in rate between rotors with equal number of rotator terminals. The
change from the 5,10-dipyridyl (<i>cis</i>) to 5,15-dipyridyl
(<i>trans</i>) zinc porphyrin rotator enhances the rotational
frequency by almost 1000-fold. Density functional theory computational
results suggest that not only coordinative N<sub>py</sub> →
[Cu(phen)]<sup>+</sup> interactions but also dispersive attraction
influence the barrier of rotation.
2017-05-17 00:00:00
zinc porphyrin rotator
Self-Assembled Four-Component Nanorotors
phenanthroline metal complexes concept
dispersive attraction influence
Coordinative Versus Dispersive Interactions Four-component nanorotors
variable-temperature 1 H NMR
rotator terminals