Serena Silvi

Light-powered autonomous and directional molecular motion of a dissipative self-assembling system

Biomolecular motors convert energy into directed motion and operate away from thermal equilibrium. The development of dynamic chemical systems that exploit dissipative (non-equilibrium) processes is a challenge in supramolecular chemistry and a premise for the realization of artificial nanoscale motors. Here, we report the relative unidirectional transit of a non-symmetric molecular axle through a macrocycle powered solely by light. The molecular machine rectifies Brownian fluctuations by energy and information ratchet mechanisms and can repeat its working cycle under photostationary conditions. The system epitomizes the conceptual and practical elements forming the basis of autonomous light-powered directed motion with a minimalist molecular design.

An Artificial Molecular Transporter

Abstract The transport of substrates is one of the main tasks of biomolecular machines in living organisms. We report a synthetic small‐molecule system designed to catch, displace, and release molecular cargo in solution under external control. The system consists of a bistable rotaxane that behaves as an acid–base controlled molecular shuttle, whose ring component bears a tether ending with a nitrile group. The latter can be coordinated to a ruthenium complex that acts as the load, and dissociated upon irradiation with visible light. The cargo loading/unloading and ring transfer/return processes are reversible and can be controlled independently. The robust coordination bond ensures that the cargo remains attached to the device while the transport takes place.

Light-powered, artificial molecular pumps: a minimalistic approach

Summary The realization of artificial molecular motors capable of converting energy into mechanical work is a fascinating challenge of nanotechnology and requires reactive systems that can operate away from chemical equilibrium. This article describes the design and construction of a simple, supramolecular ensemble in which light irradiation causes the directional transit of a macrocycle along a nonsymmetric molecular axle, thus forming the basis for the development of artificial molecular pumps.

Synthesis by ring closing metathesis and properties of an electroactive calix[6]arene [2]catenane

Abstract Tris-(N-phenylureido)-calix[6]arenes are heteroditopic non-symmetric molecular wheels that, in apolar media, bind viologen-based molecular axles in a pseudorotaxane-type fashion. Because of the precise kinetic requirements associated with the threading process, in apolar solvents, the dicationic portion of the axle enters the calixarene annulus exclusively from the upper rim. With the general aim to develop new prototypes of molecular devices and machines whose functions could be governed through a wider set of control elements, we envisaged that the unique properties of these calixarene wheels could be transferred to the synthesis of new catenanes for the construction of unidirectional rotary motors. Herein, we describe the synthesis of a tris(N-phenylureido)calix[6]arene-based catenane by applying the intramolecular ring-closing metathesis reaction for the catenation step on a pre-formed pseudorotaxane.

Dethreading of a Photoactive Azobenzene-Containing Molecular Axle from a Crown Ether Ring: A Computational Investigation

Pseudorotaxanes formed by a dibenzo[24]crown-8 ring (R) and a dialkylammonium axle bearing either two E- or two Z-azobenzene units (EE-A or ZZ-A) revealed useful for the construction of light-powered molecular machines and motors, as they provide the opportunity of photocontrolling self-assembly/disassembly processes. The potential energies profiles for the dethreading of these complexes have been investigated by adopting a combination of first-principles molecular dynamics, metadynamics and quantum-chemical geometry optimization approaches. While the dethreading of the EE-A axle is associated with a monotonic energy increase, for that of the ZZ-A axle a transition state and an intermediate structure, in which the components are still threaded together, are found. The rate determining step for the dethreading of the ZZ axle has a higher energy barrier than that of the EE axle, in agreement with the experimental kinetic data. Moreover, the results suggest that the elliptic shape of the ring cavity is important for discriminating between the E and Z terminal azobenzene during dethreading.

Making and operating molecular machines: a multidisciplinary challenge

Abstract Movement is one of the central attributes of life, and a key feature in many technological processes. While artificial motion is typically provided by macroscopic engines powered by internal combustion or electrical energy, movement in living organisms is produced by machines and motors of molecular size that typically exploit the energy of chemical fuels at ambient temperature to generate forces and ultimately execute functions. The progress in several areas of chemistry, together with an improved understanding of biomolecular machines, has led to the development of a large variety of wholly synthetic molecular machines. These systems have the potential to bring about radical innovations in several areas of technology and medicine. In this Minireview, we discuss, with the help of a few examples, the multidisciplinary aspects of research on artificial molecular machines and highlight its translational character.

Interfacing Luminescent Quantum Dots with Functional Molecules for Optical Sensing Applications

Semiconductor quantum dots possess unique size-dependent electronic properties and are of high potential interest for the construction of functional nanodevices. Photoinduced electron- and energy-transfer processes between quantum dots and surface-bound molecular species open up attractive routes to implement chemical switching of luminescence, which is at the basis of luminescence sensing. In this article, we discuss the general principles underlying the rational design of this kind of multicomponent species. Successively, we illustrate a few prominent examples, taken from the recent literature, of luminescent chemosensors constructed by attaching molecular species to the surface of quantum dots.

Calixarene Threading by Viologen-Based Axles

The purpose of this chapter is to show the achievement gained over 15 years or so on the use of tris(N-phenylureido)-calix[6]arene derivatives as components for oriented pseudorotaxanes and rotaxanes synthesis. A particular emphasis is placed on the exploitation of the chemical and structural information stored in these calix[6]arene derivatives for the unidirectional threading of viologen-based axles that yield oriented pseudorotaxanes. The thermodynamic and kinetic parameters associated with these threading processes will be reported, together with their functioning as prototype of molecular machines under the action of external energy inputs.

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle

Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle—the ‘track’ ring—endowed with two distinct recognition sites (a bipyridinium and an ammonium) for a calix[6]arene—the ‘shuttle’ ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

Dethreading of a Photoactive Azobenzene-Containing Molecular Axle from a Crown Ether Ring

Green open access version of the article:Dethreading of a Photoactive Azobenzene-Containing Molecular Axle from a Crown Ether Ring: A Computational Investigationxa0 published in:xa0ChemPhysChem 2016, 17, 1913-1919. DOI: 10.1002/cphc.201501160xa0which should be cited to refer to this work. The links below refer to: the paper at publishers site; supporting data; popular summaries of the research; two movies of the dethreading process of the two rotaxanes; high resolution figures