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1.
Artigo em Inglês | MEDLINE | ID: mdl-32396687

RESUMO

The general principles guiding the design of molecular machines based on interlocked structures are well known. Nonetheless, the identification of suitable molecular components for a precise tuning of the energetic parameters that determine the mechanical link is still challenging. Indeed, what are the reasons of the "all-or-nothing" effect, which turns a molecular "speed-bump" into a stopper in pseudorotaxane-based architectures? Here we investigate the threading and dethreading processes for a representative class of molecular components, based on symmetric dibenzylammonium axles and dibenzo[24]crown-8 ether, with a joint experimental-computational strategy. From the analysis of quantitative data and an atomistic insight, we derive simple rules correlating the kinetic behaviour with the substitution pattern, and provide rational guidelines for the design of modules to be integrated in molecular switches and motors with sophisticated dynamic features.

2.
Chem Commun (Camb) ; 55(84): 12595-12602, 2019 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-31580358

RESUMO

Molecular machines powered by light are appropriately designed multicomponent molecular structures that exploit photochemical processes to perform controlled movements. We discuss the advances in the design and investigation of light-driven molecular machines by presenting a selection of examples from the past decade.

3.
J Am Chem Soc ; 141(23): 9129-9133, 2019 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-31129959

RESUMO

We exploit a reversible acid-base triggered molecular shuttling process to switch an appropriately designed rotaxane between prochiral and mechanically planar chiral forms. The mechanically planar enantiomers and their interconversion, arising from ring shuttling, have been characterized by NMR spectroscopy. We also show that the supramolecular interaction of the positively charged rotaxane with optically active anions causes an imbalance in the population of the two enantiomeric coconformations. This result represents an unprecedented example of chiral molecular recognition and can disclose innovative approaches to enantioselective sensing and catalysis.

4.
Photochem Photobiol Sci ; 18(9): 2281-2286, 2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-30968923

RESUMO

Shape-persistent azobenzene tetramers functionalized at the periphery with alkyloxy substituents of different lengths have been synthesized and their photochemical behaviour has been investigated. Efficient E→Z photoisomerization of the azobenzene units takes place both in solution and in the solid state, a highly desirable yet uncommon property for azobenzene-type photochromic compounds. The solid state E→Z photoisomerization is accompanied by an isothermal crystal-amorphous phase transformation; successively, anisotropic crystals can be grown upon promoting the Z→E isomerization by thermal annealing of the irradiated samples. These results validate the strategy of engineering multiphotochromic architectures with a rigid star-shaped geometry to preserve the solution-based photoreactivity also in the solid state. The observed unexpected photoinduced alignment makes these materials potentially attractive for the development of photo-patternable and photo-responsive surfaces.

5.
Photochem Photobiol Sci ; 17(6): 734-740, 2018 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-29722402

RESUMO

Among the plethora of photochromes reported so far, azobenzene has been proven to be the most suitable photoswitch for molecular systems and materials, due to its highly efficient and clean E-Z photoisomerization. Here we report two ammonium-based molecular axles bearing one or two p-cyanoazobenzene units at the extremities, able to form pseudorotaxanes with a crown ether macrocycle. The photochemistry of these compounds was studied in the isolated forms and in the pseudorotaxanes, showing that the functionalization speeds up the threading process without affecting the photochemical properties of the system. These results suggest that the investigated pseudorotaxanes can form the basis of new prototypes of artificial molecular-level pumps.

6.
ChemistryOpen ; 7(2): 169-179, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-29435402

RESUMO

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.

7.
Eur J Inorg Chem ; 2018(42): 4589-4603, 2018 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-31007574

RESUMO

Molecular and supramolecular-based systems and materials that can perform predetermined functions in response to light stimulation have been extensively studied in the past three decades. Their investigation continues to be a highly stimulating topic of chemical research, not only because of the inherent scientific value related to a bottom-up approach to functional nanostructures, but also for the prospective applications in diverse fields of technology and medicine. Light is an important tool in this context, as it can be conveniently used both for supplying energy to the system and for probing its states and transformations. In this microreview we recall some basic aspects of light-induced processes in (supra)molecular assemblies, and discuss their exploitation to implement novel functionalities with nanostructured devices, machines and materials. To this aim we illustrate a few examples from our own recent work, which are meant to illustrate the trends of current research in the field.

8.
Chemistry ; 22(3): 1030-6, 2016 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-26637108

RESUMO

A versatile and simple methodology for the creation of mixed monolayers on glassy carbon (GC) surfaces was developed, using an osmium-bipyridyl complex and anthraquinone as model redox probes. The work consisted in the electrochemical grafting on GC of a mixture of mono-protected diamine linkers in varying ratios which, after attachment to the surface, allowed orthogonal deprotection. After optimisation of the deprotection conditions, it was possible to remove one of the protecting groups selectively, couple a suitable osmium complex and cap the residual free amines. The removal of the second protecting group allowed the coupling of anthraquinone. The characterisation of the resulting surfaces by cyclic voltammetry showed the variation of the surface coverage of the two redox centres in relation to the initial ratio of the linking amine in solution.

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