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1.
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.

2.
Org Biomol Chem ; 15(32): 6753-6763, 2017 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-28766652

RESUMO

A substrate can modify its chemical features, including a change of its reactivity, as a consequence of non-covalent interactions upon inclusion within a molecular host. Since the rise of supramolecular chemistry, this phenomenon has stimulated the ingenuity of scientists to emulate the function of enzymes by designing supramolecular systems in which the energetics and selectivity of reactions can be manipulated through programmed host-guest interactions and/or steric confinement. In this paper we investigate how the engulfment of a positively charged pyridinium-based guest inside the π-rich cavity of a tris-(N-phenylureido)calix[6]arene host affects its reactivity towards a SN2 reaction. We found that the alkylation of complexed substrates leads to the formation of pseudorotaxanes and rotaxanes with faster kinetics and higher yields with respect to the standard procedures exploited so far. More importantly, the strategy described here expands the range of efficient synthetic routes for the formation of mechanically interlocked species with a strict control of the mutual orientation of their non-symmetric molecular components.

3.
Chem Commun (Camb) ; 53(45): 6172-6174, 2017 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-28530282

RESUMO

We describe the active template effect of a calix[6]arene host towards the alkylation of a complexed pyridylpyridinium guest. The acceleration of the reaction within the cavity is significant and rim-selective, enabling the efficient preparation of rotaxanes with full control of the mutual orientation of their nonsymmetric components.

4.
Chemistry ; 23(26): 6380-6390, 2017 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-28263437

RESUMO

A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond-like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments.

5.
ChemistryOpen ; 6(1): 64-72, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-28168152

RESUMO

Tris-(N-phenylureido)-calix[6]arene derivatives are heteroditopic non-symmetric molecular hosts that can form pseudorotaxane complexes with 4,4'-bipyridinium-type guests. Owing to the unique structural features and recognition properties of the calix[6]arene wheel, these systems are of interest for the design and synthesis of novel molecular devices and machines. We envisaged that the incorporation of photoactive units in the calixarene skeleton could lead to the development of systems the working modes of which can be governed and monitored by means of light-activated processes. Here, we report on the synthesis, structural characterization, and spectroscopic, photophysical, and electrochemical investigation of two calix[6]arene wheels decorated with three naphthyl groups anchored to either the upper or lower rim of the phenylureido calixarene platform. We found that the naphthyl units interact mutually and with the calixarene skeleton in a different fashion in the two compounds, which thus exhibit a markedly distinct photophysical behavior. For both hosts, the inclusion of a 4,4'-bipyridinium guest activates energy- and/or electron-transfer processes that lead to non-trivial luminescence changes.

7.
Chemphyschem ; 17(12): 1913-9, 2016 06 17.
Artigo em Inglês | MEDLINE | ID: mdl-26918775

RESUMO

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.

8.
Beilstein J Nanotechnol ; 6: 2096-104, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26665081

RESUMO

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.

9.
Nat Chem ; 7(8): 634-40, 2015 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-26201739

RESUMO

The development of solid materials that can be reversibly interconverted by light between forms with different physico-chemical properties is of great interest for separation, catalysis, optoelectronics, holography, mechanical actuation and solar energy conversion. Here, we describe a series of shape-persistent azobenzene tetramers that form porous molecular crystals in their E-configuration, the porosity of which can be tuned by changing the peripheral substituents on the molecule. Efficient E→Z photoisomerization of the azobenzene units takes place in the solid state and converts the crystals into a non-porous amorphous melt phase. Crystallinity and porosity are restored upon Z→E isomerization promoted by visible light irradiation or heating. We demonstrate that the photoisomerization enables reversible on/off switching of optical properties such as birefringence as well as the capture of CO2 from the gas phase. The linear design, structural versatility and synthetic accessibility make this new family of materials potentially interesting for technological applications.

10.
Nat Nanotechnol ; 10(1): 70-5, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25420035

RESUMO

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.

11.
Top Curr Chem ; 354: v-vii, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25392864
12.
Chemistry ; 20(34): 10737-44, 2014 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-24931834

RESUMO

Pseudorotaxanes are the simplest prototypes for the construction of molecular machines based on threaded species. Investigation on molecular motions in these model systems is a necessary action for an efficient design of working molecular machines and motors. Herein we report on photoactive pseudorotaxanes based on the interaction between bipyridinium and cucurbit[7]uril (CB7). The molecular axle is composed of a central bipyridinium unit and two azobenzene moieties at the extremities. CB7 can form two different complexes with this molecule: a [2]pseudorotaxane, in which the macrocycle shuttles fast along the length of the axle, and a [3]pseudorotaxane, in which two CB7 s are confined at the extremities of the axle. Upon trans to cis isomerization of the azobenzene moieties, the [3]pseudorotaxane is destabilized, and only one CB7 resides on the axle, surrounding the bipyridinium unit. The system was successfully inserted into the core of liposomes, and preliminary investigations confirmed that it maintains its switching ability.

13.
Chemistry ; 20(23): 7054-60, 2014 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-24825676

RESUMO

The tetrahedral, shape-persistent molecule 1(4+), containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm(-1)) and a very strong fluorescence (Φem = 40 %), compared with the monomer 2(+) (Φem = 0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1(4+) and 2(+) show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.


Assuntos
Hidrocarbonetos Aromáticos com Pontes/química , Imidazóis/química , Compostos de Piridínio/química , Técnicas Eletroquímicas , Espectroscopia de Ressonância Magnética , Oxirredução , Compostos de Piridínio/síntese química , Teoria Quântica , Água/química
14.
Chem Soc Rev ; 43(12): 4068-83, 2014 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-24590055

RESUMO

The development of multicomponent (supramolecular) systems that can perform predetermined functions under external control - i.e., molecular devices - is a challenging task in chemistry and a fascinating objective in the frame of a bottom-up approach to nanostructures. In this context light signals can be conveniently used both for supplying energy to the system and for probing its states and transformations. The aim of this tutorial review is to recall a few basic aspects of light-induced processes that can be used to "write" and "read" onto molecular and supramolecular systems. These principles are illustrated through some examples of artificial molecular devices and machines taken from our work, which provide a flavour of current research. They are molecular and supramolecular systems that operate and/or perform valuable functions by exploiting photoinduced energy- or electron-transfer processes, photoisomerization reactions, or photoinduced proton transfer. The choice of these examples was based on both their intrinsic importance for the referred topic and their educational value. In the last section of the review potential applications, limitations and future directions of the research in the field of artificial molecular devices and machines are also discussed.


Assuntos
Materiais Biomiméticos/química , Luz , Substâncias Macromoleculares/química , Dendrímeros/química , Transporte de Elétrons/efeitos da radiação , Transferência de Energia/efeitos da radiação , Isomerismo , Complexos de Proteínas Captadores de Luz/química , Complexos de Proteínas Captadores de Luz/metabolismo , Teoria Quântica
15.
Top Curr Chem ; 354: 1-34, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24531754

RESUMO

Rotaxanes and related species represent the most common implementation of the concept of artificial molecular machines, because the supramolecular nature of the interactions between the components and their interlocked architecture allow a precise control on the position and movement of the molecular units. The use of light to power artificial molecular machines is particularly valuable because it can play the dual role of "writing" and "reading" the system. Moreover, light-driven machines can operate without accumulation of waste products, and photons are the ideal inputs to enable autonomous operation mechanisms. In appropriately designed molecular machines, light can be used to control not only the stability of the system, which affects the relative position of the molecular components but also the kinetics of the mechanical processes, thereby enabling control on the direction of the movements. This step forward is necessary in order to make a leap from molecular machines to molecular motors.

16.
Org Biomol Chem ; 11(35): 5944-53, 2013 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-23903288

RESUMO

We have designed and synthesized two amphiphilic calix[6]arene derivatives, CA8 and CA18, that combine the potential to act as wheel components for pseudorotaxane structures with the self-assembly features typical of surfactant molecules in aqueous solution. Their endo-cavity recognition and selfaggregation properties were compared with those of a non-amphiphilic analogue, C8. TEM, DLS, and fluorescence experiments show that in water the amphiphilic calixarenes form vesicle- and micelle-like aggregates. The size, nature and properties of such aggregates depend on the length of the alkyl chain anchored at the lower rim of the calix[6]arene skeleton, as well as on the inclusion of a molecular guest into the wheel. Specifically, the release of a fluorescent guest entrapped inside the CA8 vesicles is accelerated in the presence of dioctylviologen axles that can pierce the calixarene cavity.


Assuntos
Calixarenos/química , Fenóis/química , Tensoativos/química , Água/química , Calixarenos/síntese química , Micelas , Fenóis/síntese química , Tensoativos/síntese química
17.
J Am Chem Soc ; 135(26): 9924-30, 2013 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-23751139

RESUMO

We have investigated the self-assembly of pseudorotaxanes composed of viologen-type axle and calix[6]arene wheel components. The distinctive feature of this system is that both components are structurally nonsymmetric; hence, their self-assembly can follow four distinct pathways and eventually give rise to two different orientational pseudorotaxane isomers. We found that the alkyl side chains of the viologen recognition site on the molecular axle act as strict kinetic control elements in the self-assembly, thereby dictating which side of the axle pierces the calixarene cavity. Specifically, nonsymmetric axles with alkyl side chains of different length thread the wheel with the shorter chain. Such a selectivity, in combination with the face-selective threading of viologen-type axles afforded by tris(N-phenylureido)calix[6]arenes, enables a strict directional control of the self-assembly process for both the face of the wheel and the side of the axle. This kinetic selectivity allows both intramolecular self-sorting between two different side chains in a nonsymmetric axle and intermolecolar self-sorting among symmetric axles with alkyl substituents of different length.


Assuntos
Calixarenos/química , Fenóis/química , Estrutura Molecular
18.
Chemistry ; 19(9): 3131-8, 2013 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-23325701

RESUMO

The photophysical properties of a multicomponent [1]rotaxane bearing a ß-cyclodextrin ring covalently connected to an axle comprising an azobenzene photoisomerisable moiety and a naphthalimide-type fluorescent stopper are investigated by a combined experimental and computational study. The absorption and fluorescence spectra, and particularly the induced circular dichroism (ICD) signal, are determined. The latter shows a sign relation that cannot be rationalised in terms of the simple general rules commonly employed to analyse the ICD spectra of achiral guests encircled by chiral hosts. To assist the interpretation of experimental results, DFT and time-dependent (TD) DFT calculations are performed to explore the availability of low-energy conformations and to model their spectroscopic response. Molecular dynamics simulations performed in water show the interconversion of a number of conformers, the contribution of which to the ICD signal is in agreement with the observation.

19.
Chemistry ; 18(52): 16911-21, 2012 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-23136090

RESUMO

We designed and synthesized the three molecular tweezers 1 a-c(4+) containing an electron acceptor 4,4'-bipyridinium (BPY(2+)) unit in each of the two arms and an (R)-2,2'-dioxy-1,1'-binaphthyl (BIN) unit that plays the role of chiral centre and the hinge of the structure. Each BPY(2+) unit is connected to the BIN hinge by an alkyl chain formed by two- (1 a(4+)), four- (1 b(4+)), or six-CH(2) (1 c(4+)) groups. The behavior of 1 a-c(4+) upon chemical or photochemical reduction in the absence and in the presence of cucurbit[8]uril (CB[8]) or cucurbit[7]uril (CB[7]) as macrocyclic hosts for the bipyridinium units has been studied in aqueous solution. A detailed analysis of the UV/Vis absorption and circular dichroism (CD) spectra shows that the helicity of the BIN unit can be reversibly modulated by reduction of the BPY(2+) units, or by association with cucurbiturils. Upon reduction of 1 a-c(4+) compounds, the formed BPY(+·) units undergo intramolecular dimerization with a concomitant change in the BIN dihedral angle, which depends on the length of the alkyl spacers. The alkyl linkers also play an important role in association to cucurbiturils. Compound 1 a(4+), because of its short carbon chain, associates to the bulky CB[8] in a 1:1 ratio, whereas in the case of the smaller host compound CB[7] a 1:2 complex is obtained. Compounds 1 b(4+) and 1 c(4+), which have longer linkers, associate to two cucurbiturils regardless of their sizes. In all cases, association with CB[8] causes an increase of the BIN dihedral angle, whereas the formation of CB[7] complexes causes an angle decrease. Reduction of the CB[8] complexes results in an enhancement of the BPY(+·) dimerization with respect to free 1 a-c(4+) and causes a noticeable decrease of the BIN dihedral angle, because the BPY(+·) units of the two arms have to enter into the same macrocycle. The dimer formation in the CB[8] complexes characterized by a 1:2 ratio implies the release of one macrocycle showing that the binding stoichiometry of these host-guest complexes can be switched from 1:2 to 1:1 by changing the redox state of the guest. When the reduction is performed on the CB[7] complexes, dimer formation is totally inhibited, as expected because the CB[7] cavity cannot host two BPY(+·) units.


Assuntos
Hidrocarbonetos Aromáticos com Pontes/química , Imidazóis/química , Substâncias Macromoleculares/síntese química , Naftalenos/química , Paraquat/química , Absorção , Dicroísmo Circular , Técnicas Eletroquímicas , Substâncias Macromoleculares/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Oxirredução , Processos Fotoquímicos , Estereoisomerismo
20.
Chemistry ; 18(50): 16203-13, 2012 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-23090856

RESUMO

The development of a pseudorotaxane motif capable of performing unidirectional threading and dethreading processes under control of external stimuli is particularly important for the construction of processive linear motors based on rotaxanes and, at least in principle, it discloses the possibility to access to rotary motors based on catenanes. Here, we report a strategy to obtain the solvent-controlled unidirectional transit of a molecular axle through a molecular wheel. It is based on the use of appropriately designed molecular components, the essential feature of which is their non-symmetric structure. Specifically they are an axle containing a central electron-acceptor 4,4'-bipyridinium core functionalized with a hexanol chain at one side, and a stilbene unit connected through a C6 chain at the other side, and a heteroditopic tris(phenylureido)-calix[6]arene wheel. In apolar solvents the axle threads into the wheel from its upper rim and with the end carrying the OH group, giving an oriented pseudorotaxane structure. After a stoppering reaction, which replaces the small hydroxy group with a bulky diphenylacetyl moiety, and replacement of the apolar solvent with a polar one, dethreading occurs through the slippage of the stilbene unit from the lower rim of the wheel, that is, in the same direction of the threading process. The essential role played by the stilbene unit to achieve the unidirectional transit of the axle through the wheel, and to tune the dethreading rate by light is also demonstrated.


Assuntos
Rotaxanos/química , Solventes/química , Estilbenos/química , Luz , Modelos Moleculares , Estrutura Molecular
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