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Langmuir ; 34(26): 7698-7707, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29889539


We combine ambient (air) and ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) and spectroscopy (STS) investigations together with density functional theory (DFT) calculations to gain a subnanometer insight into the structure and dynamic of two-dimensional (2D) surface-supported molecular networks. The planar tetraferrocene-porphyrin molecules employed in this study undergo spontaneous self-assembly via the formation of hydrogen bonded networks at the gold substrate-solution interface. To mimic liquid phase ambient deposition conditions, film formation was accomplished in UHV by electro-spraying a solution of the molecule in chloroform onto an Au(111) substrate, thereby providing access to the full spectroscopic capabilities of STM that can be hardly attained under ambient conditions. We show that molecular assembly on Au (111) is identical in films prepared under the two different conditions, and in good agreement with the theoretical predictions. However, we observe the contrast found for a given STM bias condition to be different in ambient and UHV conditions despite the similarity of the structures, and we propose possible origins of the different imaging contrast. This approach could be valuable for the thorough characterization of surface systems that involve large molecules and are prepared mainly in ambient conditions.

Chemistry ; 24(46): 11954-11960, 2018 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-29603481


Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2-phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self-assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air-stable [Al(Salophen)] derivatives capable of undergoing spontaneous self-assembly at the graphite/solution interface forming highly-ordered nanopatterns. The new synthetic approach relies on the use of [MeAlIII (Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five-coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self-assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.

Phys Chem Chem Phys ; 20(12): 8071-8076, 2018 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-29516066


A mechanism based on the sequential absorption of two photons by the components of a redox couple has been recently proposed for catalysis of the energetically demanding reduction of aryl halides. Here, we analyze the suggested photochemical mechanism of this reaction, which employs perylenediimide (PDI) as a photocatalyst, on the basis of spectroscopic, electrochemical and electron paramagnetic resonance data. Our results indicate that the photoexcited PDI radical anion (*PDI˙-) cannot play the role of a photosensitizer in the aforementioned process. Instead, the reduction of 4'-bromoacetophenone likely involves *PDI˙- decomposition products. The extremely short lifetime of the photoexcited transient species, as *PDI˙-, is a major general limitation for photocatalytic schemes based on sequential two-photon excitation. In order to better understand the potential of such schemes, we discuss them in the context of the Z-scheme in natural photosynthesis.

Chem Rec ; 16(3): 1228-43, 2016 06.
Artigo em Inglês | MEDLINE | ID: mdl-27062088


What do quantum cellular automata (QCA), "on water" reactions, and SN 1-type organocatalytic transformations have in common? The link between these distant arguments is the practical access to useful intermediates and key products through the use of stabilized carbenium ions. Over 10 years, starting with a carbenium ion bearing a ferrocenyl group, to the 1,3-benzodithiolylium carbenium ion, our group has exploited the use of these intermediates in useful and practical synthetic transformations. In particular, we have applied the use of carbenium ions to stereoselective organocatalytic alkylation reactions, showing a possible solution for the "holy grail of organocatalysis". Examples of the use of these quite stabilized intermediates are now also considered in organometallic chemistry. On the other hand, the stable carbenium ions are also applied to tailored molecules adapted to quantum cellular automata, a new possible paradigm for computation. Carbenium ions are not a problem, they can be a/the solution!

Chem Asian J ; 9(4): 984-95, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24677815


In recent years there has been an accelerated rate of development in the field of organocatalysis, with asymmetric organocatalysis now reaching full maturity. The invention of new organocatalytic reactions and the exploration of new concepts now appear in tandem with the application of organocatalytic techniques in the synthesis of natural products and active pharmaceutical ingredients (APIs). After a "golden rush" in organocatalysis, researchers are now starting to combine different methods, thereby taking advantage of the significant benefits of synergy. Metals are used in combination with organocatalytic processes, thus reaching complexity that is found in nature, where enzymes take advantage of the presence of certain metals to increase the arsenal of organic transformations available. In this Focus review, we illustrate the possibility of a "happy marriage" between Lewis acids and organocatalytic stereoselective processes. Questions have been raised about the combination of Lewis acids and organocatalysis owing to the presence of water and/or strong bases in these processes. Some Lewis acids have been shown to be compatible with organocatalysis and concepts relating to their use will be illustrated herein. To summarize the fruitful use of Lewis acids in stereoselective organocatalytic processes, we will draw attention to the advantages and selectivity achieved using this method.

Ácidos de Lewis/química , Aminas/química , Catálise , Complexos de Coordenação/química , Reação de Cicloadição , Ouro/química , Cetonas/química , Estereoisomerismo
Chirality ; 26(10): 607-13, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-24639288


Recently, the direct substitution of allylic, benzylic, and tertiary alcohols has been achieved via SN 1-type reactions with catalytic amounts of Brønsted or Lewis acids. When a new stereogenic center is formed most of these transformations produce the desired product as a racemate, as these reactions proceed through carbenium ions. The arsenal of activation modes available in organocatalysis can be used to set up suitable reaction conditions in which chiral nucleophiles (enamine catalysis) or chiral electrophiles (iminium catalysis, chiral counterion catalysis) can easily be generated. Recently, we have used stabilized carbenium ions, directly available or obtained from the corresponding alcohols, in new organocatalytic stereoselective SN 1-type reactions. The commercially available carbenium ion benzodithiolylium tetrafluoroborate can be used for the straightforward organocatalytic stereoselective alkylation of aldehydes. In this account we will illustrate the application of this methodology in the total synthesis of natural products and the preparation of valuable starting materials.