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1.
Langmuir ; 34(26): 7698-7707, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29889539

RESUMO

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.

2.
Chemistry ; 24(46): 11954-11960, 2018 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-29603481

RESUMO

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.

3.
J Phys Chem Lett ; 8(14): 3347-3355, 2017 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-28678507

RESUMO

Electrochemically exfoliated graphene (EEG) possesses optical and electronic properties that are markedly different from those of the more explored graphene oxide in both its pristine and reduced forms. EEG also holds a unique advantage compared to other graphenes produced by exfoliation in liquid media: it can be obtained in large quantities in a short time. However, an in-depth understanding of the structure-properties relationship of this material is still lacking. In this work, we report physicochemical characterization of EEG combined with an investigation of the electronic properties of this material carried out both at the single flake level and on the films. Additionally, we use for the first time microwave irradiation to reduce the EEG and demonstrate that the oxygen functionalities are not the bottleneck for charge transport in EEG, which is rather hindered by the presence of structural defects within the basal plane.

4.
ACS Nano ; 10(12): 10768-10777, 2016 12 27.
Artigo em Inglês | MEDLINE | ID: mdl-28024344

RESUMO

Ultrasound-induced liquid-phase exfoliation (UILPE) is an established method to produce single- (SLG) and few-layer (FLG) graphene nanosheets starting from graphite as a precursor. In this paper we investigate the effect of the ultrasonication power in the UILPE process carried out in either N-methyl-2-pyrrolidone (NMP) or ortho-dichlorobenzene (o-DCB). Our experimental results reveal that while the SLGs/FLGs concentration of the NMP dispersions is independent of the power of the ultrasonic bath during the UILPE process, in o-DCB it decreases as the ultrasonication power increases. Moreover, the ultrasonication power has a strong influence on the lateral size of the exfoliated SLGs/FLGs nanosheets in o-DCB. In particular, when UILPE is carried out at ∼600 W, we obtain dispersions composed of graphene nanosheets with a lateral size of 180 nm, whereas at higher power (∼1000 W) we produce graphene nanodots (GNDs) with an average diameter of ∼17 nm. The latter nanostructures exhibit a strong and almost excitation-independent photoluminescence emission in the UV/deep-blue region of the electromagnetic spectrum arising from the GNDs' intrinsic states and a less intense (and strongly excitation wavelength dependent) emission in the green/red region attributed to defect states. Notably, we also observe visible emission with near-infrared excitation at 850 and 900 nm, a fingerprint of the presence of up-conversion processes. Overall, our results highlight the crucial importance of the solvent choice for the UILPE process, which under controlled experimental conditions allows the fine-tuning of the morphological properties, such as lateral size and thickness, of the graphene nanosheets toward the realization of luminescent GNDs.

5.
Chem Commun (Camb) ; 52(74): 11163-6, 2016 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-27561126

RESUMO

Polygonal supramolecular architectures of a Pt(ii) complex including trimers, tetramers, pentamers and hexamers were self-assembled via hydrogen bonding between isocytosine moieties; their structure at the solid/liquid interface was unravelled by in situ scanning tunneling microscopy imaging. Density functional theory calculations provided in-depth insight into the thermodynamics of their formation by exploring the different energy contributions attributed to the molecular self-assembly and adsorption processes.

6.
Small ; 12(1): 83-95, 2016 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-26488679

RESUMO

The self-assembly of small organic molecules interacting via non-covalent forces is a viable approach towards the construction of highly ordered nanostructured materials. Among various molecular components, natural and unnatural nucleobases can undergo non-covalent self-association to form supramolecular architectures with ad hoc structural motifs. Such structures, when decorated with appropriate electrically/optically active units, can be used as scaffolds to locate such units in pre-determined positions in 2D on a surface, thereby paving the way towards a wide range of applications, e.g., in optoelectronics. This review discusses some of the basic concepts of the supramolecular engineering of natural and unnatural nucleobases and derivatives thereof as well as self-assembly processes on conductive solid substrates, as investigated by scanning tunnelling microscopy in ultra-high vacuum and at the solid/liquid interface. By unravelling the structure and dynamics of these self-assembled architectures with a sub-nanometer resolution, a greater control over the formation of increasingly sophisticated functional systems is achieved. The ability to understand and predict how nucleobases interact, both among themselves as well as with other molecules, is extremely important, since it provides access to ever more complex DNA- and RNA-based nanostructures and nanomaterials as key components in nanomechanical devices.


Assuntos
Nucleotídeos/química , Guanina/química , Ligação de Hidrogênio , Microscopia de Tunelamento , Propriedades de Superfície
7.
Small ; 12(3): 343-50, 2016 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-26596683

RESUMO

A joint experimental and computational study is reported on the concentration-dependant self-assembly of a flat C3 -symmetric molecule on a graphite surface. As a model system a tripodal molecule, 1,3,5-tris(pyridin-3-ylethynyl)benzene, has been chosen, which can adopt either C3h or Cs symmetry when planar, as a result of pyridyl rotation along the alkynyl spacers. Density functional theory (DFT) simulations of 2D nanopatterns with different surface coverage reveal that the molecule can generate different types of self-assembled motifs. The stability of fourteen 2D patterns and the influence of concentration are analyzed. It is found that ordered, densely packed monolayers and 2D porous networks are obtained at high and low concentrations, respectively. A concentration-dependent scanning tunneling microscopy (STM) investigation of this molecular self-assembly system at a solution/graphite interface reveals four supramolecular motifs, which are in perfect agreement with those predicted by simulations. Therefore, this DFT method represents a key step forward toward the atomically precise prediction of molecular self-assembly on surfaces and at interfaces.

8.
J Am Chem Soc ; 137(26): 8450-9, 2015 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-26076095

RESUMO

The self-assembly of multiple molecular components into complex supramolecular architectures is ubiquitous in nature and constitutes one of the most powerful strategies to fabricate multifunctional nanomaterials making use of the bottom-up approach. When spatial confinement in two dimensions on a solid substrate is employed, this approach can be exploited to generate periodically ordered structures from suitably designed molecular tectons. In this study we demonstrate that physisorbed directional periodic arrays of monometallic or heterobimetallic coordination polymers can be generated on a highly oriented pyrolitic graphite surface by combinations of a suitably designed directional organic tecton or metallatecton based on a porphyrin or nickel(II) metalloporphyrin backbone bearing both a pyridyl unit and a terpyridyl unit acting as coordinating sites for CoCl2. The periodic architectures were visualized at the solid/liquid interface with a submolecular resolution by scanning tunneling microscopy and corroborated by combined density functional and time-dependent density functional theory calculations. The capacity to nanopattern the surface for the first time with two distinct metallic centers exhibiting different electronic and optical properties is a key step toward the bottom-up construction of robust multicomponent and, thus, multifunctional molecular nanostructures and nanodevices.

9.
Chem Commun (Camb) ; 51(58): 11677-80, 2015 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-26102583

RESUMO

We report on the synthesis and self-assembly of three novel lipophilic guanosine derivatives exposing a ferrocene moiety in the C(5') position of the sugar unit. Their self-association in solution, and at the solid/liquid interface, can be tuned by varying the size and nature of the C(8)-substituent, leading to the generation of either G-ribbons, lamellar G-dimer based arrays or the G4 cation-free architectures.


Assuntos
Compostos Ferrosos/química , Guanosina/química , Ligação de Hidrogênio , Metalocenos
10.
Angew Chem Int Ed Engl ; 54(16): 4865-9, 2015 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-25728405

RESUMO

Here we report for the first time a submolecularly resolved scanning tunneling microscopy (STM) study at the solid/liquid interface of the in situ reversible interconversion between two isomers of a diarylethene photoswitch, that is, open and closed form, self-assembled on a graphite surface. Prolonged irradiation with UV light led to the in situ irreversible formation of another isomer as by-product of the reaction, which due to its preferential physisorption accumulates at the surface. By making use of a simple yet powerful thermodynamic model we provide a quantitative description for the observed surface-induced selection of one isomeric form.

11.
Nat Chem ; 6(11): 1017-23, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-25343608

RESUMO

Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.

12.
Chem Commun (Camb) ; 50(82): 12250-3, 2014 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-24969396

RESUMO

The nanostructuring of the graphite surface with 2D coordination networks, based on a combination of an acentric porphyrin tecton bearing two divergently oriented monodentate pyridyl units and a CoCl2 metallatecton, behaving as a four connecting node, was achieved at the solid-liquid interface and characterized by scanning tunnelling microscopy.

14.
Nanoscale ; 6(5): 2660-8, 2014 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-24441565

RESUMO

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.

15.
ACS Nano ; 7(9): 8190-8, 2013 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-23987501

RESUMO

We provide insight into surface-catalyzed dehalogenative polymerization, analyzing the organometallic intermediate and its evolution into planar polymeric structures. A combined study using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and first-principles calculations unveils the structural conformation of substrate-bound phenylene intermediates generated from 1,4-dibromobenzene precursors on Cu(110), showing the stabilizing role of the halogen. The appearance of covalently bonded conjugated structures is followed in real time by fast-XPS measurements (with an acquisition time of 2 s per spectrum and heating rate of 2 K/s), showing that the detaching of phenylene units from the copper substrate and subsequent polymerization occur upon annealing above 460 ± 10 K.

16.
Chem Asian J ; 8(8): 1813-7, 2013 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-23757211

RESUMO

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)-O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)-O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule-substrate interactions on Cu(110)-O(2×1) as opposed to bare Cu(110). The effect of oxygen-passivation is to suppress debromination and it can be a convenient approach for investigating other self-assembly processes on copper-based substrates.

17.
ACS Nano ; 5(1): 424-8, 2011 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-21105746

RESUMO

The formation of a large scale pattern on Si(111)-7 × 7 reconstruction is still a challenge. We report herein a new solution to achieve this type of nanostructuration by using of zwitterionic molecules. The formation of a large-scale pattern is successfully obtained due to the perfect match between the molecular geometry and the surface topology and to electrostatic interactions between molecules and surface. The adsorption is described by high-resolution scanning tunneling microscopy (STM) images and supported by density functional theory and STM calculations.

18.
Chemphyschem ; 11(12): 2568-72, 2010 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-20665618

RESUMO

A single 4-pyridylazobenzene molecule is observed at room temperature on a Si(111)-B surface by using scanning tunnel microscopy. The reversible conformational switching of this molecule is induced by tunneling electrons and observed at room temperature. This process is based on an intramolecular rotation of a single phenyl group without isomerization of the N=N double bond.

19.
Langmuir ; 26(2): 943-9, 2010 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-20067309

RESUMO

The formation of compact and large-scale self-assembled monolayers (SAMs) adsorbed on a mica surface has been achieved by insertion of alkyl chains on azobenzene derivatives, leading to strong intermolecular van der Waals interactions and hydrogen bonding. The reversible photoswitching of monolayers was investigated by monitoring the variation of the thickness of the SAMs during the cis-trans isomerization of the azobenzene cores with an atomic force microscope (AFM). The absence of covalent bonds between molecules and substrate induces a molecular diffusion which leads to the complete isomerization of the molecules constituting the SAMs.


Assuntos
Silicatos de Alumínio/química , Compostos Azo/química , Membranas Artificiais , Fotoquímica/métodos , Adsorção , Ligação de Hidrogênio , Espectroscopia de Ressonância Magnética , Microscopia de Força Atômica , Modelos Teóricos , Espectrofotometria Ultravioleta , Raios Ultravioleta
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