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Alberto Credi

Publications and source records attributed to Alberto Credi.

12 recordsLinked to original sources
PubMed2004

Photochemical and electronic properties of conjugated bis(azo) compounds: an experimental and computational study.

We have investigated the photophysical, photochemical and electrochemical properties of two bis(azo) derivatives, (E,E)-m-1 and (E,E)-p-1. The two compounds, which can be viewed as being composed of a pair of azobenzene units sharing one of their phenyl rings, differ only for the relative position of the two azo groups on the central phenyl ring-meta and para for m-1 and p-1, respectively. The UV-visible absorption spectra and photoisomerisation properties are noticeably different for the two structural isomers; (E,E)-m-1 behaves similarly to (E)-azobenzene, while (E,E)-p-1 exhibits a substantial red shift in the absorption bands and a decreased photoreactivity. The three geometric isomers of m-1, namely the E,E, E,Z and Z,Z isomers, cannot be resolved in a mixture by absorption spectroscopy, while the presence of three distinct species can be revealed by analysis of the absorption changes observed upon photoisomerisation of (E,E)-p-1. Quantum chemical ZINDO/1 calculations of vertical excitation energies nicely reproduce the observed absorption changes and support the idea that, while the absorption spectra of the geometrical isomers of m-1 are approximately given by the sum of the spectra of the constituting azobenzene units in their relevant isomeric form, this is not the case for p-1. From a detailed study on the E-->Z photoisomerisation reaction it was observed that the photoreactivity of an azo unit in m-1 is influenced by the isomeric state of the other one. Such observations indicate a different degree of electronic coupling and communication between the two azo units in m-1 and p-1, as confirmed by electrochemical experiments and quantum chemical calculations. The decreased photoisomerisation efficiency of (E,E)-p-1 compared to (E,E)-m-1 is rationalised by modelling the geometry relaxation of the lowest pi-pi* state. These results are expected to be important for the design of novel oligomers and polymers, based on the azobenzene unit, with predetermined photoreactivity.

Journal Article↗
PubMed2004

A mechanically interlocked bundle.

The prototype of an artificial molecular machine consisting of a trisammonium tricationic component interlocked with a tris(crown ether) component to form a molecular bundle with averaged C(3v) symmetry has been designed and synthesized. The system is based on noncovalent interactions, which include 1) N(+)-H...O hydrogen bonds; 2) C-H...O interactions between the CH(2)NH(2) (+)CH(2) protons on three dibenzylammonium-ion-containing arms, which are attached symmetrically to a benzenoid core, and three dibenzo[24]crown-8 macrorings fused onto a triphenylene core; and 3) pi...pi stacking interactions between the aromatic cores. The template-directed synthesis of the mechanically interlocked, triply threaded bundle involves post-assembly covalent modification, that is, the efficient conversion of three azide functions at the ends of the arms of the bound and threaded trication into bulky triazole stoppers, after 1,3-dipolar cycloaddition with di-tert-butylacetylenedicarboxylate to the extremely strong 1:1 adduct that is formed in dichloromethane/acetonitrile (3:2), on account of a cluster effect associated with the paucivalent adduct. Evidence for the averaged C(3v) symmetry of the molecular bundle comes from absorption and luminescence data, as well as from electrochemical experiments, (1)H NMR spectroscopy, and mass spectrometry. The photophysical properties of the mechanically interlocked bundle are very similar to those of the superbundle that precedes the formation of the bundle in the process of supramolecular assistance to covalent synthesis. Although weak non-nucleophilic bases (e.g., nBu(3)N and iPr(2)NEt) fail to deprotonate the bundle, the strong tBuOK does, as indicated by both luminescence and (1)H NMR spectroscopy. While deprotonation undoubtedly loosens up the interlocked structure of the molecular bundle by replacing relatively strong N(+)-H...O hydrogen bonds by much weaker N-H...O ones, the pi...pi stacking interactions ensure that any structural changes are inconsequential, particularly when the temperature of the solution of the neutral molecular bundle in dichloromethane is cooled down to considerably below room temperature.

Journal Article↗
PubMed2004

A molecular elevator.

We report the incrementally staged design, synthesis, characterization, and operation of a molecular machine that behaves like a nanoscale elevator. The operation of this device, which is made of a platformlike component interlocked with a trifurcated riglike component and is only 3.5 nanometers by 2.5 nanometers in size, relies on the integration of several structural and functional molecular subunits. This molecular elevator is considerably more complex and better organized than previously reported artificial molecular machines. It exhibits a clear-cut on-off reversible behavior, and it could develop forces up to around 200 piconewtons.

Journal Article↗
PubMed2004

Polyvalent scaffolds. Counting the number of seats available for eosin guest molecules in viologen-based host dendrimers.

We have prepared and investigated two dendrimers based on a 1,3,5-trisubstituted benzenoid-type core, containing 9 and 21 viologen units in their branches, respectively, and terminated with tetraarylmethane derivatives. We have shown that, in dichloromethane solution, such highly charged cationic species give rise to strong host-guest complexes with the dianionic form of the red dye eosin. Upon complexation, the absorption spectrum of eosin becomes broader and is slightly displaced toward lower energies, whereas the strong fluorescence of eosin is completely quenched. Titration experiments based on fluorescence measurements have shown that each viologen unit in the dendrimers becomes associated with an eosin molecule, so that the number of positions ("seats") available for the guest molecules in the hosting dendrimer is clearly established, e.g., 21 for the larger of the two dendrimers. The host-guest interaction can be destroyed by addition of chloride ions, a procedure which permits eosin to escape from the dendrimer's interior in a controlled way and to regain its intense fluorescence. When chloride anions are precipitated out by addition of silver cations, eosin molecules re-enter the dendrimer's interior and their fluorescence again disappears.

Journal Article↗
PubMed2003

Controlling multivalent interactions in triply-threaded two-component superbundles.

We have investigated the (1)H NMR spectra, the absorption spectra, the fluorescence spectra and decays, and the electrochemical properties of i). a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core, ii). a trifurcated trication wherein three dibenzylammonium ions are linked 1,3,5 to a central benzenoid core, and iii). their 1:1 adduct which constitutes a triply-threaded, two-component supramolecular bundle. X-Ray crystallography has established the precise geometry of this paucivalent recognition motif in the solid state. In addition to [N(+)-H...O] hydrogen bonding and [C-H...O] interactions between the NH(2) (+) centers on the three dibenzylammonium ion containing arms of the trication and the three crown ether rings in the tritopic receptor, there is a stabilizing [pi...pi] stacking interaction between the two aromatic cores. Mass spectrometry and (1)H NMR spectroscopy have confirmed the integrity of the 1:1 adduct beyond the solid state, provided the solvents are relatively apolar (e.g., chloroform and acetonitrile). The intense fluorescence emissions of the two recognition components are quenched upon association with the concomitant appearance of a lower energy, broad fluorescence band originating from the pi-pi stacking in the 1:1 adduct of the aromatic cores in the two matching components. Titration experiments, including Job plots, establish the 1:1 stoichiometry of the adduct, an observation which is also confirmed by electrochemical experiments. The electrochemical results show that, both in the tritopic receptor and in the superbundle itself, the first oxidation process is associated with the hexaalkoxytriphenylene core. The successive oxidation processes of the peripheral dioxybenzene units are affected by charge-transfer interactions in the tritopic receptor, whereas, in the superbundle, such units are not interacting. In acetonitrile solution, dethreading/rethreading of the 1:1 adduct can be controlled quantitatively by addition of base and acid. Dethreading and rethreading is also observed by (1)H NMR spectroscopy when dimethylsulfoxide is added to a solution of the 1:1 adduct in equal volumes of acetonitrile and chloroform. A trifurcated trication where methyl groups are located on the para positions of the three dibenzylammonium ions, which are linked 1,3,5 to the neutral benzenoid core, has been employed to demonstrate that dethreading of the 1:1 adduct involves doubly-threaded and singly-threaded species, that is, the paucivalent site is dismembered in a sequence of logical steps involving stable intermediates. This molecular recognition system is a rare example of a supramolecular entity based on a cooperative binding motif that can be switched on and off by chemical means.

Journal Article↗
PubMed2003

Molecular logic circuits.

Miniaturization has been an essential ingredient in the outstanding progress of information technology over the past fifty years. The next, perhaps ultimate, limit of miniaturization is that of molecules, which are the smallest entities with definite size, shape, and properties. Recently, great effort has been devoted to design and investigate molecular-level systems that are capable of transferring, processing, and storing information in binary form. Some of these nanoscale devices can, in fact, perform logic operations of remarkable complexity. This research--although far from being transferred into technology--is attracting interest, as the nanometer realm seems to be out of reach for the "top-down" techniques currently available to microelectronics industry. Moreover, such studies introduce new concepts in the "old" field of chemistry and stimulate the ingenuity of researchers engaged in the "bottom-up" approach to nanotechnology.

Journal Article↗
PubMed2002

The bottom-up approach to molecular-level devices and machines.

The macroscopic concepts of a device and a machine can be extended to the molecular level. Molecular-level devices and machines are constructed by a bottom-up approach. The atom-by-atom bottom-up approach is unrealistic from the chemical viewpoint. The bottom-up approach molecule-by-molecule following the guidelines of supramolecular (multicomponent) chemistry has proved to be successful. The extension of the concepts of a device and a machine to the molecular level is of interest not only for basic research, but also for the growth of nanoscience and the development of nanotechnology.

Journal Article↗
PubMed2002

Photoinduced electron transfer in a triad that can be assembled/disassembled by two different external inputs. Toward molecular-level electrical extension cables.

We have designed, synthesized, and investigated a self-assembling supramolecular system which mimics, at a molecular level, the function performed by a macroscopic electrical extension cable. The system is made up of three components, 12+, 2-H3+, and 3. Component 12+ consists of two moieties: a [Ru(bpy)3]2+ unit, which plays the role of an electron donor under light excitation, and a DB24C8 crown ether, which fulfills the function of a socket. The wire-type component 2-H3+ is also composed of two moieties, a secondary dialkylammonium-ion center and a bipyridinium unit, which thread into the DB24C8 crown-ether socket of 12+ and the 1/5DN38C10 crown-ether socket 3, respectively. The photochemical, photophysical, and electrochemical properties of the three separated components, of the 12+ superset 2-H3+ and 2-H3+ subset 3 dyads, and of the 12+ superset 2-H3+ subset 3 triad have been investigated in CH2Cl2 solution containing 2% MeCN. Reversible connection/disconnection of the two plug/socket systems can be controlled independently by acid/base and redox stimulation. The behavior of the various different dyads and triad has been monitored by light absorption and emission spectroscopies, as well as by electrochemical techniques. In the fully connected 12+ superset 2-H3+ subset 3 triad, light excitation of the [Ru(bpy)3]2+ unit of component 12+ is followed by electron transfer (k = 2.8 x 108 s-1) to the bipyridinium unit of component 2-H3+, which is plugged into component 3. Possible schemes to obtain improved molecular-level electrical extension cables are discussed.

Journal Article↗
PubMed2002

Ferrocene-containing carbohydrate dendrimers.

Aliphatic amines, incorporating one or three (branched) acylated beta-D-glucopyranosyl residues, were coupled with the acid chloride of ferrocenecarboxylic acid and with the diacid chloride of 1,1'-ferrocenedicarboxylic acid to afford four dendrimer-type, carbohydrate-coated ferrocene derivatives in good yields (54-92%). Deprotection of the peracylated beta-D-glucopyranosyl residues was achieved quantitatively by using Zemplén conditions, affording four water-soluble ferrocene derivatives. When only one of the two cyclopentadienyl rings of the ferrocene unit is substituted, strong complexes are formed with beta-cyclodextrin in H2O, as demonstrated by liquid secondary ion mass spectrometry (LSIMS), 1H NMR spectroscopy, electrochemical measurements, and circular dichroism spectroscopy. Molecular dynamics calculations showed that the unsubstituted cyclopentadienyl ring is inserted through the cavity of the toroidal host in these complexes. The electrochemical behavior of the protected and deprotected ferrocene-containing dendrimers was investigated in acetonitrile and water, respectively. The diffusion coefficient decreases with increasing molecular weight of the compound. The potential for oxidation of the ferrocene core, the rate constant of heterogeneous electron transfer, and the rate constant for the energy-transfer reaction with the luminescent excited state of the [Ru(bpy)3]2+ complex (bpy = 2,2'-bipyridine) are strongly affected by the number (one or two) of substituents and by the number (one or three) of carbohydrate branches present in the substituents. These effects are assigned to shielding of the ferrocene core by the dendritic branches. Electrochemical evidence for the existence of different conformers for one of the dendrimers in aqueous solution was obtained.

Carbohydrates↗
PubMed1998

Diastereoselective Formation and Photophysical Behavior of a Chiral Copper(I) Phenanthroline Complex.

The Friedländer condensation of (1R,5S)-(+)- and (1S,5R)-(-)-nopinone with 8-aminoquinoline-7-carbaldehyde leads to the corresponding enantiomerically pure (2,3-b)-pineno-1,10-phenanthrolines. Coordination of these ligands with Cu(I) affords non-interconvertable chiral complexes which show equal and opposite Cotton effects in their CD spectra as well as identical half-wave oxidation potentials of +0.37 V and identical MLCT absorptions at 442 nm. Both complexes are nonemissive at 298 and 77 K. Stern-Volmer quenching studies were carried out with optically pure Delta- and Lambda-[Ru(bpy)(3)](2+) and racemic [Ru(dpb)(3)](2+) as donors (bpy = 2,2'-bipyridine and dpb = 4,4'-diphenyl-bpy). Neither study provides any evidence of enantioselective quenching, indicating that energy or electron transfer may be occurring through a distance where chiral recognition is unimportant.

Journal Article↗
PubMed1997

Luminescent and Redox-Active Iridium(III)-Cyclometalated Compounds with Terdentate Ligands.

Two novel bis-terdentate Ir(III)-cyclometalated complexes, [Ir(L1)(L1(-))](2+) (1) and [Ir(L1(-))(2)](+) (2), have been prepared (L1 is 2,6-bis(7'-methyl-4'-phenyl-2'-quinolyl)pyridine; L1(-) is its mono-anion, see Figure 1). To the best of our knowledge, 1 and 2 are the first luminescent and redox-active Ir(III)-cyclometalated bis-terdentate compounds. In acetonitrile solution, on oxidation, 2undergoes a reversible, metal-centered, one-electron oxidation at +1.40 V, whereas 1 does not exhibit any oxidation process up to +2.00 V. On reduction, both compounds undergo four reversible ligand-centered one-electron processes. The absorption spectra of the compounds are dominated by moderately intense (epsilon in the 10(3)-10(4) M(-)(1) cm(-)(1) range) spin-allowed metal-to-ligand charge-transfer (MLCT) bands at wavelengths longer than 350 nm and by intense (epsilon in the 10(4)-10(5) M(-)(1) cm(-)(1) range) ligand-centered (LC) bands at shorter wavelengths. The complexes exhibit an intense luminescence both at 77 K in MeOH/EtOH, 4:1 (v/v), rigid matrix (1, lambda(max) = 592 nm, tau = 20 &mgr;s; 2, lambda(max) = 598 nm, tau = 9 &mgr;s) and at room temperature in deoxygenated acetonitrile solution (1, lambda(max) = 620 nm, tau = 325 ns, Phi = 0.005; 2, lambda(max) = 630 nm, tau = 2.3 &mgr;s, Phi = 0.066). In all cases, the emission is assigned to triplet MLCT levels (namely, Ir --> L1 and Ir --> L1(-) in 1 and 2, respectively).

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