In situ spectroscopic characterization of rectifying molecular monolayers self-assembled on gold.

We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism.     

Molecular rectification: self-assembled monolayers in which donor-(pi-bridge)-acceptor moieties are centrally located and symmetrically coupled to both gold electrodes

Self-assembled monolayers (SAMs) obtained from 1-(10-acetylsulfanyldecyl)-4-[2-(4-dimethylaminophenyl)vinyl]quinolinium iodide exhibit asymmetric current-voltage (I-V) characteristics. The rectification may be reversibly switched: it is suppressed when the film is exposed to HCl vapor, the intramolecular charge-transfer axis being inhibited by protonation, but restored when exposed to NH(3). The behavior is intrinsic to the donor-(pi-bridge)-acceptor moiety, and ambiguity in the assignment has been excluded by matching the alkyl tails on the substrate and contacting STM tip to locate the chromophore midway between the electrodes: Au-S-C(10)H(21)//D-pi-A-C(10)H(20)-S-Au. Films contacted by gold tips exhibit rectification ratios of ca. 18 at +/-1 V, whereas those contacted by pentanethiolate (Au-S-C(5)H(11))- and decanethiolate (Au-S-C(10)H(21))-coated tips have corresponding ratios of ca. 11 and 5, respectively. The I-V curves are different, but when adjusted for thickness the current versus electric field dependence is indistinguishable. Seven dyes are reported: SAMs with sterically hindered D-pi-A moieties, in which the donor and acceptor are twisted out of plane, exhibit rectification, whereas those that are planar or have a weak donor-acceptor combination do not.     

Asymmetrical flow field-flow fractionation as a novel technique for the analysis of PS-b-PI copolymers

Asymmetrical flow field-flow fractionation (AF4) was used as a fractionation technique to investigate the molecular heterogeneity of poly(styrene-b-isoprene) diblock copolymers synthesized by either sequential living anionic polymerization or coupling of living precursor blocks. AF4 coupled to multi-angle laser light scattering (MALLS), refractive index (RI), and ultraviolet (UV) detectors was used to separate the diblock copolymers from the homopolymers and coupling products, and the molar masses of the different components were analyzed. In order to get more information about the separated block copolymers, homopolymers, and coupling products, fractions were collected directly after the AF4 channel. The collected fractions were analyzed offline by ¹H NMR to provide identification of the different species and additional information on the true chemical composition, and the microstructure of the diblock copolymer was obtained.

Submicrometer fiber-optic Fabry-Perot interferometer formed by use of the Langmuir-Blodgett technique

The fabrication of an optical cavity at the distal end of an optical fiber has been achieved by Langmuir-Blodgett (LB) deposition of tricosanoic acid. This technique allows nanometer-scale control over the cavity length to a total thickness of ~0.5 microm . The cavity has been shown to act interferometrically and, thus, has potential sensing applications.     

Second-harmonic generation from monolayer Langmuir–Blodgett films of various push–pull pyridine and terpyridine metal complexes

The new ligands (E)-4-[2-(4-(N-methyl-N-hexadecylaminophenyl)ethenyl]pyridine (L¹) and 4′-(C₆H₄-p-N(Me)(hexadecyl))-2,2′:6′,2″-terpyridine (L²) were prepared along with their complexes [cis-Ir(CO)₂ClL¹], [fac-Os(CO)₃Cl₂L¹], [ZnCl₂L²] and [IrCl₃L²]. Whereas these complexes show a large second-order nonlinear optical (NLO) response at the molecular level, similar to that of related organic alkylated salts as evidenced by the Electric Field Induced Second-Harmonic (EFISH) generation technique, their Langmuir–Blodgett (LB) film susceptibility is lower than that of the salts.     

Molecules that mimic Schottky diodes

Self-assembled monolayers of cationic donor-(pi-bridge)-acceptor dyes coupled with anionic donors exhibit asymmetric current-voltage (I-V) characteristics when contacted by Au or PtIr probes. Rectification ratios of 3000 at +/- 1 V are obtained from Au-S-C10H20-A+-pi-D|D-|Au structures in which the cationic moiety is 5-(4-dimethylaminobenzylidene)-5,6,7,8-tetrahydro-isoquinolinium and the counterion is copper phthalocyanine-3,4',4',4'-tetrasulfonate (SAM ). Similar behaviour, with a high rectification ratio of 700-900 at +/- 1 V, is also obtained for the CuPc(SO3-)4 salt of 4-[2-(4-dimethylaminonaphthalen-1-yl)-vinyl]-quinolinium (SAM ). The properties are dependent upon the D-pi-A+ moieties which, for these highly rectifying salts, have sterically locked non-planar structures causing the conjugation to be effectively broken. Its effect on the electrical asymmetry is less spectacular when the cationic species is sterically unhindered: the rectification ratio decreases to 15-70 at +/- 1 V for films of the 4-[2-(4-dimethylaminophenyl)-vinyl]-pyridinium salt (SAM ), which has single-ring substituents on opposite sides of the -CH=CH- bridge and an almost planar D-pi-A+ structure. Rectification ratios from the sterically hindered structures are on a par with electrical asymmetries from metal-insulator-metal (MIM) devices where oxide-induced Schottky barriers dominate the behaviour.     

Organic rectifying junctions from an electron-accepting molecular wire and an electron-donating phthalocyanine

Self-assembled monolayers (SAMs) of arylene-ethynylene oligomers that incorporate electron-accepting 9-fluorenone and 9-[(4-pyridyl)methylene]fluorene units in the backbone exhibit symmetrical current-voltage (I-V) characteristics, but rectifying junctions with current ratios of 20-80 at +/-1 V have been obtained by protonating these wire-like molecules and ionically coupling with anionic donors.