Conducting and Magnetic Langmuir−Blodgett Films

Talham, Daniel R.

doi:10.1021/cr030665u

Cited by 199 publications

(114 citation statements)

References 196 publications

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“…The average area per molecule at collapse (A c ) was obtained by extrapolating the steepest part of the curve down to zero pressure. [3,14] The pyridine head-group of the ligand seems to have interfered little with the packing of the monolayer, and the observed area of [23][24][25] 2 molecule À1 is comparable to the packing reported for a carboxylic acid with an equivalent number of carbon atoms. [40] The formal film collapse happened at 45-50 mN m…”

Section: Q3dmentioning

confidence: 81%

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Interfacial Behavior and Film Patterning of Redox‐Active Cationic Copper(II)‐Containing Surfactants

Driscoll¹,

Allard²,

Wu³

et al. 2008

Chemistry A European J

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Herein, we describe the synthesis and characterization of a novel series of single-tail amphiphiles LPyCn (Py=pyridine, Cn=C18, C16, C14, C10) and their copper(II)-containing complexes, which are of relevance for patterned films. The N-(pyridine-2-ylmethyl)alkyl-1-amine ligands and their complexes [CuIICl2(LPyC18)] (1), [CuIICl2(LPyC16)] (2), [CuIICl2(LPyC14)] (3), [CuIIBr2(LPyC18)] (4), [CuIIBr2(LPyC16)] (5), and [CuIIBr2(LPyC10)] (6) were synthesized, isolated, and characterized by means of mass spectrometry, IR and NMR spectroscopies, and elemental analysis. Complexes 1, 2, 3, and 6 had their molecular structure solved by X-ray diffraction methods, which showed that the local geometry around the metal center is distorted square planar. With the aim of using these species as precursors for redox-responsive films, an assessment of their electrochemical properties involved cyclic voltammetry in different solvents, with different supporting electrolytes and scan rates. Density functional theory calculations of relevant species in bulk and at interfaces were used to evaluate their electronic structure and dipole moments. The morphology and order of the resulting films at the air/water interface were studied by isothermal compression and Brewster angle microscopy. Biphasic patterned Langmuir films were observed for all complexes except 3 and 6, and dependence on the chain length and the nature of the halogen coligand determine the characteristics of the isotherms and their intricate topology. Complexes 3 and 6, which have shorter chain lengths, failed to exhibit organization. These results exemplify the first comprehensive study of the behavior of single-tail metallosurfactants, which are likely to lead to high-end technological applications based on their patterned films.

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Section: Q3dmentioning

confidence: 81%

“…[3] Similarly, an effort is being made toward understanding the cooperativity between transition-metal ions and amphiphilic organic scaffolds. This interaction leads to redox, [4] optical, [5,6] and magnetic [7] behavior and distinctive order, and has been explored thus far in thixotropic, [8] mesogenic, [9] and micellar [10] design.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Behavior and Film Patterning of Redox‐Active Cationic Copper(II)‐Containing Surfactants

Driscoll¹,

Allard²,

Wu³

et al. 2008

Chemistry A European J

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“…For LB films of phthalocyanines, peripheral substituents such as bulky tert-butyl group and long alkyl chains are required to be dissolved in hydrophobic organic solvent, so that the solution can be spread at air-water interface. Under compression of the Langmuir film on the water, phthalocyanine molecules usually form columnar stacking assembly due to π-π interaction between the macrocycles [7]. In order to control the molecular orientation in LB films, it would be effective to select proper peripheral substituents because characters of substituents such as length, flexibility, and hydrophilicity have crucial effects on molecular orientation at air-water interface, resulting in peculiar surface pressure-area isotherms (π-A curves) [8].…”

Section: Introductionmentioning

confidence: 99%

Effect of Central Metals on Langmuir-Blodgett Monolayers of Phthalocyanines with Flexible Substituents

Kojima

Fukumura

Hasegawa

2015

e-J. Surf. Sci. Nanotech.

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Langmuir-Blodgett (LB) monolayers of octaoctyloxy metallophthalocyanines (MOOPc, M = Cu, Zn) and copper tetra(tert-butyl) phthalocyanine were deposited on glass substrates. MOOPcs showed gradual increase in their surface pressure-area isotherms reflecting their flexible substituents. In spite of the similar molecular structure, Cu and ZnOOPc indicated different isotherms at lower pressure, manifested by the surface morphology. At high surface pressure, ZnOOPc monolayer became denser than CuOOPc monolayer, as was estimated by the optical absorption. These results represents that the central metals have a crucial effect on structures of LB monolayers.

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“…In the solid state, hydrogen bonds have been used to influence the disposition of TTF units with varying degrees of success, [41][42][43][44][45][46][47] one example being that of amide bonds which aid the formation of stacks of molecules. [48] On the other hand, fibres have been formed in Langmuir films [49,50] and gels [51] with a random orientation, and gels of TTFs have shown some alignment of the fibres. [52] In two cases xerogels based on TTF derivatives have been proven to conduct electricity.…”

Section: Introductionmentioning

confidence: 99%

Chemical and Constitutional Influences in the Self‐Assembly of Functional Supramolecular Hydrogen‐Bonded Nanoscopic Fibres

Puigmartí‐Luis

Minoia

Pino

et al. 2006

Chemistry A European J

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A new series of secondary amides bearing long alkyl chains with pi-electron-donor cores has been synthesized and characterised, and their self-assembly upon casting at surfaces has been studied. The different supramolecular assemblies of the materials have been visualized by using atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is possible to obtain well-defined fibres of these aromatic core molecules as a result of the hydrogen bonds between the amide groups. Indeed, by altering the alkyl-chain lengths, constitutions, concentrations and solvent, it is possible to form different rodlike aggregates on graphite. Aggregate sizes with a lower limit of 6-8 nm width have been reached for different amide derivatives, while others show larger aggregates with rodlike morphologies which are several micrometers in length. For one compound that forms nanofibres, doping was performed by using a chemical oxidant, and the resulting layer on graphite was shown to exhibit metallic-like spectroscopy curves when probed with current-sensing AFM. This technique also revealed current maps of the surface of the molecular material. Fibre formation not only takes place on the graphite surface: nanometre scale rods have been imaged by using TEM on a grid after evaporation of solutions of the compounds in chloroform. Molecular modelling proves the importance of the hydrogen bonds in the generation of the fibres, and indicates that the constitution of the molecules is vital for the formation of the desired columnar stacks, results that are consistent with the images obtained by microscopic techniques. The results show the power of noncovalent bonds in self-assembly processes that can lead to electrically conducting nanoscale supramolecular wires.

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Conducting and Magnetic Langmuir−Blodgett Films

Cited by 199 publications

References 196 publications

Interfacial Behavior and Film Patterning of Redox‐Active Cationic Copper(II)‐Containing Surfactants

Interfacial Behavior and Film Patterning of Redox‐Active Cationic Copper(II)‐Containing Surfactants

Effect of Central Metals on Langmuir-Blodgett Monolayers of Phthalocyanines with Flexible Substituents

Chemical and Constitutional Influences in the Self‐Assembly of Functional Supramolecular Hydrogen‐Bonded Nanoscopic Fibres

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