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Atindra D Shukla

Publications and source records attributed to Atindra D Shukla.

9 recordsLinked to original sources
PubMed2006

Controlling structure from the bottom-up: structural and optical properties of layer-by-layer assembled palladium coordination-based multilayers.

Layer-by-layer assembly of two palladium coordination-based multilayers on silicon and glass substrates is presented. The new assemblies consist of rigid-rod chromophores connected by terminal pyridine moieties to palladium centers. Both colloidal palladium and PdCl2(PhCN)2 were used in order to determine the effect of the metal complex precursor on multilayer structure and optical properties. The multilayers were formed by an iterative wet-chemical deposition process at room temperature in air on a siloxane-based template layer. Twelve consecutive deposition steps have been demonstrated resulting in structurally regular assemblies with an equal amount of chromophore and palladium added in each molecular bilayer. The optical intensity characteristics of the metal-organic films are clearly a function of the palladium precursor employed. The colloid-based system has a UV-vis absorption maximum an order of magnitude stronger than that of the PdCl2-based multilayer. The absorption maximum of the PdCl2-based film exhibits a significant red shift of 23 nm with the addition of 12 layers. Remarkably, the structure and physiochemical properties of the submicron scale PdCl2-based structures are determined by the configuration of the approximately 15 angstroms thick template layer. The refractive index of the PdCl2-based film was determined by spectroscopic ellipsometry. Well-defined three-dimensional structures, with a dimension of 5 microm, were obtained using photopatterned template monolayers. The properties and microstructure of the films were studied by UV-vis spectroscopy, spectroscopic ellipsometry, atomic force microscopy (AFM), X-ray reflectivity (XRR), scanning electron microscopy (SEM), and aqueous contact angle measurements (CA).

Journal Article↗
PubMed2006

Strategies for electrooptic film fabrication. Influence of pyrrole-pyridine-based dibranched chromophore architecture on covalent self-assembly, thin-film microstructure, and nonlinear optical response.

The new dibranched, heterocyclic "push-pull" chromophores bis{1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (1), 1-(pyrid-4-yl)-2-(N-methyl-5-formylpyrrol-2-yl)ethylene (2), {1-(N-methylpyridinium-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}{(1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (3), N-methyl-2-[1-(N-methylpyrid-4-yl)ethen-2-yl]-5-[pyrid-4-yl]ethen-2-yl]pyrrole iodide (4), bis{1-(N-methyl-4-pyridinio)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane iodide (5), and N-methyl-2,5-[1-(N-methylpyrid-4-yl)ethen-2-yl]pyrrole iodide (6) have been synthesized and characterized. The neutral (1 and 2) and monomethyl salts (3 and 4) undergo chemisorptive reaction with iodobenzyl-functionalized surfaces to afford chromophore monolayers SA-1/SA-2 and SA-3/SA-4, respectively. Molecular structures and other physicochemical properties have been defined by (1)H NMR, optical spectroscopy, and XRD. Thin-film characterization by a variety of techniques (optical spectroscopy, specular X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and angle-dependent polarized second harmonic generation) underscore the importance of the chromophore molecular architecture as well as film growth method on film microstructure and optical/electrooptic response.

Journal Article↗
PubMed2006

Site affinity effects upon charge injection into siloxane-based monolayers.

Submolecular electrical information is successfully derived by applying element-specific, chemically resolved electrical measurements to a covalently bound stilbazole-based monolayer on a silicon substrate. Pronounced affinity effects are found in the response of adjacent atomic sites to external charge injection, accompanied by intramolecular polarization variations. These noncontact electrical read-out capabilities may provide a first entry toward the realization of organic devices based on submolecular electrical units.

Journal Article↗
PubMed2005

Mixed-ligand complexes of ruthenium(II) containing new photoactive or electroactive ligands: synthesis, spectral characterization and DNA interactions.

Mixed-ligand ruthenium(II) complexes of three photoactive ligands, viz., (E)-1-[2-(4-methyl-2-pyridyl)-4-pyridyl]-2-(1-naphthyl)-1-ethene (mppne), (E)-1-(9-anthryl)-2-[2-(4-methyl-2-pyridyl)-4-pyridyl]-1-ethene (mppae) and (E)-1-[2-(4-methyl-2-pyridyl)-4-pyridyl]-2-(1-pyrenyl)-1-ethene (mpppe), in which a 2,2'-bipyridyl unit is linked via an ethylinic linkage to either a naphthalene, an anthracene or a pyrene chromophore and three electroactive ligands, viz., 4-(4-pyridyl)-1,2-benzenediol (catpy), 5,6-dihydroxy-1,10-phenanthroline (catphen) and 1,2-benzenediol (cat), were synthesized in good to moderate yields. Complexes [Ru(bpy)(2)(mppne)](2+) (bpy is 2, 2'-bipyridyl), [Ru(bpy)(2)(mppae)](2+), [Ru(bpy)(2)(mpppe)](2+), [Ru(bpy)(2)(sq-py)](+), [Ru(bpy)(2)(sq-phen)](+) and [Ru(phen)(2)(bsq)](+) (phen is 1,10-phenanthroline) were fully characterized by elemental analysis, IR, (1)H NMR, fast-atom bombardment or electron-impact mass, UV-vis and cyclic voltammetric methods. In the latter three complexes, the ligands catpy, catphen and cat are actually bound to the metal center as the corresponding semiquinone species, viz., 4-(4-pyridyl)-1,2-benzenedioleto(+I) (sq-py), 1,10-phenanthroline-5,6-dioleto(+I) (sq-phen) and 1,2-benzenedioleto(+I) (bsq), thus making the overall charge of the complexes formally equal to + 1 in each case. These three complexes are electron paramagnetic resonance active and exhibit an intense absorption band between 941 and 958 nm owing to metal-to-ligand charge transfer (MLCT, d (Ru)-->pi*(sq)) transitions. The other three ruthenium(II) complexes containing three photoactive ligands, mppne, mppae and mpppe, exhibit MLCT (d (Ru)-->pi*(bpy) ) bands in the 454-461-nm region and are diamagnetic. These can be characterized by the (1)H NMR method. [Ru(bpy)(2)(mppne)](2+), [Ru(bpy)(2)(mppae)](2+) and [Ru(bpy)(2)(mpppe)](2+) exhibit redox waves corresponding to the Ru(III)/Ru(II) couple along with the expected ligand (bpy and substituted bpy) based ones in their cyclic and differential pulse voltammograms (CH(3)CN, 0.1 M tetrabutylammonium hexafluorophosphate)-corresponding voltammograms of [Ru(bpy)(2)(sq-py)](+), [Ru(bpy)(2)(sq-phen)](+) and [Ru(phen)(2)(bsq)](+) are mainly characterized by waves corresponding to the quinone/semiquinone (q/sq) and semiquinone/1,2-diol (sq/cat) redox processes. The results of absorption and fluorescence titration as well as thermal denaturation studies reveal that [Ru(bpy)(2)(mppne)](2+) and [Ru(bpy)(2)(mppae)](2+) are moderate-to-strong binders of calf thymus DNA with binding constants ranging from 10(5) to 10(6) M(-1). Under the identical conditions of drug and light dose, the DNA (supercoiled pBR 322) photocleavage activities of these two complexes follow the order:[Ru(bpy)(2)(mppne)](2+)>[Ru(bpy)(2)(mppae)](2+), although the emission quantum yields follow the reverse order. The other ruthenium(II) complexes containing the semiquinone-based ligands are found to be nonluminescent and inefficient photocleavage agents of DNA. However, experiments shows that [Ru(bpy)(2)(sq)](+)-based complexes oxidize the sugar unit and could be used as mild oxidants for the sugar moiety of DNA. Possible explanations for these observations are presented.

DNA↗
PubMed2005

A comparative Langmuir-Blodgett study on a set of covalently linked porphyrin-based amphiphiles: a detailed atomic force microscopic study.

A set of covalently linked phenyl-amidophenyl-substituted porphyrin amphiphiles with n-C15H31 tails have been synthesized and completely characterized. These amphiphiles form good Langmuir-Blodgett (LB) films at the air/water interface. Mean molecular areas for the series were measured from the isotherms and found to increase as the number of aliphatic chains increased from one to four. No influence of the subphase pH was observed on the isotherms. LB films can be transferred successfully onto different solid surfaces. The LB films were characterized using tapping mode atomic force microscopy (AFM). Bis-, tris-, and tetra-substituted porphyrins were found to be fairly good film-forming amphiphiles, whereas irregular aggregates were seen in the case of the monosubstituted porphyrin amphiphile. Multilayers were also formed with tetra-substituted amphiphiles on mica. Detailed AFM studies of tetra-substituted amphiphiles have been carried out to investigate the effect of preparation procedure and solid substrates on film formation and transfer. The absorption and fluorescence spectra for the amphiphiles in solution and LB films deposited onto mica and glass were recorded, which demonstrated the successful transfer of LB films onto the substrates and provided more information about the arrangement of porphyrin molecules within the LB films. For comparison, self-assembled monolayers (SAMs) and the cast thin films of the amphiphiles were prepared and characterized.

Journal Article↗
PubMed2005

Synthesis, characterization, physicochemical, and photophysical studies of redox switchable NIR dye derived from a ruthenium-dioxolene-porphyrin system.

Newly synthesized semi-quinone derivatives of the ruthenium polypyridyl, covalently linked to a porphyrin core, show very high epsilon values (59,000-83,500 M(-1)cm(-1)) for the absorption band in the near infrared (NIR) region of the spectrum. Further, complexes 1-4 show an interesting reversible electrochromic behavior as a function of the redox state of the coordinated dioxolene functionality, and a switching phenomenon between bleaching and the restoration of the NIR peak could be achieved electrochemically. Thus, complexes 1-4 could be ideal candidate materials for NIR-active electrochromic devices. Ultrafast studies on 1 and its mononuclear components, 5-(3,4-dihydroxyphenyl)-10,15,20-triphenyl-21H,23H-porphyrin (H2L1) and Ru(bpy)2(bsq)+, reveal that there is no electron or energy transfer from the porphyrin to the Ru(bpy)2sq+ (bpy is 2,2'-bipyridine and sq is the deprotonated species of a substituted semi-quinone fragment) fragment or vice versa in 1. The observed decrease in the luminescence quantum yield for 1 compared to that of H2L1 can be ascribed to the increased nonradiative pathway due to higher vibronic coupling because of the direct linkage of the metal center to the porphyrin moiety.

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