Electrochromic Os(II)-Based Metallo-Supramolecular Polymers.

This work presents the preparation of a series of novel Os(II)-based metallo-supramolecular polymers (polyOss: linear polyOsL1100% and hyperbranched polyOsL1x% L2y% ) that show a broad absorption spanning 312 to 677 nm and a low Os(II)/(III) redox potential of 0.94 V. The electrochromic properties of a polyOs film cast on an ITO substrate is investigated. The change in transmittance (ΔT) of polyOsL1100% is 49.9%, and the switching times for coloration (t c ) and bleaching (t b ) are 0.70 and 0.82 s, respectively. The introduction of a 10% branching structure (polyOsL190% L210% ) further enhanced the electrochromic performance with ΔT = 59.4%, t c  = 0.41 s, and t b  = 0.54 s. The coloration efficiency (η) increased from 396.1 to 467.5 cm2  C-1 upon branching. A solid-state electrochromic device with polyOsL1100% is successfully fabricated to use the polymer for potential applications.

Modulation of a coordination structure in a europium(iii)-based metallo-supramolecular polymer for high proton conduction.

Developing high proton conducting solid materials is significant in the field of fuel cells. A europium(iii)-based metallo-supramolecular polymer with uncoordinated carboxylic acids (PolyEu-H) was successfully synthesized by modifying the synthesis conditions. The proton conductivity was enhanced with increasing the relative humidity (RH) from 30 to 95% RH. PolyEu-H showed about 104 times higher proton conductivity than the polymer with coordinated carboxylic acids (PolyEu) and about 400 times higher than the polymer without carboxylic acids (PolyEu-2). The proton conductivity of PolyEu-H reached 4.45 × 10-2 S cm-1 at 95% RH and 25 °C and 5.6 × 10-2 S cm-1 at 75 °C. The activation energy, E a was ultralow (0.04 eV), which indicates proton conduction based on the Grotthuss mechanism. The results indicate that efficient proton conduction occurs through proton channels formed by moisture in PolyEu-H.

One-Dimensional Anhydrous Proton Conducting Channel Formation at High Temperature in a Pt(II)-Based Metallo-Supramolecular Polymer and Imidazole System.

One dimensional (1D) Pt(II)-based metallo-supramolecular polymer with carboxylic acids (polyPtC) was synthesized using a new asymmetrical ditopic ligand with a pyridine moiety bearing two carboxylic acids. The carboxylic acids in the polymer successfully served as apohosts for imidazole loaded in the polymer interlayer scaffold to generate highly ordered 1D imidazole channels through the metallo-supramolecular polymer chains. The 1D structure of imidazole loaded polymer (polyPtC-Im) was analyzed in detail by thermogravimetric analysis, powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and ultraviolet-visible and photoluminescence spectroscopic measurements. PolyPtC-Im exhibited proton conductivity of 1.5 × 10-5 S cm-1 at 120 °C under completely anhydrous conditions, which is 6 orders of magnitude higher than that of the pristine metallo-supramolecular polymer.

Selective DNA Recognition and Cytotoxicity of Water-Soluble Helical Metallosupramolecular Polymers.

Water-soluble helical Fe(II)-based metallosupramolecular polymers ((P)- and (M)-polyFe) were synthesized by 1:1 complexation of Fe(II) ions and bis(terpyridine)s bearing a (R)- and (S)-BINOL spacer, respectively. The binding affinity to calf thymus DNA (ct-DNA) was investigated by titration measurements. (P)-PolyFe with the same helicity as B-DNA showed 40-fold higher binding activity (Kb = 13.08 × 107 M-1) to ct-DNA than (M)-polyFe. The differences in binding affinity were supported by electrochemical impedance spectroscopy analysis. The charge-transfer resistance (Rct) of (P)-polyFe increased from 2.5 to 3.9 kΩ upon DNA binding, while that of (M)-polyFe was nearly unchanged. These results indicate that ionically strong binding of (P)-polyFe to DNA chains decreased the mobility of ions in the conjugate. Unique rod-like images were obtained by atomic force microscopy measurement of the DNA conjugate with (P)-polyFe, likely because of the rigid binding between DNA chains and the polymer. Differences in polymer chirality lead to significantly different cytotoxicity levels in A549 cells. (P)-PolyFe showed higher binding affinity to B-DNA and much higher cytotoxicity than (M)-polyFe. The helicity in metallosupramolecular polymer chains was important not only for chiral recognition of DNA but also for coordination to a biological target in the cellular environment.

Proton Conductive Nanosheets Formed by Alignment of Metallo-Supramolecular Polymers.

Linear Fe(II)-based metallo-supramolecular polymer chains were precisely aligned by the simple replacement of the counteranion with an N,N'-bis(4-benzosulfonic acid)perylene-3,4,9,10-tetracarboxylbisimide (PSA) dianion, which linked the polymer chains strongly. A parallel alignment of the polymer chains promoted by the PSA dianions yielded nanosheets formation. The nanosheets' structure was analyzed with FESEM, HRTEM, UV-vis, and XRD in detail. The nanosheets showed more than 5 times higher proton conductivity than the original polymer due to the smooth ionic conduction through the aligned polymer chains. The complex impedance plot with two semicircles also suggested the presence of grain boundaries in the polymer nanosheets.

Vice versa donor acceptor fluorene-ferrocene alternate copolymer: a twisted ribbon for electrical switching.

Two donor-acceptor type copolymers (PFFC-1 and PFFC-2) containing ferrocene and fluorene moieties have been successfully synthesized to evaluate the redox triggered optical and electronic properties. Interestingly, PFFC-1 shows a twisted ribbon-like morphology at the liquid interface and switches to a micellar structure on oxidation.

Graphene quantum dot-doped polyaniline nanofiber as high performance supercapacitor electrode materials.

Graphene quantum dot-doped polyaniline composites have been prepared by the chemical oxidation of aniline. Synthesized novel fibrous composites show an excellent specific capacitance value of ∼1044 F g(-1) at a current density of 1 A g(-1) as well as moderate cyclic stability with a retention of life time of 80.1% after 3000 cycles.

Facile Decoration of Polyaniline Fiber with Ag Nanoparticles for Recyclable SERS Substrate.

Facile synthesis of polyaniline@Ag composite has been successfully demonstrated by a simple solution-dipping method using high-aspect-ratio benzene tetracarboxylic acid-doped polyaniline (BDP) fiber as a nontoxic reducing agent as well as template cum stabilizer. In BDP@Ag composite, BDP fibers are decorated with spherical Ag nanoparticles (Ag NPs), and the population of Ag NPs on BDP fibers is controlled by changing the molar concentration of AgNO3. Importantly, Ag-NP-decorated BDP fibers (BDP@Ag composites) have been evolved as a sensitive materials for the detection of trace amounts of 4-mercaptobenzoic acid and rhodamine 6G as an analyte of surface-enhanced Raman scattering (SERS), and the detection limit is down to nanomolar concentrations with excellent recyclability. Furthermore, synthesized BDP@Ag composites are applied simultaneously as an active SERS substrate and a superior catalyst for reduction of 4-nitrothiophenol.

Effects of process parameters on the defects in graphene oxide-polyaniline composites investigated by positron annihilation spectroscopy.

Graphene oxide (GO)-polyaniline (PANI) composites were prepared with different relative abundance of PANI and GO by in situ polymerization of aniline in the presence of GO and ammonium persulphate at different temperatures. In the process, GO also got reduced to graphene. Positron lifetimes and coincidence Doppler broadening of the electron-positron annihilation gamma ray spectra originating from the composite samples were measured and the results are reported. The positron lifetimes indicated the presence of very large size defects in the form of vacancy clusters within the samples. Another interesting observation was the increase of relative intensity of the defect specific positron lifetime component when an increase in relative abundance of PANI led to increased reduction of GO to graphene. The reduction also shrank the volume occupied by GO and the free volume thereby released added to the overall defect concentration, resulting in a simultaneous increase of the intensity of the positron lifetime component. The variation of the positron lifetime and its intensity with the synthesis temperature suggested an optimum temperature suitable for the process. The above observations are corroborated by other experimental investigations like electron microscopy, X-ray diffraction and electrical conductivity.

Graphene oxide/polyaniline nanostructures: transformation of 2D sheet to 1D nanotube and in situ reduction.

The formation of unique polyaniline nanotubes has been reported in presence of graphene oxide (GO) which plays crucial dual role as dopant and soft template, simultaneously. GO in nanotubes is in situ reduced to reduced GO with restoration of electrical conductivities and enhanced thermal stabilities.

Azo anion radical complex of rhodium as a molecular memory switching device: isolation, characterization, and evaluation of current-voltage characteristics.

Two rare examples of azo anion diradical complexes of Rh(III) are reported. These complexes showed excellent memory switching properties with a large ON/OFF ratio and are suitable for RAM/ROM applications. Their electronic structures have been elucidated using a host of physical methods, including X-ray crystallography, variable-temperature magnetic susceptibility measurement, cyclic voltammetry, electron paramagnetic resonance spectroscopy, and density functional theory. The results indicate a predominant triplet state description of the systems with two ferromagnetically coupled radicals.