MODs vs. NPs: Vying for the Future of Printed Electronics

This Minireview compares two distinct ink types, namely metal-organic decomposition (MOD) and nanoparticle (NP) formulations, for use in the printing of some of the most conductive elements: silver, copper and aluminium. Printing of highly conductive features has found purpose across a broad array of electronics and as processing times and temperatures reduce, the avenues of application expand to low-cost flexible substrates, materials for wearable devices and beyond. Printing techniques such as screen, aerosol jet and inkjet printing are scalable, solution-based processes that historically have employed NP formulations to achieve low resistivity coatings printed at high resolution. Since the turn of the century, the rise in MOD inks has vastly extended the range of potentially applicable compounds that can be printed, whilst simultaneously addressing shelf life and sintering issues. A brief introduction to the field and requirements of an ink will be presented followed by a detailed discussion of a wide array of synthetic routes to both MOD and NP inks. Unindustrialized materials will be discussed, with the challenges and outlook considered for the market leaders: silver and copper, in comparison with the emerging field of aluminium inks.     

High-yield syntheses and reactivity studies of Fe10 "ferric wheels": structural, magnetic, and computational characterization of a star-shaped Fe8 complex

Convenient, high-yield routes have been developed to [Fe 10(OMe) 20(O 2CR) 10] ( 1) "ferric wheels" involving the alcoholysis of [Fe 3O(O 2CR) 6(H 2O) 3] (+) salts in MeOH in the presence of NEt 3. Reactivity studies have established [Fe 10(OMe) 20(O 2CMe) 10] ( 1a) to undergo clean carboxylate substitution with a variety of other RCO 2H groups to the corresponding [Fe 10(OMe) 20(O 2CR) 10] product. In contrast, the reaction with phenol causes a nuclearity change to give a smaller [Fe 8(OH) 4(OPh) 8(O 2CR) 12] ( 2) wheel. Similarly, reactions of [Fe 10(OMe) 20(O 2CR) 10] with the bidentate chelate ethylenediamine (en) cause a structural change to give either [Fe 8O 5(O 2CMe) 8(en) 8](ClO 4) 6 ( 3) or [Fe 2O(O 2CBu (t))(en) 4](NO 3) 3 ( 4), depending on conditions. Complex 3 possesses a "Christmas-star" Fe 8 topology comprising a central planar [Fe 4(mu 4-O)] (10+) square subunit edge-fused to four oxide-centered [Fe 3(mu 3-O)] (7+) triangular units. Variable-temperature, solid-state dc and ac magnetization studies on complexes 1a- 4 in the 5.0-300 K range established that all the complexes possess an S = 0 ground state. The magnetic susceptibility data for 4 were fit to the theoretical chi M versus T expression derived by the use of an isotropic Heisenberg spin Hamiltonian and the Van Vleck equation, and this revealed an antiferromagnetic exchange parameter with a value of J = -107.7(5) cm (-1). This value is consistent with that predicted by a previously published magnetostructural relationship. Theoretically computed values of the exchange constants in 3 were obtained with the ZILSH method, and the pattern of spin frustration within its core and the origin of its S = 0 ground state have been analyzed in detail.     

Effect of High Humidity Exposure to Wheat Starch Based High Conducting Flexible Polymer-in-Salt-Electrolyte

Polymer-in-salt-electrolytes (PISEs) are an important class of electrolytes as they carry the promise of faster and single ion transport. Unfortunately, due to unavailability of a suitable polymer host PISE has still not reached to commercial level. In the present work, using a novel synthesis protocol developed by the group, glutaraldehyde crosslinked wheat starch has been successfully modified with sodium iodide (NaI) to synthesize a flexible PISE membrane with desired electrochemical properties. Present paper reports the effect of crosslinker and exposure to high humidity ambience on electrochemical and morphological properties. It has been established that on exposure to higher humidity atmosphere starch-based PISEs stabilize at lower resistance value, but with higher ion relaxation time, which indicates that effect of high humidity treatment is more on salt dissociation instead of assisting the ion transport. The studied materials have conductivity ≈0.01 S cm⁻¹ range with ESW >2.5 V, ensuring its usability in electrochemical devices. The developed synthesis protocol does not require any complicated synthesis route and/or sophisticated instrument hence the overall process is economical also, adding up to its potentiality for energy device fabrication.     

Synthesis and evaluation of novel tetrapropoxycalix[4]arene enones and cinnamates for protection from ultraviolet radiation

A series of novel calix[4]arene enones (5-7) and cinnamates (12-14) have been synthesized and evaluated for ensuring protection from ultraviolet radiation (UVR). Spectroscopic analyses has revealed that compound 6 absorbs ultraviolet radiations between 280 and 350 nm with an absorption maximum at 312 nm. Its molar absorption coefficient (ε) (>5 × 10(4)M(-1)cm(-1)) and bandwidth are larger than those for the commercially used sun protectants (oxybenzone (OB), 2-ethylhexyl 4-methoxycinnamate (OMC) and avobenzone). The in vitro Sun Protection Factor (SPF) measurement revealed an SPF of 5.2 at 2% concentration of 6 in home made emulsion formulations while combination of 2% each of 6 and OMC gave an SPF of 8.8. Lower sun protection seems to be compensated by significant protection from more harmful UVA radiations (UVA/UVB absorbance ratio of 0.62).     

Raising the spin of Fe(III)7 disklike clusters: the power of molecular spin frustration

Two clusters with a new type of Fe(III)(7) disklike structure have been prepared; in contrast to other Fe(III)(7) disks, they possess high ground-state spins (S = (15)/(2) and (21)/(2)), which have been rationalized by analysis of the spin-frustration patterns.     

Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In ‘chemistry of nanoparticles’ we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In ‘development of new synthetic approaches’ our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO₂ and ZrO₂ as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H₂MoO₄, H2WO₄, MoS₂, and WS₂ giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.     

Microwave and flow syntheses of Pseudomonas quinolone signal (PQS) and analogues

Expedient syntheses of Pseudomonas quinolone signal (PQS) and related structural analogues using microwave and flow methods are reported.     

Pt-catalyzed O-silylation of oximes by tri-substituted organosilanes

Silylated derivatives of oximes are important intermediates in organic synthesis, and have found application in the preparation of various nitrogen containing compounds including nitriles, amines, nitrones, and hydroxylamines. An efficient method for the O-silylation of aldoximes and ketoximes through a platinum-catalyzed reaction using trisubstituted-hydrosilanes is described. The reaction works well with a range of aliphatic and aromatic oximes when using triethylsilane as a silylating agent. Furthermore, a number of tri-substituted organosilanes including triisopropylsilane, diethoxymethylsilane, triphenylsilane, and triethoxysilane were also explored.