Critical phenomena in FINEMET alloy

The Fe_73.5Cu₁Nb₃Si_13.5B₉ FINEMET alloy has been prepared by the rapid solidification technique. The critical behaviour of this alloy in the amorphous as well as in its nanocrystalline states has been studied near their respective Curie temperatures. From the values of the critical exponents one can conclude that the alloy behaves like a 3D Heisenberg ferromagnet in the amorphous and nanocrystalline states. But there exists a slight increase in the value of β for the alloy annealed at 823 K (the nanocrystalline state) as observed in most of the amorphous alloys.     

Enhanced mechanical strength of hydroxyapatite nanorods reinforced with polyethylene

Hydroxyapatite (HAp) nanostructures may be an advanced candidate in biomedical applications for an apatite substitute of bone and teeth than other form of HAp. In contrast, well-defined size and shape control in synthesizing HAp nanostructures is always difficult. In this study, hydroxyapatite nanorods (HAp NRs) were prepared by simple hydrothermal method with controlling the reaction time without using any surfactant or templating agents. The nanostructure clearly depicts the growth stages of the HAp NRs by increasing the reaction time. The synthesized HAp has the rod like morphology with uniform size distribution with the aspect ratio of about 8–10. Transmission electron microscopic (TEM) and high resolution TEM (HRTEM) images show that the growth direction of the HAp is parallel to the (001) plane. The interplanar distances measured in segments (fringes) of the HRTEM micrograph were ~0.35 nm, corresponding to the interplanar spacing of the (002) plane of the hexagonal HAp. X-ray diffraction (XRD) measurements indicate that the improved crystallinity of the HAp by increasing the reaction time. The mechanical studies reveal that the improved tensile strength and the abrasion resistance are observed for the HAp nanorods reinforcing with high molecular weight polyethylene (HMWPE).     

Unusual face-to-face pi-pi stacking interactions within an indigo-pillared M3(tpt)-based triangular metalloprism

A triangular metalloprism, [((CO)3Re(mu-2)Re(CO)3)3(mu3-1)2], self-assembled from Re2(CO)10, 2,4,6-tri-4-pyridyl-1,3,5-triazine (tpt, 1), and indigo (H2(2)), represents a fairly novel example of strong face-to-face pi-pi interactions between the central triazine rings of the tpt ligands that bow significantly inward distorting the prismatic structure.     

CH...pi interaction for rhenium-based rectangles: an interaction that is rarely designed into a host-guest pair

Alkoxy- and thiolato-bridged Re(I) molecular rectangles [{(CO)3Re(mu-ER)2Re(CO)3}2(mu-bpy)2] (ER = SC4H9, 1a; SC8H17, 1b; OC4H9, 2a; OC12H25, 2b; bpy = 4,4'-bipyridine) exhibit strong interactions with several planar aromatic molecules. The nature of their binding was studied by spectral techniques and verified by X-ray diffraction analysis. Standard absorption and fluorescence titrations showed that a relatively strong 1:1 interaction occurs between aromatic guests such as pyrene and these rectangles. The results of a single-crystal X-ray diffraction analysis show that the recognition of 1 with a pyrene molecule is mainly due to CH...pi interactions and the face of the guest pyrene is located over the edges of the bpy linkers of 1. This is a fairly novel example of an interaction that is rarely designed into a host-guest pair. Furthermore, the interaction of 1 with Ag+ results in the self-organization of supramolecular arrays, as revealed by solid-state data.     

Giant metal-organic frameworks with bulky scaffolds: from microporous to mesoporous functional materials

New concepts on the design and synthesis of crystalline metal-organic frameworks (MOFs) have made them a subject of considerable interest in the growing field of materials science. By creating larger cavity sizes by a nearly infinite combination of metal nodes and organic linkers, many innovative characteristics of microporous MOFs have been revealed. The primary goal of this perspective article is to highlight the frontiers in the development of giant MOFs that are deliberately constructed from metallated or metal-free bulky scaffolds. Incorporating these types of distinct bulky ligands into giant MOFs may lead to MOFs with a large cavity size, intriguing properties and new framework topology. Emerging applications of these materials in catalysis, adsorption, and sensors are also discussed.     

Tandem Knoevenagel-[3+2] cycloaddition-elimination reactions: one-pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles

Sodium azide has been found to catalyse Knoevenagel condensation between aromatic aldehyde and cyano compound with active methylene hydrogens and this has led to a successful route for the one pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles from aldehydes through Knoevenagel-[3+2]cycloaddition-elimination sequence. In the formation of 5-aryl-2H-1,2,3-triazole-4-carbonitrile derivatives, the reaction has been found to occur efficiently in water.     

Synthesis and photophysical properties of neutral luminescent rhenium-based molecular rectangles

A series of neutral luminescent molecular rectangles [[Re(CO)(3)(mu-bpy)Br][Re(CO)(3)(mu-L)Br]](2) (1-4) having fac-Re(CO)(3)Br as corners and 4,4'-bipyridine (bpy) as the bridging ligand on one side and other bipyridyl ligands of varying length (L) on the other side have been synthesized and characterized. The crystal structure of 1 shows a rectangular cavity with the dimensions of 11.44 x 7.21 A. When the cavity size is tuned from 1 to 4, a dimension of 11.4 x 20.8 A could be achieved, as revealed by the molecular modeling. These rectangles exhibit luminescence in solution at room temperature. In particular, compound 4 containing 1,4-bis(4'-pyridylethynyl)benzene (bpeb) as bridging ligand shows the excited-state lifetime of 495 ns. Fine-tuning of the cavity size of the rectangles improves their excited-state properties. These properties facilitate the study of excited-state electron-transfer reactions with electron acceptors and donors and host-guest binding. Crystallographic information: 1.6CH(3)COCH(3) is monoclinic, P2(1)/c, with a = 12.0890(2), b = 24.2982(2), and c = 12.8721(2) A, beta = 107.923(1) degrees, and Z = 2.     

Gondola-shaped luminescent tetrarhenium metallacycles with crown-ether-like multiple recognition sites

The self-assembly of gondola-shaped tetrarhenium metallacyclophanes was achieved in near quantitative yield from Re(CO)3 corners, a ditopic heterocyclic clip, and a bischelating-bridging unit using an orthogonal-bonding approach. The highly luminescent metallacycles contain crown-ether-like recognition sites, which are capable of selectively recognizing metal ions and planar aromatic molecules.     

Hydrophobic Metal−Organic Frameworks and Derived Composites for Microelectronics Applications

The extraordinary characteristic features of metal−organic frameworks (MOFs) make them applicable for use in a variety of fields but their conductivity in microelectronics over a wide relative humidity (RH) range has not been extensively explored. To achieve good performance, MOFs must be stable in water, i. e., under humid conditions. However, the design of ultrastable hydrophobic MOFs with high conductivity for use in microelectronics as conducting and dielectric materials remains a challenge. In this Review, we discuss applications of an emerging class of hydrophobic MOFs with respect to their use as active sensor coatings, tunable low-κ dielectrics and conductivity, which provide high-level roadmap for stimulating the next steps toward the development and implementation of hydrophobic MOFs for use in microelectronic devices. Several methodologies including the incorporation of long alkyl chain and fluorinated linkers, doping of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ), the use of guest molecules, and conducting polymers or carbon materials in the pores or surface of MOFs have been utilized to produce hydrophobic MOFs. The contact angle of a water droplet and a coating can be used to evaluate the degree of hydrophobicity of the surface of a MOF. These unique advantages enable hydrophobic MOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Classic representative examples of each category are discussed in terms of coordination structures, types of hydrophobic design, and potential microelectronic applications. Lastly, a summary and outlook as concluding remarks in this field are presented. We envision that future research in the area of hydrophobic MOFs promise to provide important breakthroughs in microelectronics applications.