Monocyclometalated Gold(III) Monoaryl Complexes—A New Class of Triplet Phosphors with Highly Tunable and Efficient Emission Properties

Highly tunable and rich phosphorescent emission properties based on the stable monocyclometalated gold(III) monoaryl structural motif are reported. Monochloro complexes of the type cis‐[(N^C)Au(C₆H₂(CF₃)₃)(Cl)] N^C=2‐phenylpyridine (ppy)] ( 1 ), [N^C=benzo[h]quinoline (bzq)] ( 2 ), [N^C=2‐(5‐Methyl‐2‐thienyl)pyridine (5m‐thpy)] ( 3 ) were successfully prepared in modest to good yields by reacting an excess of 2, 4, 6‐tris(trifluoromethyl)phenyl lithium (LiFmes) with the corresponding dichloride complexes cis‐[(N^C)AuCl₂]. Subsequent replacement of the chloride ligand in 1 with strong ligand field strength such as cyanide and terminal alkynes resulted in complexes of the type cis‐[(ppy)Au(Fmes)(R)] R=CN ( 4 ), I ( 5 ), C?C?C₆H₅ ( 6 ) and C?C?C₆H₄N(C₆H₅)‐p ( 7 ). Single crystal X‐ray diffraction studies of all the complexes except 7 were performed to further corroborate their chemical identity. Thermogravimetric analysis (TGA) studies of the uncommon cis configured aryl alkyne complex 7 confirmed the high stability of this complex. Detailed photophysical investigations carried out in solution at room temperature, at 77 K (2‐MeTHF) in rigidified media, solid state and 5 wt % PMMA revealed the phosphorescent nature of emission in these complexes. Additionally, their behavior was found to be governed based on both the nature of the cyclometalated ligand and the electronic properties of the ancillary ligands. Highly efficient interligand charge transfer in complex 7 provides access to a wide range of emission colors (solvent‐dependent) from deep blue to red with phosphorescence emission quantum yield of 30 % (441 nm) and 39 % (622 nm) in solution and solid state, respectively, and is the highest reported for any Au^III complexes. DFT and TDDFT calculations carried out further validated the observations and assignments based on the photophysical experimental findings.     

Directing Group Assisted Unsymmetrical Multiple Functionalization of Arene C−H Bonds

Multiple C?H bond functionalizations promptly install diverse groups on the molecular framework and consequently fabricate complex molecular entities. This review briefly surveys the conceptual development of directing group assisted unsymmetrical multiple functionalization of arene C(sp²)?H bonds, which is exceedingly appealing and highly important.     

Cu(II)‐Metallacryptands Self‐Assembled to Vesicular Aggregates Capable of Encapsulating and Transporting an Anticancer Drug Inside Cancer Cells

Crystallographically characterized M₂L₄ type cationic Cu(II)‐metallacryptands [MC(X)] derived from a series of bis‐pyridyl‐bis‐urea ligands (L_X; X = O, S, C) are self‐assembled to single‐layered vesicular aggregates in DMSO, DMSO/water, and DMSO/DMEM (biological media). One such vesicle is MC(O)‐vesicle that is demonstrated to be able to load and release (pH responsive) an anticancer drug, namely doxorubicin hydrochloride (DOX). DOX‐loaded MC(O)‐vesicle is also successfully transported within MDA‐MB‐231 cells—a highly aggressive human breast cancer cell line. Such self‐assembling behavior to form vesicular aggregates by metallacryptands (MCs) is hitherto unknown.     

Incorporation of active metal sites in MOFs via in situ generated ligand deficient metal-linker complexes

Two novel 3D MOFs, namely MOF-647A and MOF-648 (previously unknown trinodal 4-connected net), comprised of Cu ions and pyrazole-3,5-dicarboxylate were synthesized and characterized. A strategy for incorporating open metal sites in MOFs was investigated by utilizing an in situ generated metal-linker complex as a precursor to construct MOF-648.     

Foldamer structuring by covalently bound macromolecules

We used fluorescence and electronic absorption spectroscopy to study the molecular weight dependence of macromolecule-induced folding in a chain-centered meta-phenylene ethynylene (mPE) oligomer. Analogous to the ability of intrinsically unstructured proteins (IUPs) to induce folding of globular proteins in cellular environments, we show that macromolecules attached to both ends of an mPE dodecamer induce the foldamer to collapse into a presumed helical conformation. The collapse is especially prominent once the macromolecule segments become larger than ca. 50 kDa. For sufficiently large macromolecules, the conformational structuring occurs even in solvents that normally denature the foldamer. Based on these findings, chain-centered foldamers might find use as models to investigate the fundamental macromolecular physics of IUPs.     

Anionic and hidden hydrogen in ZnO

First-principles calculations are performed to study energetics and kinetics of hydrogen in ZnO, in particular, the H(-) anion and the H(2) molecule on the interstitial site and in the oxygen vacancy. We show that the H(2) molecule kinetically trapped in the oxygen vacancy, rather than interstitial H(2), can explain a variety of experimental observations on "hidden" hydrogen in ZnO. The accumulation of shallow donors, especially the substitutional H, near the ZnO surface is important to the formation of hidden hydrogen in the ZnO bulk and can also lead to persistent photoconductivity.     

Modeling and simulation of long-wave infrared InAs/GaSb strained layer superlattice photodiodes with different passivants

Current–voltage characteristics of long-wave infrared (LWIR) InAs/GaSb strained layer superlattice photodiodes (cut-off wavelength ∼10 μm), passivated with different surface passivants, have been modeled and simulated using ATLAS software from SILVACO. The simulated results are fitted to previous experimental results obtained on unpassivated devices and those passivated by silicon-dioxide (SiO₂), silicon nitride (Si_xN_y) and zinc sulfide (ZnS). Surface parameters in terms of surface recombination velocity, shunt resistance and interface trap density are extracted for different passivants. The performance of silicon-dioxide passivated diode is solely dominated by a shunt leakage path with a shunt resistance value of 0.56 Ω-cm². Extracted electron and hole surface recombination velocities have values of 10⁵ cm/s and 10⁷ cm/s for unpassivated, 10³ cm/s and 10⁵ cm/s for Si_xN_y passivated and 10² cm/s and 10³ cm/s for ZnS passivated devices. Interface trap density follows a similar trend with values of 10¹⁵ cm⁻², 8.5 × 10¹⁴ cm⁻² and 10¹⁰ cm⁻² for unpassivated, Si_xN_y passivated and ZnS passivated devices respectively. The suitability and limitations of the simulation tool are discussed.     

Rational Approach Towards Designing Metallogels From a Urea‐Functionalized Pyridyl Dicarboxylate: Anti‐inflammatory,Anticancer, and Drug Delivery

A structural rationale was adopted to design a series of metallogels from a newly synthesized urea‐functionalized dicarboxylate ligand, namely, 5‐[3‐(pyridin‐3‐yl)ureido]isophthalic acid ( PUIA ), that produces metallogels upon reaction with various metal salts (Cu^II, Zn^II, Co^II, Cd^II, and Ni^II salts) at room temperature. The gels were characterized by dynamic rheology and transmission electron microscopy (TEM). The existence of a coordination bond in the gel state was probed by FTIR and ¹H NMR spectroscopy in a Zn^II metallogel (i.e., MG2 ). Single crystals isolated from the reaction mixture of PUIA and Co^II or Cd^II salts characterized by X‐ray diffraction revealed lattice inclusion of solvent molecules, which was in agreement with the hypothesis based on which the metallogels were designed. MG2 displayed anti‐inflammatory response (prostaglandin E₂ assay) in the macrophage cell line (RAW 264.7) and anticancer properties (cell migration assay) on a highly aggressive human breast cancer cell line (MDA‐MB‐231). The MG2 metallogel matrix could also be used to load and release (pH responsive) the anticancer drug doxorubicin. Fluorescence imaging of MDA‐MB‐231 cells treated with MG2 revealed that it was successfully internalized.     

Gravity duals for nonrelativistic conformal field theories

We attempt to generalize the anti-de Sitter/conformal field theory correspondence to nonrelativistic conformal field theories which are invariant under Galilean transformations. Such systems govern ultracold atoms at unitarity, nucleon scattering in some channels, and, more generally, a family of universality classes of quantum critical behavior. We construct a family of metrics which realize these symmetries as isometries. They are solutions of gravity with a negative cosmological constant coupled to pressureless dust. We discuss realizations of the dust, which include a bulk superconductor. We develop the holographic dictionary and find two-point correlators of the correct form. A strange aspect of the correspondence is that the bulk geometry has two extra noncompact dimensions.     

Metallogels Derived from Silver Coordination Polymers of C3‐Symmetric Tris(pyridylamide) Tripodal Ligands: Synthesis of Ag Nanoparticles and Catalysis

By applying a recently developed crystal engineering rationale, four C₃ symmetric tris(pyridylamide) ligands namely 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐trimethylbenzene, and 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐trimethylbenzene, which contain potential hydrogen‐bonding sites, were designed and synthesized for generating Ag^I coordination polymers and coordination‐polymer‐based gels. The coordination polymers thus obtained were characterized by single‐crystal X‐ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X‐ray diffraction, energy dispersive X‐ray and X‐ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4‐nitrophenolate to 4‐aminophenolate without the use of any exogenous reducing agent.