Mechanistic Insight into the Formation and Deposition of Conductive, Layered Metal-Organic Framework Nanocrystals.

This paper describes the use of the layered conductive metal-organic framework (MOF) (nickel)-(hexahydroxytriphenylene) [Ni(HHTP)] as a model system for understanding the process of self-assembly within this class of materials. We confirm and quantify experimentally the role of the oxidant in the synthetic process. Monitoring the deposition of Ni(HHTP) with infrared spectroscopy revealed that MOF formation is characterized by an initial induction period, followed by linear growth with respect to time.

Gas-Induced Electrical and Magnetic Modulation of Two-Dimensional Conductive Metal-Organic Framework.

Controlled modulation of electronic and magnetic properties in stimuli-responsive materials provides valuable insights for the design of magnetoelectric or multiferroic devices. This paper demonstrates the modulation of electrical and magnetic properties of a semiconductive, paramagnetic metal-organic framework (MOF) Cu(CO) with small gaseous molecules, NH, HS, and NO. This study merges chemiresistive and magnetic tests to reveal that the MOF undergoes simultaneous changes in electrical conductance and magnetization that are uniquely modulated by each gas.

Fabrication of Multifunctional Electronic Textiles Using Oxidative Restructuring of Copper into a Cu-Based Metal-Organic Framework.

This paper describes a novel synthetic approach for the conversion of zero-valent copper metal into a conductive two-dimensional layered metal-organic framework (MOF) based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to form Cu(HHTP). This process enables patterning of Cu(HHTP) onto a variety of flexible and porous woven (cotton, silk, nylon, nylon/cotton blend, and polyester) and non-woven (weighing paper and filter paper) substrates with microscale spatial resolution. The method produces conductive textiles with sheet resistances of 0.

Epitaxial Self-Assembly of Interfaces of 2D Metal-Organic Frameworks for Electroanalytical Detection of Neurotransmitters.

This paper identifies the electrochemical properties of individual facets of anisotropic layered conductive metal-organic frameworks (MOFs) based on M(2,3,6,7,10,11-hexahydroxytriphenylene) (M(HHTP)) (M = Co, Ni). The electroanalytical advantages of each facet are then applied toward the electrochemical detection of neurochemicals. By employing epitaxially controlled deposition of M(HHTP) MOFs on electrodes, the contribution of the basal plane ({001} facets) and edge sites ({100} facets) of these MOFs can be individually determined using electrochemical characterization techniques.

Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing.

This paper describes the design, synthesis, characterization, and performance of a novel semiconductive crystalline coordination network, synthesized using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligands interconnected with bismuth ions, toward chemiresistive gas sensing. Bi(HHTP) exhibits two distinct structures upon hydration and dehydration of the pores within the network, Bi(HHTP)-α and Bi(HHTP)-β, respectively, both with unprecedented network topology (2,3-c and 3,4,4,5-c nodal net stoichiometry, respectively) and unique corrugated coordination geometries of HHTP molecules held together by bismuth ions, as revealed by a crystal structure resolved via microelectron diffraction (MicroED) (1.00 Å resolution).

Bimetallic Two-Dimensional Metal-Organic Frameworks for the Chemiresistive Detection of Carbon Monoxide.

This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal-organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm levels of carbon monoxide (CO). Devices achieve a sub-part-per-million (ppm) limit of detection (LOD) of 0.53 ppm toward CO at a low driving voltage of 0.

Employing Conductive Metal-Organic Frameworks for Voltammetric Detection of Neurochemicals.

This paper describes the first implementation of an array of two-dimensional (2D) layered conductive metal-organic frameworks (MOFs) as drop-casted film electrodes that facilitate voltammetric detection of redox active neurochemicals in a multianalyte solution. The device configuration comprises a glassy carbon electrode modified with a film of conductive MOF (MHXTP; M = Ni, Cu; and X = NH, 2,3,6,7,10,11-hexaiminotriphenylene (HITP) or O, 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)). The utility of 2D MOFs in voltammetric sensing is measured by the detection of ascorbic acid (AA), dopamine (DA), uric acid (UA), and serotonin (5-HT) in 0.

Dendritic architectures by orthogonal thiol-maleimide "click" and furan-maleimide dynamic covalent chemistries.

A set of dendrons and dendrimers is synthesized divergently using an orthogonal combination of kinetically-driven thiol-maleimide "click" chemistry and thermodynamically reversible furan-maleimide cycloaddition/retrocycloaddition reactions. Growth is controlled by taking advantage of the selective thiol-ene addition of thiols to the electron withdrawn alkene of maleimide in the presence of electron rich alkene of oxanorbornene. Subsequent activation of growing dendrons/dendrimers requires only heat to induce the dynamic covalent liberation of peripheral furan protecting groups.

Two-Dimensional Chemiresistive Covalent Organic Framework with High Intrinsic Conductivity.

This paper describes the synthesis of a novel intrinsically conductive two-dimensional (2D) covalent organic framework (COF) through the aromatic annulation of 2,3,9,10,16,17,23,24-octa-aminophthalocyanine nickel(II) and pyrene-4,5,9,10-tetraone. The intrinsic bulk conductivity of the COF material (termed ) reached 2.51 × 10 S/m, and increased by 3 orders of magnitude with I doping.

Electrically-Transduced Chemical Sensors Based on Two-Dimensional Nanomaterials.

Electrically-transduced sensors, with their simplicity and compatibility with standard electronic technologies, produce signals that can be efficiently acquired, processed, stored, and analyzed. Two dimensional (2D) nanomaterials, including graphene, phosphorene (BP), transition metal dichalcogenides (TMDCs), and others, have proven to be attractive for the fabrication of high-performance electrically-transduced chemical sensors due to their remarkable electronic and physical properties originating from their 2D structure. This review highlights the advances in electrically-transduced chemical sensing that rely on 2D materials.

Experimental and theoretical studies of selective thiol-ene and thiol-yne click reactions involving N-substituted maleimides.

A combination of experimental and computational methods has been used to understand the reactivity and selectivity of orthogonal thiol-ene and thiol-yne ″click″ reactions involving N-allyl maleimide (1) and N-propargyl maleimide (2). Representative thiols methyl-3-mercaptopropionate and β-mercaptoethanol are shown to add exclusively and quantitatively to the electron poor maleimide alkene of 1 and 2 under base (Et3N) initiated thiol-Michael conditions. Subsequent radical-mediated thiol-ene or thiol-yne reactions can be carried out to further functionalize the remaining allyl or propargyl moieties in near quantitative yields (>95%).