Lanthanide‐based metal–organic compounds and architectures are promising systems for sensing, heterogeneous catalysis, photoluminescence, and magnetism. Herein, the fabrication of interfacial 2D ...lanthanide‐carboxylate networks is introduced. This study combines low‐ and variable‐temperature scanning tunneling microscopy (STM) and X‐ray photoemission spectroscopy (XPS) experiments, and density functional theory (DFT) calculations addressing their design and electronic properties. The bonding of ditopic linear linkers to Gd centers on a Cu(111) surface gives rise to extended nanoporous grids, comprising mononuclear nodes featuring eightfold lateral coordination. XPS and DFT elucidate the nature of the bond, indicating ionic characteristics, which is also manifest in appreciable thermal stability. This study introduces a new generation of robust low‐dimensional metallosupramolecular systems incorporating the functionalities of the f‐block elements.
On‐surface assembly of robust 2D lanthanide‐carboxylate coordination networks. The codeposition of TDA linker species and Gd on Cu(111) results in the formation of reticular networks, based on Gd–carboxylate interactions featuring a unique eightfold mononuclear node, which are thermally stable up to 400 K. X‐ray photoemission spectroscopy experiments and density functional theory calculations reveal the predominant ionic nature of the bond.
► Avoiding complicated processes and forgoing the need for special instruments. ► Existence of a relationship between structures of the target products and the raw materials. ► Being more appropriate ...for the phase control of products. ► Having better control over the process conditions, particle size, particle crystal structure, and purity.
In this review we present methods for preparation of nano inorganic materials in which metal–organic coordination polymers are used as precursors. Here we summarize the effects of various factors such as structure, temperature, morphology and size of precursor on the morphology and size of the nano-materials produced. A review of the literature concludes that coordination polymers are suitable precursors for production of nanoscale materials with optimized morphologies and properties.
In situ toxification of less toxic substance for the generation of effective anticarcinogens at the specific tumor tissue has been a novel paradigm for combating cancer. Significant efforts have been ...recently dedicated to turning clinical‐approved drugs into anticancer agents in specific tumor microenvironment by chemical reactions. Herein, a hollow mesoporous Prussian blue (HMPB)‐based therapeutic nanoplatform, denoted as DSF@PVP/Cu‐HMPB, is constructed by encapsulating alcohol‐abuse drug disulfiram (DSF) into the copper‐enriched and polyvinylpyrrolidone (PVP)‐decorated HMPB nanoparticles to achieve in situ chemical reaction‐activated and hyperthermia‐amplified chemotherapy of DSF. Upon tumor accumulation of DSF@PVP/Cu‐HMPB, the endogenous mild acidity in tumor condition triggers the biodegradation of the HMPB nanoparticle and the concurrent co‐releases of DSF and Cu2+, thus forming cytotoxic bis(N,N‐diethyl dithiocarbamato)copper(II) complexes (CuL2) via DSF‐Cu2+ chelating reaction. Moreover, by the intrinsic photothermal‐conversion effect of PVP/Cu‐HMPBs, the anticancer effect of DSF is augmented by the hyperthermia generated upon near‐infrared irradiation, thus inducing remarkable cell apoptosis in vitro and tumor elimination in vivo on both subcutaneous and orthotopic tumor‐bearing models. This strategy of in situ drug transition by chemical chelation reaction and photothermal‐augmentation provides a promising paradigm for designing novel cancer‐therapeutic nanoplatforms.
This work provides an intriguing paradigm of in situ conversion of disulfiram into an effective anticarcinogen combined with therapeutic efficacy amplification for tumor eradication and excellent biosafety, which is also expected to contribute to the future design of novel in situ‐activated and external‐stimulus‐augmented therapeutic nanoplatforms.
Organic cathode materials are plagued by their low cycle stability and poor electronic conductivity, even though they have attracted increasing attention in the context of lithium‐ion batteries ...(LIBs). Herein, a coordination polymer cobalt‐hexaazatriphenylene hexacarbonitrile (Co(HAT‐CN)) is prepared via a facile solvothermal method, which is composed of the redox‐active HAT‐CN linker and the Co(II) ion center. The fabricated material shows excellent structural stability and high conductivity. Moreover, graphene oxide (GO) is introduced as a substrate, and in‐situ loading of Co(HAT‐CN) on its surface shows enhanced cycling stability. For Co(HAT‐CN)/GO, a high specific capacity of 204 mAh g–1 can be retained even after 200 cycles at a current density of 40 mA g–1 in a voltage window of 1.2–3.9 V. Ex situ and in situ analyses are applied to probe the reversibility of the pyrazine redox‐active center during the cycling process and the lithium storage process. Density functional theory calculations reveal that the high conductivity of Co(HAT‐CN) should be ascribed to the narrow LUMO‐HOMO gap (0.61 eV), and strong binding of lithiated molecules.
The metal‐organic coordination polymer cobalt‐hexaazatriphenylene hexacarbonitrile (Co(HAT‐CN)) shows high conductivity due to the narrow LUMO‐HOMO gap (0.61 eV). The Co(HAT‐CN) also shows long‐term cycling stability due to the high insolubility in liquid electrolytes. Graphene oxide can further enhance the stability of Co(HAT‐CN) in liquid electrolytes and improve the cycling performance.
In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which has led to the discovery of unprecedented transformations as well as ...the improvement of known reactions. In this subfield of photocatalysis, a transition metal complex serves a double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via a single catalytic cycle, thus contrasting the established dual photocatalysis in which an exogenous photosensitizer is employed. In addition, this approach often synergistically combines catalyst-substrate interaction with photoinduced process, a feature that is uncommon in conventional photoredox chemistry. This Review describes the early development and recent advances of this emerging field.
Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is ...challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, 2+2 cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.
Both intrapersonal and interpersonal coordination dynamics have traditionally been investigated using relative phase patterns of in-phase (
ϕ
= 0°) and/or anti-phase (
ϕ
= 180°). Numerous ...investigations have demonstrated that coordination tasks that require other relative phase patterns (e.g., 90°) are difficult or near impossible to perform without extended practice. Recent findings, however, have demonstrated that an individual can produce a wide range of intrapersonal bimanual patterns within a few minutes of practice when provided integrated feedback. The present experiment was designed to directly compare intra- and interpersonal coordination performance and variability when provided Lissajous feedback or pacing metronome. Single participants (
N
= 12) and pairs of participants (
N
= 24, 12 pairs) were required to produce relative phase patterns between 0° and 180° in 30° increments using either pacing metronomes or Lissajous displays. The Lissajous displays involved a goal template and a cursor providing integrated feedback regarding the position of the two effectors. The results indicated both single and pairs of participants could effectively produce a large range of coordination patterns that typically act as repellers after only 6 min of practice when provided integrated feedback. However, single participants performed the in-phase coordination pattern more accurately and with less variability than paired participants, regardless of the feedback condition. These results suggest an advantage for intrapersonal coordination when performing in-phase coordination, possibly due to the stabilizing effect occurring via the neuro-muscular linkage between effectors.
PDF
