Node-Dependent Photoinduced Electron Transfer in Third-Generation 2D MOFs Containing Earth-Abundant Metal Ions.

Five isostructural 2D metal-organic frameworks (MOFs), based on a photoactive CuI metallolinker and mixed mono-/dinuclear secondary building units (SBUs), are reported. The MOFs 1(M) (M = Mn, Co, Cu, Zn, and Cd) exhibit broad absorption across the visible-light spectrum and emission centered at ca. 730 nm. Upon photoexcitation, the rigidity of the framework hinders the pseudo-Jahn-Teller distortion of the metallolinker's excited state, providing efficient intersystem crossing into the triplet state. Rapid luminescence quenching in 1(Cu) and 1(Co) suggests photoinduced electron transfer (PET) to the SBUs, whereas lifetimes of up to 22.2 ns are observed in 1(Zn). The quantum yields relative to the parent photosensitizer (PS) decrease for metal nodes containing transition metal ions with partially occupied d-orbitals but increase for the d10 systems CdII and ZnII by a factor of up to 6. Importantly, the excited state decay rates directly correlate with the occupancy of the [MII(OH2)]x moieties in the MOFs providing nonradiative decay pathways via O-H oscillators. Cyclovoltammetry reveals minor changes in CuI/II oxidation potential, with excited-state reduction potentials for 1(M) rivalling Ru analogues. These results establish bis(diimine)copper(I) photosensitizers as viable metallolinkers for MOFs and present a rare example of an isostructural series obtained from a photosensitive metallolinker.

Light-harvesting, 3rd generation RuII/CoII MOF with a large, tubular channel aperture.

A photoactive, hetero-metallic CoII/RuII-based metal-organic framework (MOF) with a large channel aperture, ca. 21 Å, is reported. The photophysical properties of the MOF are derived from the RuII nodes giving rise to emission centred at ca. 620 nm and relatively long triplet 3MLCT lifetimes. In addition to the optical attributes, the 1H-imidazo [4,5-f][1,10]-phenanthroline ligand imparts structural functionality to the MOF which is composed of alternating CoII- and RuII-based nodes of Δ and Λ helicity. The framework maintains its integrity upon activation and shows gas sorption behaviour that is characteristic of mesoporous materials promoting high CO2 sorption capacities and selectivities over N2.

Oxide-mediated recovery of field-effect mobility in plasma-treated MoS2.

Precise tunability of electronic properties of two-dimensional (2D) nanomaterials is a key goal of current research in this field of materials science. Chemical modification of layered transition metal dichalcogenides leads to the creation of heterostructures of low-dimensional variants of these materials. In particular, the effect of oxygen-containing plasma treatment on molybdenum disulfide (MoS2) has long been thought to be detrimental to the electrical performance of the material. We show that the mobility and conductivity of MoS2 can be precisely controlled and improved by systematic exposure to oxygen/argon plasma and characterize the material using advanced spectroscopy and microscopy. Through complementary theoretical modeling, which confirms conductivity enhancement, we infer the role of a transient 2D substoichiometric phase of molybdenum trioxide (2D-MoO x ) in modulating the electronic behavior of the material. Deduction of the beneficial role of MoO x will serve to open the field to new approaches with regard to the tunability of 2D semiconductors by their low-dimensional oxides in nano-modified heterostructures.

Ag colloids and arrays for plasmonic non-radiative energy transfer from quantum dots to a quantum well.

Non-radiative energy transfer (NRET) can be an efficient process of benefit to many applications including photovoltaics, sensors, light emitting diodes and photodetectors. Combining the remarkable optical properties of quantum dots (QDs) with the electrical properties of quantum wells (QWs) allows for the formation of hybrid devices which can utilize NRET as a means of transferring absorbed optical energy from the QDs to the QW. Here we report on plasmon-enhanced NRET from semiconductor nanocrystal QDs to a QW. Ag nanoparticles in the form of colloids and ordered arrays are used to demonstrate plasmon-mediated NRET from QDs to QWs with varying top barrier thicknesses. Plasmon-mediated energy transfer (ET) efficiencies of up to ∼25% are observed with the Ag colloids. The distance dependence of the plasmon-mediated ET is found to follow the same d -4 dependence as the direct QD to QW ET. There is also evidence for an increase in the characteristic distance of the interaction, thus indicating that it follows a Förster-like model with the Ag nanoparticle-QD acting as an enhanced donor dipole. Ordered Ag nanoparticle arrays display plasmon-mediated ET efficiencies up to ∼21%. To explore the tunability of the array system, two arrays with different geometries are presented. It is demonstrated that changing the geometry of the array allows a transition from overall quenching of the acceptor QW emission to enhancement, as well as control of the competition between the QD donor quenching and ET rates.

Influence of plasmonic array geometry on energy transfer from a quantum well to a quantum dot layer.

A range of seven different Ag plasmonic arrays formed using nanostructures of varying shape, size and gap were fabricated using helium-ion lithography (HIL) on an InGaN/GaN quantum well (QW) substrate. The influence of the array geometry on plasmon-enhanced Förster resonance energy transfer (FRET) from a single InGaN QW to a ∼80 nm layer of CdSe/ZnS quantum dots (QDs) embedded in a poly(methyl methacrylate) (PMMA) matrix is investigated. It is shown that the energy transfer efficiency is strongly dependent on the array properties and an efficiency of ∼51% is observed for a nanoring array. There were no signatures of FRET in the absence of the arrays. The QD acceptor layer emission is highly sensitive to the array geometry. A model was developed to confirm that the increase in the QD emission on the QW substrate compared with a GaN substrate can be attributed solely to plasmon-enhanced FRET. The individual contributions of direct enhancement of the QD layer emission by the array and the plasmon-enhanced FRET are separated out, with the QD emission described by the product of an array emission factor and an energy transfer factor. It is shown that while the nanoring geometry results in an energy transfer factor of ∼1.7 the competing quenching by the array, with an array emission factor of ∼0.7, results in only an overall gain of ∼14% in the QD emission. The QD emission was enhanced by ∼71% for a nanobox array, resulting from the combination of a more modest energy transfer factor of 1.2 coupled with an array emission factor of ∼1.4.