A Tripodal Ruthenium(II) Polypyridyl Complex with pH Controlled Emissive Quenching

A tripodal podand has been prepared and complexed to ruthenium(II) creating a metal complex with C3-symmetry and an enclosed cavity. The complex shows the anticipated enhanced emission when compared to [Ru(bipy)3]2+ in acetonitrile. The emission from this cryptand like structure is invariant to the introduction of monovalent cations in aqueous solution, but a significant drop in the emission was observed with increasing pH over a very broad pH range (3 to 12). This is attributed to an N to t2g electron transfer in the excited-state in the unprotonated form with a transfer rate of the order of 4.2 x 105 s-1. The crystal structure indicates the inclusion of water within the cavity suggesting that the protonation of a tertiary amine can be effectively moderated by a water molecule held in close proximity within a rigid cavit

Heterodimensional charge-carrier confinement in stacked submonolayer InAs in GaAs

Charge-carrier confinement in nanoscale In-rich agglomerations within a lateral InGaAs quantum well (QW) formed from stacked submonolayers (SMLs) of InAs in GaAs is studied. Low-temperature photoluminescence (PL) and magneto-PL clearly demonstrate strong vertical and weak lateral confinement, yielding two-dimensional (2D) excitons. In contrast, high-temperature (400 K) magneto-PL reveals excited states that fit a Fock-Darwin spectrum, characteristic of a zero-dimensional (0D) system in a magnetic field. This paradox is resolved by concluding that the system is heterodimensional: the light electrons extend over several In-rich agglomerations and see only the lateral InGaAs QW, i.e., are 2D, while the heavier holes are confined within the In-rich agglomerations, i.e., are 0D. This description is supported by single-particle effective-mass and eight-band k⋅p calculations. We suggest that the heterodimensional nature of nanoscale SML inclusions is fundamental to the ability of respective optoelectronic devices to operate efficiently and at high speed