The Chemistry of CO2 Capture in an Amine-Functionalized Metal-Organic Framework under Dry and Humid Conditions.

The use of two primary alkylamine functionalities covalently tethered to the linkers of IRMOF-74-III results in a material that can uptake CO2 at low pressures through a chemisorption mechanism. In contrast to other primary amine-functionalized solid adsorbents that uptake CO2 primarily as ammonium carbamates, we observe using solid state NMR that the major chemisorption product for this material is carbamic acid. The equilibrium of reaction products also shifts to ammonium carbamate when water vapor is present; a new finding that has impact on control of the chemistry of CO2 capture in MOF materials and one that highlights the importance of geometric constraints and the mediating role of water within the pores of MOFs.

Efficient Triplet Exciton Fusion in Molecularly Doped Polymer Light-Emitting Diodes.

Solution-processed polymer organic light-emitting diodes (OLEDs) doped with triplet-triplet annihilation (TTA)-upconversion molecules, including 9,10-diphenylanthracene, perylene, rubrene and TIPS-pentacene, are reported. The fraction of triplet-generated electroluminescence approaches the theoretical limit. Record-high efficiencies in solution-processed OLEDs based on these materials are achieved. Unprecedented solid-state TTA-upconversion quantum yield of 23% (TTA-upconversion reaction efficiency of 70%) at electrical excitation well below one-sun equivalent is observed.

Effect of Selenium Substitution on Intersystem Crossing in π-Conjugated Donor-Acceptor-Donor Chromophores: The LUMO Matters the Most.

This study explores the effect of substitution of selenium (Se) for sulfur (S) on the photophysical properties of a series of π-conjugated donor-acceptor-donor chromophores based on 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT). The effect of Se substitution is studied systematically, where the substitution is in the thiophene donors only, the benzothiadiazole acceptor only, and in all of the positions. The fluorescence quantum yield decreases with an increase in Se substitution. Nanosecond-microsecond transient absorption and singlet oxygen sensitization experiments show that the effect of Se is due to an increase in the rate and efficiency of intersystem crossing with increased Se substitution. The relationship between intersystem crossing efficiency and heteroatom substitution pattern shows that the effects are largest when the heavy atom Se is in the acceptor benzothiadiazole unit. DFT calculations support the hypothesis that the effect arises because the LUMO is concentrated in the acceptor moiety, enhancing the spin-orbit coupling effect imparted by the Se atom.

Improved Open- Circuit Voltage in ZnO-PbSe Quantum Dot Solar Cells by Understanding and Reducing Losses Arising from the ZnO Conduction Band Tail.

Colloidal quantum dot solar cells (CQDSCs) are attracting growing attention owing to significant improvements in efficiency. However, even the best depleted-heterojunction CQDSCs currently display open-circuit voltages (VOCs) at least 0.5 V below the voltage corresponding to the bandgap. We find that the tail of states in the conduction band of the metal oxide layer can limit the achievable device efficiency. By continuously tuning the zinc oxide conduction band position via magnesium doping, we probe this critical loss pathway in ZnO-PbSe CQDSCs and optimize the energetic position of the tail of states, thereby increasing both the VOC (from 408 mV to 608 mV) and the device efficiency.