No abstract

The hydrocarbons 1-cyclopentylidene-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene and 1-cyclobutylidene-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene undergo photolysis in solution at ambient temperature to produce cyclohexyne and cyclopentyne, respectively. These strained cycloalkynes, formed via the putative cycloalkylidenecarbenes, were intercepted as Diels-Alder adducts. Calculations at the CCSD(T)/cc-pVTZ//B3LYP/6-31+G* level of theory show that singlet cyclopentylidenecarbene has to overcome a barrier of 9.1 kcal mol to rearrange into cyclohexyne (with ΔE for ring expansion=-15.1 kcal mol ). By contrast, cyclobutylidenecarbene only needs to surmount a barrier of 1.6 kcal mol to rearrange into cyclopentyne (with ΔE for ring expansion=-6.2 kcal mol ).

Various cathode interface materials have been used in organic solar cells (OSCs) to realize high performance. However, most cathode interface materials have their respective weaknesses in maximizing the efficiency or stability of OSCs. Herein, three kinds of alcohol-soluble cathode interfacial materials are combined with bathocuproine (BCP) to serve as multifunctional bilayer cathode buffers for the regular OSCs, and thus greatly enhanced power conversion efficiencies over 10.11% and significantly improved device stability have been achieved. By utilizing double interlayers, both light absorption and light distribution in active layer are improved. Furthermore, double interlayers offer favorable energy-level alignment, alcohol treatment, and duplicate protection of active layer, resulting in significantly reduced leakage current, suppressed recombination, and efficient charge collection. The improved device stability is related to the blocking effect of the complex formed between BCP and the metal electrode and the additional protection effect of the underlying alcohol-soluble materials. In view of the universal use of alcohol-soluble organic electrolyte as cathode buffer layers and by courtesy of the superiority of the double cathode layers relative to the monolayer controls, the double interlayer strategy demonstrated here opens a new way to fully exploiting the potential of OSCs and is believed to be extended to a wider application.

The strained heterocyclic alkyne, 3-oxacyclohexyne, was generated photochemically for the first time using a cyclopropanated phenanthrene precursor, and trapped by cyclopentadienones as Diels-Alder adducts. The precursor initially produced the putative 3-oxacyclopentylidenecarbene that subsequently rearranged to the cycloalkyne. Computational studies indicate that the carbene favors a singlet state, and the barrier for its ring expansion by a 1,2-shift of the carbon proximal to oxygen is lower in energy than the corresponding shift of the distal carbon.