Schwich Torsten, Barlow Adam, Cifuentes Marie P, Szeremeta Janusz, Samoc Marek, Humphrey Mark G
Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wroclaw University of Science and Technology, Wroclaw, 50-370, Poland.
Chemistry. 2017 Jun 22;23(35):8395-8399. doi: 10.1002/chem.201702039. Epub 2017 Jun 1.
Very large molecular two- and three-photon absorption cross-sections are achieved by appending ligated bis(diphosphine)ruthenium units to oligo(p-phenyleneethynylene) (OPE)-based "stars" with arms up to 7 phenyleneethynylene (PE) units in length. Extremely large three- and four-photon absorption cross-sections, through the telecommunications wavelengths range and beyond, are obtained for these complexes upon optimizing OPE length and the ruthenium-coordinated peripheral ligand. Multi-photon absorption (MPA) cross-sections are optimized with stars possessing arms 2 PE units in length. Peripheral ligand variation modifies MPA merit and, in particular, 4-nitrophenylethynyl ligand incorporation enhances maximal MPA values and "switches on" four-photon absorption (4PA) in these low molecular-weight complexes. The 4-nitrophenylethynyl-ligated 2PE-armed star possesses a maximal four-photon absorption cross-section of 1.8×10 cm s at 1750 nm, and significant MPA activity extending beyond 2000 nm.
通过将连接的双（二膦）钌单元附加到基于寡聚（对苯撑乙炔）（OPE）的“星型”分子上，实现了非常大的分子双光子和三光子吸收截面，这些“星型”分子的臂长可达7个亚苯基乙炔（PE）单元。在优化OPE长度和钌配位的外围配体后，这些配合物在电信波长范围及更长波长范围内获得了极大的三光子和四光子吸收截面。多光子吸收（MPA）截面通过臂长为2个PE单元的“星型”分子进行优化。外围配体的变化改变了MPA性能，特别是引入4-硝基苯乙炔配体提高了最大MPA值，并在这些低分子量配合物中“开启”了四光子吸收（4PA）。带有4-硝基苯乙炔连接的2PE臂“星型”分子在1750 nm处具有1.8×10⁻⁵⁰ cm⁸ s⁴的最大四光子吸收截面，并且在超过2000 nm处具有显著的MPA活性。
