Yui Tatsuto, Takeda Hiroyuki, Ueda Yutaro, Sekizawa Keita, Koike Kazuhide, Inagaki Shinji, Ishitani Osamu
Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology , 2-12-1-NE1 O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
ACS Appl Mater Interfaces. 2014 Feb 12;6(3):1992-8. doi: 10.1021/am405065a. Epub 2014 Jan 30.
A new method for the hybridization of a ruthenium(II) polypyridyl complex (Ru(bpy)2((CH2PO3H2)2-bpy) (RuP2(2+): bpy =2,2'-bipyridine; (CH2PO3H2)2-bpy =2,2'-bipyridine-4,4'di(metylphosphonic acid)) with biphenylene-bearing periodic mesoporous organosilica (Bp-PMO made from 4,4'bis(triethoxysilyl)biphenyl [(C2H5O)3Si-(C6H4)2-Si(OC2H5)3]) was developed. Efficient and secure fixation of the ruthenium(II) complex with methylphosphonic acid groups (RuP2(2+)) in the mesopores of Bp-PMO occurred. This method introduced up to 660 μmol of RuP2(2+) in 1 g of Bp-PMO. Two modes of adsorption of RuP2(2+) in the mesopores of Bp-PMO were observed: one is caused by the chemical interaction between the methylphosphonic acid groups of RuP2(2+) and the silicate moieties of Bp-PMO and the other is attributed to aggregation of the RuP2(2+) complexes. In the case of the former mode, adsorbed RuP2(2+) (up to 80-100 μmol g(-1)) did not detach from Bp-PMO after washing with acetonitrile, dimethylformamide, or even water. Emission from the excited biphenylene (Bp) units was quantitatively quenched by the adsorbed RuP2(2+) molecules in cases where more than 60 μmol g(-1) of RuP2(2+) was adsorbed, and emission from RuP2(2+) was observed. Quantitative emission measurements indicated that emission from approximately 100 Bp units can be completely quenched by only one RuP2(2+) molecule in the mesopore, and photons absorbed by approximately 400 Bp units are potentially accumulated in one RuP2(2+) molecule.
开发了一种将钌（II）多吡啶配合物（Ru(bpy)2((CH2PO3H2)2-bpy)（RuP2(2+)：bpy = 2,2'-联吡啶；(CH2PO3H2)2-bpy = 2,2'-联吡啶-4,4'-二（甲基膦酸））与含联亚苯基的周期性介孔有机硅（由4,4'-双（三乙氧基硅基）联苯[(C2H5O)3Si-(C6H4)2-Si(OC2H5)3]制成的Bp-PMO）进行杂交的新方法。钌（II）配合物与甲基膦酸基团（RuP2(2+)）在Bp-PMO的介孔中实现了高效且稳定的固定。该方法在1 g Bp-PMO中引入了高达660 μmol的RuP2(2+)。观察到RuP2(2+)在Bp-PMO介孔中的两种吸附模式：一种是由RuP2(2+)的甲基膦酸基团与Bp-PMO的硅酸盐部分之间的化学相互作用引起的，另一种归因于RuP2(2+)配合物的聚集。在前一种模式下，用乙腈、二甲基甲酰胺甚至水洗涤后，吸附的RuP2(2+)（高达80 - 100 μmol g(-1)）不会从Bp-PMO上脱离。在吸附的RuP2(2+)超过60 μmol g(-1)的情况下，被吸附的RuP2(2+)分子会定量猝灭激发的联亚苯基（Bp）单元的发射，并观察到RuP2(2+)的发射。定量发射测量表明，介孔中仅一个RuP2(2+)分子就能完全猝灭大约100个Bp单元的发射，并且大约400个Bp单元吸收的光子可能会聚集在一个RuP2(2+)分子中。
