Sola-Llano Rebeca, Fujita Yasuhiko, Gómez-Hortigüela Luis, Alfayate Almudena, Uji-I Hiroshi, Fron Eduard, Toyouchi Shuichi, Pérez-Pariente Joaquín, López-Arbeloa Iñigo, Martínez-Martínez Virginia
Departamento de Química Física, Universidad del País Vasco, UPV/EHU, Apartado 644, 48080 Bilbao, Spain.
Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001Heverlee, Belgium.
ACS Photonics. 2018 Jan 17;5(1):151-157. doi: 10.1021/acsphotonics.7b00553. Epub 2017 Oct 19.
A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.
通过结晶包合方法，将一种花青染料（PIC）包合到两种具有不同孔径的一维纳米多孔含镁铝磷酸盐中（分别具有AFI和ATS沸石结构类型的MgAPO-5和MgAPO-36，其圆柱形通道直径为7.3 Å，椭圆形通道为6.7 Å×7.5 Å）。由于MgAPO骨架的孔径不同，不同的J-聚集体具有不同的光物理特性，在MgAPO-5和MgAPO-36中，发射带分别位于565 nm和610 nm处。计算结果表明，MgAPO-36样品纳米通道内的J-聚集体比MgAPO-5中的具有更线性的几何结构，这是由于前者的环境限制更大。出于同样的原因，MgAPO-36通道内550 nm处PIC单体的荧光也被激活。由于荧光PIC物种在MgAPO-36晶体中的策略性分布（一边是单体，另一边是具有有趣发射特性的J-聚集体），获得了一个高效的单向天线系统。通过沿数十微米距离的远程激发实验，证明了从单体到J-聚集体的单向能量转移过程。
