Hu Peiguang, Song Yang, Rojas-Andrade Mauricio Daniel, Chen Shaowei
Department of Chemistry and Biochemistry, University of California , 1156 High Street, Santa Cruz, California 95064, United States.
Langmuir. 2014 May 13;30(18):5224-9. doi: 10.1021/la5001123. Epub 2014 Apr 30.
Platinum nanoparticles functionalized with 4-ethynylphenylboronic acid pinacol ester (Pt-EPBAPE) were successfully synthesized by a simple chemical reduction procedure. Because of the formation of conjugated metal-ligand interfacial linkages, the resulting nanoparticles exhibited apparent photoluminescence arising from the nanoparticle-bound acetylene moieties that behaved analogously to diacetylene derivatives. Interestingly, the nanoparticle photoluminescence was markedly quenched upon the addition of fluoride ions (F⁻). In contrast, significantly less or virtually no change was observed with a variety of other anions such as Cl⁻, Br⁻, I⁻, NO₃⁻, HSO₄⁻, H₂PO₄⁻, ClO₄⁻, BF₄⁻, and PF₆⁻. The high selectivity toward fluoride ion is most probably because of the strong specific affinity of the boronic acid moiety to fluoride. The formation of B-F bonds led to the conversion of Bsp² to Bsp³, as manifested in ¹¹B NMR measurements, which impacted the intraparticle charge delocalization between the particle-bound acetylene moieties and hence the nanoparticle photoluminescence.
通过简单的化学还原法成功合成了用4-乙炔基苯硼酸频哪醇酯（Pt-EPBAPE）功能化的铂纳米颗粒。由于共轭金属-配体界面键的形成，所得纳米颗粒表现出明显的光致发光，这源于与纳米颗粒结合的乙炔部分，其行为类似于双乙炔衍生物。有趣的是，加入氟离子（F⁻）后，纳米颗粒的光致发光明显猝灭。相比之下，对于多种其他阴离子，如Cl⁻、Br⁻、I⁻、NO₃⁻、HSO₄⁻、H₂PO₄⁻、ClO₄⁻、BF₄⁻和PF₆⁻，观察到的变化明显较少或几乎没有变化。对氟离子的高选择性很可能是由于硼酸部分对氟的强特异性亲和力。B-F键的形成导致Bsp²向Bsp³的转变，如¹¹B NMR测量所示，这影响了颗粒内乙炔部分之间的电荷离域，从而影响纳米颗粒的光致发光。
