Freeley Mark, Attanzio Antonio, Cecconello Alessandro, Amoroso Giuseppe, Clement Pierrick, Fernandez Gustavo, Gesuele Felice, Palma Matteo
School of Biological and Chemical Sciences Materials Research Institute and Institute of Bioengineering Queen Mary University of London Mile End Road London E1 4NS UK.
Organisch-Chemisches Institut Westfälische Wilhelms-Universität Münster Corrensstrasse 40 48149 Münster Germany.
Adv Sci (Weinh). 2018 Aug 14;5(10):1800596. doi: 10.1002/advs.201800596. eCollection 2018 Oct.
Herein a strategy is presented for the assembly of both static and stimuli-responsive single-molecule heterostructures, where the distance and electronic coupling between an individual functional nanomoiety and a carbon nanostructure are tuned via the use of DNA linkers. As proof of concept, the formation of 1:1 nanohybrids is controlled, where single quantum dots (QDs) are tethered to the ends of individual carbon nanotubes (CNTs) in solution with DNA interconnects of different lengths. Photoluminescence investigations-both in solution and at the single-hybrid level-demonstrate the electronic coupling between the two nanostructures; notably this is observed to progressively scale, with charge transfer becoming the dominant process as the linkers length is reduced. Additionally, stimuli-responsive CNT-QD nanohybrids are assembled, where the distance and hence the electronic coupling between an individual CNT and a single QD are dynamically modulated via the addition and removal of potassium (K) cations; the system is further found to be sensitive to K concentrations from 1 pM to 25 × 10 m. The level of control demonstrated here in modulating the electronic coupling of reconfigurable single-molecule heterostructures, comprising an individual functional nanomoiety and a carbon nanoelectrode, is of importance for the development of tunable molecular optoelectronic systems and devices.
本文提出了一种用于组装静态和刺激响应性单分子异质结构的策略，其中通过使用DNA连接体来调节单个功能纳米部分与碳纳米结构之间的距离和电子耦合。作为概念验证，控制了1:1纳米杂化物的形成，其中单个量子点（QD）通过不同长度的DNA互连体连接到溶液中单个碳纳米管（CNT）的末端。在溶液中和单杂化水平上的光致发光研究证明了两种纳米结构之间的电子耦合；值得注意的是，观察到这种耦合会逐渐变化，随着连接体长度的减小，电荷转移成为主导过程。此外，组装了刺激响应性CNT-QD纳米杂化物，其中通过添加和去除钾（K）阳离子来动态调节单个CNT与单个QD之间的距离以及因此的电子耦合；进一步发现该系统对1 pM至25×10 m的K浓度敏感。本文展示的在调节包含单个功能纳米部分和碳纳米电极的可重构单分子异质结构的电子耦合方面的控制水平，对于可调谐分子光电子系统和器件的开发具有重要意义。
