Photoresponsive Biomimetic Functions by Light-Driven Molecular Motors in Three Dimensionally Printed Liquid Crystal Elastomers.

Despite the fascinating developments in design and synthesis of artificial molecular machines operating at the nanoscales, translating molecular motion along multiple length scales and inducing mechanical motion of a three-dimensional macroscopic entity remains an important challenge. The key to addressing this amplification of motion relies on the effective organization of molecular machines in a well-defined environment. By taking advantage of long-range orientational order and hierarchical structures of liquid crystals and unidirectional rotation of light-driven molecular motors, we report here photoresponsive biomimetic functions of liquid crystal elastomers (LCEs) by the repetitive unidirectional rotation of molecular motors using 3D printing. Molecular motors were built in the main chain of liquid crystals oligomers to serve as photoactuators. The oligomers were then used as the ink, and liquid crystal elastomers with different morphologies were printed. The obtained LCEs are able to conduct multiple types of motions including bending, helical coiling, closing of petals, and flipping of wings of a butterfly upon UV illumination, which paves the way for future design of responsive materials with enhanced complex actuating functions.

Photo-responsive functional materials based on light-driven molecular motors.

In the past two decades, the research and development of light-triggered molecular machines have mainly focused on developing molecular devices at the nanoscale. A key scientific issue in the field is how to amplify the controlled motion of molecules at the nanoscale along multiple length scales, such as the mesoscopic or the macroscopic scale, or in a more practical perspective, how to convert molecular motion into changes of properties of a macroscopic material. Light-driven molecular motors are able to perform repetitive unidirectional rotation upon irradiation, which offers unique opportunities for responsive macroscopic systems. With several reviews that focus on the design, synthesis and operation of the motors at the nanoscale, photo-responsive macroscopic materials based on light-driven molecular motors have not been comprehensively summarized. In the present review, we first discuss the strategy of confining absolute molecular rotation into relative rotation by grafting motors on surfaces. Secondly, examples of self-assemble motors in supramolecular polymers with high internal order are illustrated. Moreover, we will focus on building of motors in a covalently linked system such as polymeric gels and polymeric liquid crystals to generate complex responsive functions. Finally, a perspective toward future developments and opportunities is given. This review helps us getting a more and more clear picture and understanding on how complex movement can be programmed in light-responsive systems and how man-made adaptive materials can be invented, which can serve as an important guideline for further design of complex and advanced responsive materials.

Phototriggered Complex Motion by Programmable Construction of Light-Driven Molecular Motors in Liquid Crystal Networks.

Recent developments in artificial molecular machines have enabled precisely controlled molecular motion, which allows several distinct mechanical operations at the nanoscale. However, harnessing and amplifying molecular motion along multiple length scales to induce macroscopic motion are still major challenges and comprise an important next step toward future actuators and soft robotics. The key to addressing this challenge relies on effective integration of synthetic molecular machines in a hierarchically aligned structure so numerous individual molecular motions can be collected in a cooperative way and amplified to higher length scales and eventually lead to macroscopic motion. Here, we report the complex motion of liquid crystal networks embedded with molecular motors triggered by single-wavelength illumination. By design, both racemic and enantiomerically pure molecular motors are programmably integrated into liquid crystal networks with a defined orientation. The motors have multiple functions acting as cross-linkers, actuators, and chiral dopants inside the network. The collective rotary motion of motors resulted in multiple types of motion of the polymeric film, including bending, wavy motion, fast unidirectional movement on surfaces, and synchronized helical motion with different handedness, paving the way for the future design of responsive materials with enhanced complex functions.

Photo-responsive Helical Motion by Light-Driven Molecular Motors in a Liquid-Crystal Network.

Controlling sophisticated motion by molecular motors is a major goal on the road to future actuators and soft robotics. Taking inspiration from biological motility and mechanical functions common to artificial machines, responsive small molecules have been used to achieve macroscopic effects, however, translating molecular movement along length scales to precisely defined linear, twisting and rotary motions remain particularly challenging. Here, we present the design, synthesis and functioning of liquid-crystal network (LCN) materials with intrinsic rotary motors that allow the conversion of light energy into reversible helical motion. In this responsive system the photochemical-driven molecular motor has a dual function operating both as chiral dopant and unidirectional rotor amplifying molecular motion into a controlled and reversible left- or right-handed macroscopic twisting movement. By exploiting the dynamic chirality, directionality of motion and shape change of a single motor embedded in an LC-network, complex mechanical motions including bending, walking and helical motion, in soft polymer materials are achieved which offers fascinating opportunities toward inherently photo-responsive materials.