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      Great expectations: can artificial molecular machines deliver on their promise?

      Chemical Society Reviews

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          Abstract

          The development and fabrication of mechanical devices powered by artificial molecular machines is one of the contemporary goals of nanoscience. Before this goal can be realized, however, we must learn how to control the coupling/uncoupling to the environment of individual switchable molecules, and also how to integrate these bistable molecules into organized, hierarchical assemblies that can perform significant work on their immediate environment at nano-, micro- and macroscopic levels. In this tutorial review, we seek to draw an all-important distinction between artificial molecular switches which are now ten a penny-or a dime a dozen-in the chemical literature and artificial molecular machines which are few and far between despite the ubiquitous presence of their naturally occurring counterparts in living systems. At the single molecule level, a prevailing perspective as to how machine-like characteristics may be achieved focuses on harnessing, rather than competing with, the ineluctable effects of thermal noise. At the macroscopic level, one of the major challenges inherent to the construction of machine-like assemblies lies in our ability to control the spatial ordering of switchable molecules-e.g., into linear chains and then into muscle-like bundles-and to influence the cross-talk between their switching kinetics. In this regard, situations where all the bistable molecules switch synchronously appear desirable for maximizing mechanical power generated. On the other hand, when the bistable molecules switch "out of phase," the assemblies could develop intricate spatial or spatiotemporal patterns. Assembling and controlling synergistically artificial molecular machines housed in highly interactive and robust architectural domains heralds a game-changer for chemical synthesis and a defining moment for nanofabrication.

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          Most cited references83

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          Synthetic molecular motors and mechanical machines.

          The widespread use of controlled molecular-level motion in key natural processes suggests that great rewards could come from bridging the gap between the present generation of synthetic molecular systems, which by and large rely upon electronic and chemical effects to carry out their functions, and the machines of the macroscopic world, which utilize the synchronized movements of smaller parts to perform specific tasks. This is a scientific area of great contemporary interest and extraordinary recent growth, yet the notion of molecular-level machines dates back to a time when the ideas surrounding the statistical nature of matter and the laws of thermodynamics were first being formulated. Here we outline the exciting successes in taming molecular-level movement thus far, the underlying principles that all experimental designs must follow, and the early progress made towards utilizing synthetic molecular structures to perform tasks using mechanical motion. We also highlight some of the issues and challenges that still need to be overcome.
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            Secondary building units, nets and bonding in the chemistry of metal-organic frameworks.

            This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal-organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal-organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).
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              Making molecular machines work.

              In this review we chart recent advances in what is at once an old and very new field of endeavour--the achievement of control of motion at the molecular level including solid-state and surface-mounted rotors, and its natural progression to the development of synthetic molecular machines. Besides a discussion of design principles used to control linear and rotary motion in such molecular systems, this review will address the advances towards the construction of synthetic machines that can perform useful functions. Approaches taken by several research groups to construct wholly synthetic molecular machines and devices are compared. This will be illustrated with molecular rotors, elevators, valves, transporters, muscles and other motor functions used to develop smart materials. The demonstration of molecular machinery is highlighted through recent examples of systems capable of effecting macroscopic movement through concerted molecular motion. Several approaches to illustrate how molecular motor systems have been used to accomplish work are discussed. We will conclude with prospects for future developments in this exciting field of nanotechnology.
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                Author and article information

                Journal
                22116531
                10.1039/c1cs15262a

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