Multirotations of (anilinium)(crown-6) supramolecular cation structure in magnetic salt of [Ni(dmit)2]-.
ABSTRACT A solid-state dynamic supramolecular structure consisting of (anilinium)(crown-6) was arranged as the cation in a salt of [Ni(dmit)2]- (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate). With the ammonium moiety of anilinium located within the cavity of crown-6, a hydrogen-bonded supramolecular structure is formed, with an orthogonal arrangement between the pi plane of anilinium and the mean O6 plane of crown-6. In this supramolecular cation, both anilinium and crown-6 act as dynamic units with different rotational modes in the solid state. The uniform stacks of cations form an antiparallel arrangement, thus producing a layer structure. Sufficient space for the 180 degree flip-flop motion of the phenyl ring and the rotation of crown-6 was observed in the cation layer. Thermally activated 180 degree flip-flop motions, with a frequency of 6 MHz at room temperature and an activation energy of 31 kJ mol(-1), were confirmed by temperature-dependent 2H NMR spectra of ([D5]anilinium)-(crown-6)[Ni(dmit)2]. A double-minimum potential for the molecular rotation of anilinium, with a barrier of approximately 40 kJ mol(-1), was indicated by ab initio calculations. The wide-line 1H NMR spectra indicated a thermally activated rotation of crown-6 at temperatures above 250 K. Therefore, multiple molecular motions of the 180 degree flip-flop motion of the phenyl ring and the rotation of crown-6 occur simultaneously in the solid state. The temperature-dependent dielectric constants revealed that the molecular motion of crown-6, other than the flip-flop motion, dominates the dielectric response in the measured temperature and frequency range.
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ABSTRACT: Complex molecular machinery may be envisioned as densely packed, multicomponent, self-assembling systems built with high structural precision to control the dynamics of one or more internal degrees of freedom. With molecular gyroscopes as a test, we describe a general strategy to design crystals capable of supporting structurally programmed molecular motions, a practical approach to their synthesis, convenient strategies to characterize their solid-state dynamics, and potential applications based on polar structures responding collectively to external fields.Accounts of Chemical Research 07/2006; 39(6):413-22. · 20.83 Impact Factor
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ABSTRACT: The conversion of energy into controlled motion plays an important role in both man-made devices and biological systems. The principles of operation of conventional motors are well established, but the molecular processes used by 'biological motors' such as muscle fibres, flagella and cilia to convert chemical energy into co-ordinated movement remain poorly understood. Although 'brownian ratchets' are known to permit thermally activated motion in one direction only, the concept of channelling random thermal energy into controlled motion has not yet been extended to the molecular level. Here we describe a molecule that uses chemical energy to activate and bias a thermally induced isomerization reaction, and thereby achieve unidirectional intramolecular rotary motion. The motion consists of a 120 degrees rotation around a single bond connecting a three-bladed subunit to the bulky remainder of the molecule, and unidirectional motion is achieved by reversibly introducing a tether between the two units to energetically favour one of the two possible rotation directions. Although our system does not achieve continuous and fast rotation, the design principles that we have used may prove relevant for a better understanding of biological and synthetic molecular motors producing unidirectional rotary motion.Nature 10/1999; 401(6749):150-2. · 38.60 Impact Factor
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ABSTRACT: Attempts to fabricate mechanical devices on the molecular level have yielded analogues of rotors, gears, switches, shuttles, turnstiles and ratchets. Molecular motors, however, have not yet been made, even though they are common in biological systems. Rotary motion as such has been induced in interlocked systems and directly visualized for single molecules, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon-carbon double bond in a chiral, helical alkene, with each 360 degrees rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and the presence of two chiral centres are essential for the observed monodirectional behaviour of the molecular motor. Two light-induced cis-trans isomerizations are each associated with a 180 degrees rotation around the carbon-carbon double bond and are each followed by thermally controlled helicity inversions, which effectively block reverse rotation and thus ensure that the four individual steps add up to one full rotation in one direction only. As the energy barriers of the helicity inversion steps can be adjusted by structural modifications, chiral alkenes based on our system may find use as basic components for 'molecular machinery' driven by light.Nature 10/1999; 401(6749):152-5. · 38.60 Impact Factor