Crystalline Supramolecular Gyroscope with a Water Molecule as an Ultrasmall Polar Rotator Modulated by Charge-Assisted Hydrogen Bonds.

A new strategy for the construction of crystalline molecular rotors is presented. The combination of a conformation-modifiable macrocyclic host and two cooperative guests affords one supramolecular gyroscope-like compound, (t-BuNH3)(18-crown-6)[ZnCl3(H2O)], in which the coordinated water molecule functions as an ultrasmall polar rotator, revealed by its significant dielectric relaxation and the molecular dynamics simulations. In addition, such a compound can reversibly undergo a polar-to-polar phase transition triggered by the changed conformation of the 18-crown-6 host, leading to a switchable on/off rotation of water molecule, well controlled by strength and direction of charge-assisted hydrogen bonds.

[1]  P. Metrangolo,et al.  Rotational Dynamics of Diazabicyclo[2.2.2]octane in Isomorphous Halogen-Bonded Co-crystals: Entropic and Enthalpic Effects. , 2017, Journal of the American Chemical Society.

[2]  P. Sozzani,et al.  Molecular Rotors Built in Porous Materials. , 2016, Accounts of chemical research.

[3]  Leyong Wang,et al.  Gyroscope-Like Complexes Based on Dibridgehead Diphosphine Cages That Are Accessed by Three-Fold Intramolecular Ring Closing Metatheses and Encase Fe(CO)3, Fe(CO)2(NO)(+), and Fe(CO)3(H)(+) Rotators. , 2016, Journal of the American Chemical Society.

[4]  Lan Huong Lai,et al.  Crystal Fluidity Reflected by Fast Rotational Motion at the Core, Branches, and Peripheral Aromatic Groups of a Dendrimeric Molecular Rotor. , 2016, Journal of the American Chemical Society.

[5]  P. Metrangolo,et al.  Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding. , 2015, Journal of the American Chemical Society.

[6]  Sundus Erbas-Cakmak,et al.  Artificial Molecular Machines , 2015, Chemical reviews.

[7]  T. Uemura,et al.  Molecular-Level Studies on Dynamic Behavior of Oligomeric Chain Molecules in Porous Coordination Polymers , 2015 .

[8]  J. Nitschke,et al.  Stimuli-Responsive Metal-Ligand Assemblies. , 2015, Chemical reviews.

[9]  T. Inabe,et al.  Molecular motion, dielectric response, and phase transition of charge-transfer crystals: acquired dynamic and dielectric properties of polar molecules in crystals. , 2015, Journal of the American Chemical Society.

[10]  Chun He,et al.  Switchable guest molecular dynamics in a perovskite-like coordination polymer toward sensitive thermoresponsive dielectric materials. , 2015, Angewandte Chemie.

[11]  P. Lunkenheimer,et al.  Dielectric Relaxation Processes, Electronic Structure, and Band Gap Engineering of MFU‐4‐type Metal‐Organic Frameworks: Towards a Rational Design of Semiconducting Microporous Materials , 2014 .

[12]  P. Sozzani,et al.  Engineering switchable rotors in molecular crystals with open porosity. , 2014, Journal of the American Chemical Society.

[13]  L. Long,et al.  Modulating the rotation of a molecular rotor through hydrogen-bonding interactions between the rotator and stator. , 2013, Angewandte Chemie.

[14]  K. Yamaguchi,et al.  Order-disorder transition of dipolar rotor in a crystalline molecular gyrotop and its optical change. , 2013, Journal of the American Chemical Society.

[15]  M. Garcia‐Garibay,et al.  Amphidynamic crystals of a steroidal bicyclo[2.2.2]octane rotor: a high symmetry group that rotates faster than smaller methyl and methoxy groups. , 2013, Journal of the American Chemical Society.

[16]  J. Michl,et al.  Crystalline arrays of pairs of molecular rotors: correlated motion, rotational barriers, and space-inversion symmetry breaking due to conformational mutations. , 2013, Journal of the American Chemical Society.

[17]  K. Yamaguchi,et al.  A molecular balloon: expansion of a molecular gyrotop cage due to rotation of the phenylene rotor. , 2012, Journal of the American Chemical Society.

[18]  Kristopher J Harris,et al.  Metal-organic frameworks with dynamic interlocked components. , 2012, Nature chemistry.

[19]  C. Serre,et al.  Structure and Dynamics of the Functionalized MOF Type UiO-66(Zr): NMR and Dielectric Relaxation Spectroscopies Coupled with DFT Calculations , 2012 .

[20]  M. Garcia‐Garibay,et al.  Crystalline molecular machines: function, phase order, dimensionality, and composition. , 2012, Chemical Society reviews.

[21]  L. Long,et al.  Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture , 2011, Proceedings of the National Academy of Sciences.

[22]  M. Eddaoudi,et al.  Highly porous ionic rht metal-organic framework for H2 and CO2 storage and separation: a molecular simulation study. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  A. Datta,et al.  Molecular Rotor Inside a Phosphonate Cavitand: Role of Supramolecular Interactions , 2010 .

[24]  Jianwen Jiang,et al.  Upgrade of natural gas in rhozeolite-like metal–organic framework and effect of water: a computational study , 2009 .

[25]  Josef Michl,et al.  Molecular rotors and motors: recent advances and future challenges. , 2009, ACS nano.

[26]  Takayoshi Nakamura,et al.  Supramolecular approach for solid state Brownian rotators. , 2008, Dalton transactions.

[27]  Francesco Zerbetto,et al.  Synthetic molecular motors and mechanical machines. , 2007, Angewandte Chemie.

[28]  K. Houk,et al.  Importance of correlated motions on the low barrier rotational potentials of crystalline molecular gyroscopes. , 2007, Journal of the American Chemical Society.

[29]  M. Garcia‐Garibay,et al.  Rotational dynamics in a crystalline molecular gyroscope by variable-temperature 13C NMR, 2H NMR, X-ray diffraction, and force field calculations. , 2007, Journal of the American Chemical Society.

[30]  M. Garcia‐Garibay,et al.  Crystalline molecular machines: a quest toward solid-state dynamics and function. , 2006, Accounts of chemical research.

[31]  Takanori Shima,et al.  Gyroscope-like molecules consisting of PdX2/PtX2 rotators encased in three-spoke stators: synthesis via alkene metathesis, and facile substitution and demetalation. , 2006, Journal of the American Chemical Society.

[32]  Dominik Horinek,et al.  Artificial molecular rotors. , 2005, Chemical reviews.

[33]  Takanori Shima,et al.  Molecular gyroscopes: [Fe(CO)(3)] and [Fe(CO)(2)(NO)](+) rotators encased in three-spoke stators; facile assembly by alkene metatheses. , 2004, Angewandte Chemie.

[34]  M. Garcia‐Garibay,et al.  Molecular compasses and gyroscopes with polar rotors: synthesis and characterization of crystalline forms. , 2003, Journal of the American Chemical Society.

[35]  M. Garcia‐Garibay,et al.  Molecular "compasses" and "gyroscopes". I. Expedient synthesis and solid state dynamics of an open rotor with a bis(triarylmethyl) frame. , 2002, Journal of the American Chemical Society.

[36]  N. Harada,et al.  Light-driven monodirectional molecular rotor , 2022 .

[37]  Georges Wipff,et al.  High temperature annealed molecular dynamics simulations as a tool for conformational sampling. Application to the bicyclic “222” cryptand , 1990 .