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Towards a Rational Design of Molecular Switches and Sensors from their Basic Building Blocks

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Molecular Machines

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 262))

Abstract

A fundamental understanding of the thermodynamics and kinetics of mechanically interlocked molecules, such as [2]rotaxanes, will contribute to a more rational design of new molecular machines. This Chapter describes the influence of chemical modifications and the role of the physical environment on the ground state thermodynamics and the shuttling and switching kinetics of several tetrathiafulvalene- and 1,5-dioxynaphthalene-containing [2]rotaxanes. A comparison between the properties of these bistable rotaxanes and model host-guest complexes of the corresponding π-electron donating recognition units with the π-electron accepting cyclophane, cyclobis(paraquat-p-phenylene), has been made, resulting in useful guidelines for the design of new bistable rotaxanes with specific, desirable physical performances.

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Abbreviations

BPTTF:

bis(pyrrolo)tetrathiafulvalene

CT:

charge-transfer

CV:

cyclic voltammetry

E ox :

oxidation potential

Et:

ethyl

ΔG:

free energy difference

ΔGa:

free energy of association

ΔG‡:

free energy of activation

ΔH:

enthalpy difference

ΔH‡:

enthalpy of activation

ΔS:

entropy difference

ΔS‡:

entropy of activation

DEG:

diethylene glycol

DNP:

1,5-dioxynaphthalene

g:

gram(s)

GSCC:

ground-state co-conformation

h :

Planck constant (6.262 × 10− J s)

I :

current

ITC:

isothermal titration calorimetry

J:

Joule

k :

rate constant

K:

Kelvin

K :

constant

K a :

association constant

k B :

Boltzmann constant (1.381 × 10− m2 kg s−2 K−1)

K eq :

equilibrium constant (NGSCC/NMSCC)

M:

molarity

Me:

methyl

min.:

minute(s)

mol:

mole(s)

MPTTF:

mono(pyrrolo)tetrathiafulvalene

MSCC:

metastable state co-conformation

MSTJ:

molecular-switch tunnel junction

N :

population

NEMS:

nanoelectromechanical systems

NMR:

nuclear magnetic resonance

PES:

potential energy surface

R :

universal gas constant (8.3144 J mol−1 K−1)

r.t.:

room temperature

s:

second(s)

SAM:

self-assembled monolayer

T :

temperature

TRISPHAT−:

tris(tetrachlorobenzenediolato)phosphate(V)

TTF:

tetrathiafulvalene

UV/Vis:

ultraviolet/visible

VT:

variable temperature

VTT CV:

variable time and temperature cyclic voltammetry

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Acknowledgments

This research was funded by the National Science Foundation (NSF), the Molectronics Program of the Defense Advanced Research Project Agency (DARPA), the Microelectronics Advance Research Corporation (MARCO) and its Focus Center on Functional Engineered NanoArchitectonics (FENA) and the Center for Nanoscale Innovation for Defense (CNID) in the US. NNPM acknowledges the Netherlands Organization for Scientific Research (NWO) for a TALENT fellowship.

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Authors and Affiliations

  1. California NanoSystems Institute and Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, 90095--1569, Los Angeles, CA, USA

    Nicolle N. P. Moonen, Amar H. Flood, Juan M. Fernández & J. Fraser Stoddart

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  1. Nicolle N. P. Moonen
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  2. Amar H. Flood
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  3. Juan M. Fernández
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  4. J. Fraser Stoddart
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Correspondence to J. Fraser Stoddart .

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T. Ross Kelly

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Moonen, N.N.P., Flood, A.H., Fernández, J.M., Stoddart, J.F. Towards a Rational Design of Molecular Switches and Sensors from their Basic Building Blocks. In: Kelly, T.R. (eds) Molecular Machines. Topics in Current Chemistry, vol 262. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_009

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