New class of metal bound molecular switches involving H-tautomerism.
نویسندگان
چکیده
A potential end-point in the miniaturization of electronic devices lies in the field of molecular electronics, where molecules perform the function of single components. To date, hydrogen tautomerism in unimolecular switches has been restricted to the central macrocycle of porphyrin-type molecules. The present work reveals how H-tautomerism is the mechanism for switching in substituted quinone derivatives, a novel class of molecules with a different chemical structure. We hence reveal that the previous restrictions applying to tautomeric molecular switches bound to a surface are not valid in general. The activation energy of switching in a prototypical quinone derivative is determined using inelastic electron tunneling. Through computational modeling, we show that the mechanism underlying this process is tautomerization of protons belonging to two amino groups. This switching property is retained upon functionalization by the addition of side groups, meaning that the switch can be chemically modified to fit specific applications.
منابع مشابه
Bidirectional photoswitching of magnetic properties at room temperature: ligand-driven light-induced valence tautomerism† †Electronic supplementary information (ESI) available: Derivation of the non-linear regression fitting functions, crystallographic details, magnetization and electrochemical data, EPR and electronic absorption spectra. CCDC 1015850–1015852 and 1058866. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00130g
Valence tautomeric (VT) metal complexes are highly promising bistable molecular compounds for applications as molecular switches in molecular electronics and spintronics. Although VT species can be switched with light, the photoswitching in all reported systems requires very low temperatures (usually below 20 K) because photoinduced states are highly unstable at room temperature. The thermal in...
متن کاملThermodynamic Study and Total Energy Calculation for three systems of Enol↔Keto Tautomerism
Using Hartree–Fock (HF) and ِِDensity Functional Theory (DFT) calculations the thermodynamic properties such as thermal energy , , thermal enthalpy , , thermal entropy , , thermal Gibbs free energy , , heat capacity ,Cv, and molecular structures of several species involving in keto↔enol tautomerism related to acetaldehyde (A), 5,5-dimethyl-1,3-cyclohexanedione (dimedone) and acetylacetone (AA) h...
متن کاملOptically and thermally induced molecular switching processes at metal surfaces.
Using light to control the switching of functional properties of surface-bound species is an attractive strategy for the development of new technologies with possible applications in molecular electronics and functional surfaces and interfaces. Molecular switches are promising systems for such a route, since they possess the ability to undergo reversible changes between different molecular stat...
متن کاملDFT Study of Kinetic and Thermodynamic Parameters of Tautomerism in 4−acyl Pyrazolone
In the present work, DFT calculations are employed to obtain the optimized structures of 4- acyl pyrazolone tautomers (19 tautomers) using B3LYP/6-311++G** calculations. In addition, molecular parameters, IR frequencies and relative energies are extracted for all tautomers. The existence of aromatic ring, keto tautomer (versus enol tautomer), N-H bond (versus C-H bond) and C=N double bond (vers...
متن کاملA Bound for the Nilpotency Class of a Lie Algebra
In the present paper, we prove that if L is a nilpotent Lie algebra whose proper subalge- bras are all nilpotent of class at most n, then the class of L is at most bnd=(d 1)c, where b c denotes the integral part and d is the minimal number of generators of L.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Nano letters
دوره 14 2 شماره
صفحات -
تاریخ انتشار 2014