Lukáš Kobr

Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors. A Surface Inclusion

We describe an approach to regular triangular arrays of dipolar molecular rotors based on insertion of dipolar rotator carrying shafts as guests into channels of a host, tris(o-phenylenedioxy)cyclotriphosphazene (TPP). The rotor guests can either enter the bulk of the host or stay at or near the surface, if a suitable stopper is installed at the end of the shaft. Differential scanning calorimetry, solid-state NMR, and powder X-ray diffraction were used to examine the insertion of a dipolar rotor synthesized for the purpose, 1-n-hexadecyl-12-(2,3-dichlorophenyl)-p-dicarba-closo-dodecaborane, and it was found that it forms a surface inclusion compound. Rotational barriers from 1.2 to 9 kcal/mol were found by dielectric spectroscopy and were attributed to rotors inserted into the surface to different degrees, some rubbing the surface as they turn.

Fast Photodriven Electron Spin Coherence Transfer: A Quantum Gate Based on a Spin Exchange J-Jump

Photoexcitation of the electron donor (D) within a linear, covalent donor-acceptor-acceptor molecule (D-A(1)-A(2)) in which A(1) = A(2) results in sub-nanosecond formation of a spin-coherent singlet radical ion pair state, (1)(D(+•)-A(1)(-•)-A(2)), for which the spin-spin exchange interaction is large: 2J = 79 ± 1 mT. Subsequent laser excitation of A(1)(-•) during the lifetime of (1)(D(+•)-A(1)(-•)-A(2)) rapidly produces (1)(D(+•)-A(1)-A(2)(-•)), which abruptly decreases 2J 3600-fold. Subsequent coherent spin evolution mixes (1)(D(+•)-A(1)-A(2)(-•)) with (3)(D(+•)-A(1)-A(2)(-•)), resulting in mixed states which display transient spin-polarized EPR transitions characteristic of a spin-correlated radical ion pair. These photodriven J-jump experiments show that it is possible to use fast laser pulses to transfer electron spin coherence between organic radical ion pairs and observe the results using an essentially background-free time-resolved EPR experiment.

Inclusion Compound Based Approach to Forming Arrays of Artificial Dipolar Molecular Rotors: A Search for Optimal Rotor Structures

Hexagonal tris(o-phenylenedioxy)cyclotriphosphazene (TPP) is used as ahost for organizing dipolar molecular rotor guests into regular trigonal arrays. Inclusion of molecular rotors with transversely dipolar rotators into TPP channels is followed by solid-state nuclear magnetic resonance, diifferential scanning calorimetry, X-ray diffraction, and dielectric spectroscopy. The more polar of the two rotors does not form an inclusion. The second rotor forms two different inclusions differing in crystallite size and the rotational barriers.

Average orientation of a molecular rotor embedded in a Langmuir-Blodgett monolayer.

A molecular rotor in which a naphthalene rotator is attached through a silicon atom to three fatty acid chains has been synthesized, and Langmuir-Blodgett techniques were used to deposit on silica surfaces monolayers of its calcium salt, both neat and diluted with stearic acid salts. The monolayer films have been characterized by ellipsometry and Fourier transform infrared (FT-IR) grazing-incidence attenuated total internal reflection (GATR) spectroscopy on Si-SiO(2) and by UV-vis absorption spectroscopy on SiO(2). The measurements were combined with calculations of the electronic (INDO/S) and vibrational (DFT) transition moment directions to deduce the average orientation of the rotor molecules, including the naphthalene ring, relative to the surface. In both neat and mixed films, the naphthalene ring is found to preferentially tilt toward the surface, enough that its rotation is most likely hindered. A comparable picture was obtained from molecular mechanics calculations on a mixed film of the naphthalene rotor and stearic acid.

Fast photo-driven electron spin coherence transfer: The effect of electron-nuclear hyperfine coupling on coherence dephasing

Selective photoexcitation of the donor in an electron donor–acceptor1–acceptor2 (D–A1–A2) molecule, in which D = perylene and both A1 and A2 = naphthalene-1,8:4,5-bis(dicarboximide), results in sub-nanosecond formation of a spin-correlated singlet radical pair 1(D+˙–A1−˙–A2) having a large electron spin–spin exchange interaction, 2J, which precludes its observation by transient EPR spectroscopy. Subsequent selective photoexcitation of A1−˙ rapidly produces 1(D+˙–A1–A2−˙), resulting in a dramatic decrease in 2J, which allows coherent spin evolution to mix the singlet (S) radical pair state 1(D+˙–A1–A2−˙) with the T0 triplet sublevel of 3(D+˙–A1–A2−˙) in an applied magnetic field, where B ≫ 2J. A spin-polarized transient EPR spectrum characteristic of the spin-correlated radical pair D+˙–A1–A2−˙ is then observed. The time delay between the two laser pulses was incremented to measure the rate of decoherence in 1(D+˙–A1−˙–A2) in toluene at 295 K, which was found to be 8.1 × 107 s−1. Deuteration of the perylene donor or the toluene solvent decreases the decoherence rate constant of 1(D+˙–A1−˙–A2) to 4.3 × 107 s−1 and 4.6 × 107 s−1, respectively, while deuteration of both the perylene donor and the toluene solvent reduced the decoherence rate constant by more than half to 3.4 × 107 s−1. The data show that decreasing electron-nuclear hyperfine interactions significantly increases the zero quantum coherence lifetime of the spin-correlated radical pair.

Fifth Stereoactive Orbital on Silicon: Relaxation of the Lowest Singlet Excited State of Octamethyltrisilane

We address relaxation pathways in the excited singlet states S(1) of saturated molecules, specifically alkylated oligosilanes. Unlike their longer peralkylated homologues, disilanes and trisilanes do not fluoresce even at low temperatures. An examination of the S(1) potential energy surface of Si(3)Me(8) with density functional (TDDFT, LC-TDDFT), and ab initio (RICC2, RIADC(2)) methods with TZVP basis sets revealed only extremely shallow minima in the vicinity of funnels, accounting for the absence of fluorescence, rapid internal conversion, and photoproducts. Relaxed singlet excited state structures either contain one approximately trigonal bipyramidal Si atom or two that are halfway between tetrahedral and trigonal bipyramidal. Four of the ligands are those that the Si atom had in the ground state. Natural bond orbital analysis suggests that the fifth one is a nonbonding hybrid orbital of the lone-pair type and size intermediate between valence and Rydberg, with an only very small occupancy, yet stereochemically active. The fifth natural hybrid orbital is composed primarily of 4s, 4p, and usually to a lesser degree, also 3d atomic orbitals. The trigonal bipyramidal structure allows an optimal accommodation of the presence of both a negative and a positive charge in the Lewis structures. The excess negative charge on the distorted Si atom is shared between the nonbonding fifth hybrid orbital and σ* antibonding orbitals associated with its bonds. The positive charge resides in an adjacent σ SiSi bond orbital. A Rydberg minimum also occurs on the S(1) surface at the geometry of the radical cation.

Electronic and vibrational transition moment directions in 7-dimethylamino-3-methyl-N-methyl-d3-4-phenylethynylcarbostyril.

We report the synthesis and photophysical characterization of 7-dimethylamino-3-methyl-N-methyl-d(3)-4-phenylethynylcarbostyril, a chromophore of interest as a rotator in surface-mounted molecular rotors. Measurement of UV-vis absorption and fluorescence spectra, steady state fluorescence and excitation anisotropy, and linear dichroism in the IR and UV-vis permitted a determination of absolute vibrational and electronic transition moment directions in this previously unreported chromophore. The first singlet-singlet absorption and fluorescence are polarized perpendicular to the axle of the rotator. Density functional theory calculations of electronic excitation and vibrational frequencies gave results in very good agreement with those observed. Calculated IR transition moment directions showed rather poor agreement with experiment.