We examine the fluorescence anisotropy of rod-shaped guests held inside the channels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) host nanocrystals, characterized by powder X-ray diffraction and solid state NMR spectroscopy. We address two issues: (i) are light polarization measurements on an aqueous colloidal solution of TPP nanocrystals meaningful, or is depolarization by scattering excessive? (ii) Can measurements of the rotational mobility of the included guests be performed at low enough loading levels to suppress depolarization by intercrystallite energy transfer? We find that meaningful measurements are possible and demonstrate that the long axis of molecular rods included in TPP channels performs negligible vibrational motion.

• Publikační typ
• časopisecké články MeSH

Classical molecular dynamics is applied to the rotation of a dipolar molecular rotor mounted on a square grid and driven by rotating electric field E(nu) at T approximately 150 K. The rotor is a complex of Re with two substituted o-phenanthrolines, one positively and one negatively charged, attached to an axial position of Rh(2)(4+) in a [2]staffanedicarboxylate grid through 2-(3-cyanobicyclo[1.1.1]pent-1-yl)malonic dialdehyde. Four regimes are characterized by a, the average lag per turn: (i) synchronous (a < 1/e) at E(nu) = /E(nu)/ > E(c)(nu) [E(c)(nu) is the critical field strength], (ii) asynchronous (1/e < a < 1) at E(c)(nu) > E(nu) > E(bo)(nu) > kT/mu;, [E(bo)(nu) is the break-off field strength], (iii) random driven (a approximately 1) at E(bo)(nu) > E(nu) > kT/mu, and (iv) random thermal (a approximately 1) at kT/mu > E(nu). A fifth regime, (v) strongly hindered, W > kT, E(mu), (W is the rotational barrier), has not been examined. We find E(bo)(nu)/kVcm(-1) approximately (kT/(mu))/kVcm(-1) + 0.13(nu/GHz)(1.9) and E(c)(nu)/kVcm(-1) approximately (2.3kT/(mu))/kVcm(-1) + 0.87(nu/GHz)(1.6). For nu > 40 GHz, the rotor behaves as a macroscopic body with a friction constant proportional to frequency, eta/eVps approximately 1.14 nu/THz, and for nu < 20 GHz, it exhibits a uniquely molecular behavior.

• Publikační typ
• časopisecké články MeSH