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The intramolecular and long-range ferromagnetic coupling between p-phenylenediamine radical cations in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and oligo(1,4-phenylenvinylene)s between neighbors and next-nearest neighbors is described. UV/vis/near-IR experiments show that the radical cations are localized in the pendant p-phenylenediamine units of the conjugated oligomers. The ESR spectra of these oligo(1,4-phenyleneethynylene) and oligo(1, 4-phenylenvinylene) di(radical cation)s are consistent with those of a triplet state. A linear behavior is observed for the doubly integrated ESR intensity of the DeltaM(s) = +/-1 and DeltaM(s) = +/-2 signals with the inverse temperature (I approximately 1/T), consistent with Curie's law. This behavior indicates a triplet ground-state diradical with a large triplet-singlet energy gap or possibly a degeneracy of singlet and triplet states. 相似文献
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Martinez-Diaz MV Rodriguez-Morgade MS Feiters MC van Kan PJ Nolte RJ Stoddart JF Torres T 《Organic letters》2000,2(8):1057-1060
[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry. 相似文献
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C. A. Snyder N. C. Tice J. B. Maddox J. O. E. Young M. G. Mazzotta B. D. Garabato J. W. Evans L. A. Dopierala S. A. Shah Z. A. Claytor A. C. Smith 《Transition Metal Chemistry》2013,38(8):801-809
A series of 5,6-fused ring cyclopentadienyl tricarbonyl manganese and rhenium complexes, [M(CO)3{η 5-1,2-C5H3(1,4-(R)2N2C2}] (2a–3d) were isolated by employing an off-metal ring closure route. Reacting thallium cyclopentadienide (Cp) salts (1a–d) with [MBr(CO)5] (M = Mn, Re) provided pyridazyl complexes (2a–3d) in high yield (75–99 %). Spectroscopic characterization (NMR, IR, MS) confirmed the identity of the desired organometallic pyridazines. The off-metal synthetic pathway employed did improve upon the isolation of these complexes as compared to previously reported routes. The molecular and electronic structure of complexes 2a–3d and their optimal energy structures have been characterized with quantum chemistry calculations. Vibrational frequencies calculated were compared to their experimental counterparts. The excited state calculations predict that the dominant low-energy transition involves a ligand-to-metal charge transfer. 相似文献
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We propose a quantum trajectory algorithm for computing nonlinear response functions of condensed phase molecular systems based on a time-ordered expansion of the density matrix. The nth-order response function is expressed as a sum of 2(n) impulsive response pathways representing trajectories involving zero, one, and up to n interactions with short external pulses. These are evaluated using a forward propagation algorithm based upon a Liouville space extension of the Bohmian propagation method. 相似文献