Intermolecular interactions in pi-stacked conjugated molecules. Synthesis,structure, and spectral characterization of alkyl bithiazole oligomers

Syntheses are reported of new 4,4'-dialkyl-2,2'-bithiazole oligomers that have alkenoxy side chains that are capable of easy conversion to oligomers with functionalized side chains, e.g., terminally substituted hydroxy chains. The crystal structures of two representative oligomers (4,4',4' ',4' "-tetra-(2-propenoxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3P2) and 4,4',4' ',4' "-tetra-(3-hydroxypropyloxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3H2)) were determined; 3P2 crystallizes in a pi-stacked motif with two molecules per unit cell, whereas 3H2 forms pi-stacks that are linked with hydrogen bonds to form infinite two-dimensional sheets with one molecule per unit cell. A comparison of the UV-vis spectra of the compounds in solution and in the solid state provides unequivocal evidence for the presence of a Davydov splitting, W(D) approximately 0.2 eV, in solid 3P2. The spectra are interpreted in the framework of molecular exciton theory to extract a value of the intermolecular transfer integral, J approximately 0.2 eV, for a total exciton bandwidth of ca. 0.8 eV. Monte Carlo calculations were used to determine the density of states of the exciton band and the absorption and emission line shapes of the 0 <-- 0 transition. It is suggested that the "three-humped" absorption profile typical of partially crystalline, regioregular polymers is the "optical signature" of pi-stacking.     

A cationic 24-MC-8 manganese cluster with ring metals possessing three oxidation states [Mn(II)4Mn(III)6Mn(IV)2(mu4-O)2(mu3-O)4(mu3-OH)4(mu3-OCH3)2(pko)12](OH)(ClO4)3

Reaction of Mn(ClO4)2 with di-pyridyl ketone oxime, (2-py)2C=NOH, gives the novel cluster [Mn(II)4Mn(III)6Mn(IV)2(mu4-O)2(mu3-O)4(mu3-OH)4(mu3-OCH3)2(pko)12](OH)(ClO4)3 1. It is the only example of a 24-MC-8, and the first metallacrown with ring metal ions in three different oxidation states. Magnetic measurements show antiferromagnetic behavior.     

Isostructural self-assembled monolayers. 2. Methyl 1-(3-mercaptopropyl)-oligo(ethylene oxide)s

The structural order and ordering conditions of the self-assembled monolayers (SAMs) of HSCH2CH2CH2O(EO)xCH3, where EO = CH2CH2O and x = 3-9, on polycrystalline gold (Au) were determined by reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and electrochemical impedance spectroscopy. For x = 5-7, RAIRS and SE data show that the oligo(ethylene oxide) [OEO] segments adopt the near single phase, 7/2 helical conformation of the folded-chain crystal polymorph of crystalline poly(ethylene oxide), oriented normal to the substrate. These SAMs exhibit OEO segment structure and orientation identical to that found in a previous isostructural series [HS(CH2CH2O)6-8C18H37 SAMs. Vanderah, D. J., et al. Langmuir 2003, 19, 3752] and are anisotropic films for surface science metrology where structure is constant and thickness increases in 0.30 nm increments. In addition, this is the first example of OEO SAMs to attain this highly ordered, helical conformation where the (EO)x segment is separated from the Au-sulfur headgroup by a polymethylene chain. For x = 4, 8, and 9, the SAMs are largely helical but show evidence of nonhelical conformations and establish the upper and lower limits of the isostructural set. For x = 3, the SAMs are largely disordered containing some all-trans conformation. SAM order as a function of immersion time from 100% water and 95% ethanol indicates that the HSCH2CH2CH2O(EO)5-7CH3 SAMs order faster and under a wider range of conditions than omega-alkyl 1-thiaolio(ethylene oxide) [HS(EO)xCH3] SAMs, reported earlier (Vanderah, D. J., et al. Langmuir 2002, 18, 4674 and Vanderah, D. J., et al. Langmuir 2003, 19, 2612).     

Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes

The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO)(CHO). From the equilibrium constant for the hydride transfer (16.2), the DeltaGdegrees for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating ability, DeltaGdegrees(H-), is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) right arrow M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+ and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E(1/2)(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known DeltaGdegrees(H-) values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.     

Translational energy release and stereochemistry of steroids. VIII-The mechanism of the elimination of water from metastable ions in epimeric 3-hydroxy steroids of the 5α-series

The mechanism of water elimination from metastable molecular, [M ? CH₃˙]⁺ and [M ? ring D]⁺˙ ions of epimeric 3-hydroxy steroids of the 5α-series has been elucidated. Deuterium labelling, the measurement of the translational energy released during the loss of water, and collision-induced decomposition mass-analysed kinetic energy spectrometry were the techniques used. It was found that the mechanisms of water loss from metastable M⁺˙ and [M ? ring D]⁺˙ ions is different from that from [M ? CH₃˙]⁺ ions.     

Synthesis, Characterization, and Physical Properties of Two Trinuclear, Mixed-Valence Species of Type [μ3-OMnIIMnIII 2(O2CCF3)6(R)3] (R=H2O, CH3COOH)

The preparation and characterization of two new mixed-valence, trinuclear species, [Mn₃O(O₂CCF₃)₆(H₂O)₃]CF₃COOH4/3H₂O (1) and [Mn₃O(O₂CCF₃)₆(CH₃COOH)₃] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) ų, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R _int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P2₁/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) ų, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R _int value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm^–1, J=–3.4 cm^–1, and D _Mn(III)=–4.5 cm^–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm^–1, J=–5.5 cm^–1, and D _Mn(III)=–4.5 cm^–1.     

2-(1-Azulyl)ethyl tosylate methylene scrambling in the gas phase. Similarities to solution chemistry

The methylene groups in 2-(1-azulyl)ethyl tosylate are largely scrambled prior to formation of fragment ions in the mass spectrometer. This process also occurs in the 3-nitro analog, where it is dependent on sample residence time in the source and independent of electron energy. It could not be observed with the isomeric 6-substituted tosylates, the 1-substituted acetates or alcohols, or with 2-(p-anisyl)ethyl tosylate. Scrambling occurs in the neutral molecule prior to ionization and a mechanism involving absorption onto the metal surface and formation of a complexed ethylenazulonium ion is suggested.     

Influence of dipolar interactions on radical pair recombination reactions subject to weak magnetic fields

Monte Carlo simulations of the effects of weak magnetic fields on the recombination of interacting radical pairs undergoing free diffusion in solution have been performed, with the aim of determining the influence on the low field effect of the magnetic dipolar coupling between the radicals. The suppression of singlet-triplet interconversion in the radical pair by the dipolar interaction is found to be pronounced at magnetic field strengths comparable to the hyperfine interactions in the radicals, to the extent that the low field effect is completely abolished. The averaging of the dipolar coupling by the translational diffusion of the radicals around one another is relatively efficient in the presence of strong magnetic fields but becomes ineffective in weak applied fields where the strength of the dipolar interaction is independent of the orientation of the inter-radical vector. Low field effects are only likely to be observed if the motion of the radical pair is restricted in some way so as to increase the likelihood that, having separated to the large distance required for the dipolar interaction to have a negligible effect, the radicals subsequently encounter and have the opportunity to recombine.     

The Crystal and Molecular Structure of Bis(cyclopentadienyldicarbonylchromium) (CrCr)

The crystal structure of bis(cyclopentadienyldicarbonyl-chromium) has been determined by x-ray diffraction. The compound crystalizes in the triclinic system, space group P1¯(C¹_i, No. 2) with unit cell parameters: a, 7.829(3); b, 14.543(6); c, 6.588(2)Å; α, 94.67(3), β, 110.70(3); γ, 104.04°(3); V, 699.1(4)ų; z=2. There are two independent molecules per unit cell located at the inversion centers at O,O,O and O, 1/2, O. The CrCr bond distances are, respectively 2.200(3) and 2.230(3), thus supporting their formulation as triple bonds. The CpCrCr angles in the two molecules are 165.0° and 158.7°, respectively. The structural features are compared with those of Cp₂Mo₂(CO)₄, which has a linear CpMoMoCp axis; and the differences rationalized in terms of electronic interactions of the Cp-ligand with the orbitals of the M₂ unit. The differences observed in the structures of the two independent molecules are also related to the proposed bonding model and to packing considerations.