Vibrational overtone initiated unimolecular dissociation of HOCH_2OOH and HOCD_2OOH: Evidence for mode selective behavior

The vibrational overtone induced unimolecular dissociation of HMHP (HOCH2OOH) and HMHP-d2 (HOCD2OOH) into OH and HOCH2O (HOCD2O) fragments is investigated in the region of the 4nuOH and 5nuOH bands. The unimolecular dissociation rates in the threshold region, corresponding to the 4nuOH band, exhibit measurable differences associated with excitation of the OH stretch of the alcohol versus the peroxide functional group, with the higher energy alcohol OH stretching state exhibiting a slower dissociation rate compared to the lower energy peroxide OH stretch in both HMHP and HMHP-d2. Predictions using the Rice–Ramsperger–Kassel–Marcus theory give rates that are in reasonably good agreement with the measured dissociation rate for the alcohol OH stretch but considerably differ from the measured rates for the peroxide OH stretch in both isotopomers. The present results are interpreted as suggesting that the extent of intramolecular vibrational energy redistribution (IVR) is different for the two OH stretching states associated with the two functional groups in HMHP, with IVR being substantially less complete for the peroxide OH stretch. Analysis of the OH fragment product state distributions in conjunction with phase-space theory simulation gives a D0 value of 38±0.7 kcal/mole for breaking the peroxide bond in HMHP

End-to-end thiocyanato-bridged helical chain polymer and dichlorido-bridged copper(II) complexes with a hydrazone ligand: synthesis, characterisation by electron paramagnetic resonance and variable- temperature magnetic studies, and inhibitory effects on human colorectal carcinoma cells

The reactions of the tridentate hydrazone ligand, N’-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)]n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N − N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L- coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN- anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu···Cu distance of 3.402 (1). The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV– vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis

A mixed valent heterometallic Cu-II/Na-I coordination polymer with sodium-phenyl bonds

A mixed valent heterometallic Cu/Na coordination polymer (1) is generated by the reaction of a Schiff base ligand, (6,6′-(1E,1′E)-(2-hydroxypropane-1,3-diyl)bis(azan-1-yl-1-ylidene) bis(methan-1-yl-1-ylidene)bis(2-methoxyphenol)) with copper(ii) acetate and sodium perchlorate. In addition to the presence of alcohol oxygen-sodium coordination bonds, the single crystal X-ray structure reveals that the 1D coordination polymer is stabilised by the formation of phenyl-sodium η-bonds, face-to-face π-π contacts and Cu-π interactions. This journal i

OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH_2OOH) and its partially deuterated analogue, HOCD_2OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1ν_(OH) and 2ν_(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH_2OOH initiated by excitation of the 4ν_(OH) and 5ν_(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4ν_(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide