Detail of "10120-28-2"

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Matrix perdeuteration effects on the 3

Matrix perdeuteration effects on the 3.pi..pi.* .fwdarw. S0 phosphorescence of p-chlorobenzaldehyde at 4.2.degree.K. I. Phenomenology. Khalil, Omar S.; Goodman, Lionel (Wright Rieman Chem. Lab., Rutgers State Univ., New Brunswick, N. J., USA). J. Chem. Phys., 65(10), 4061-6 (English) 1976. CODEN: JCPSA6. DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) The effect of matrix perdeuteration and variation of cooling rate on the phosphorescence vibrational structure of p-chlorobenzaldehyde (PCB) are studied in methylcyclohexane (MCH) and p-xylene. PCB shows very different phosphorescence spectra in slowly-cooled MCH-h14 and MCH-d14, generally broad spectra in fast cooled samples, and a mixt. of the 2 phosphorescences (obsd. in the slowly-cooled sample) in intermediate cooled MCH-d14. In p-xylene, no change in the phosphorescence vibrational structure is obsd. on matrix perdeuteration. These observations are interpreted by postulating 2 cryst. modifications for methylcyclohexane, one of them stable in slowly-cooled MCH-h14, the other stable in slowly-cooled MCH-d14. The spectra of PCB is different in the 2 modifications. 62285-60-3 and 10120-28-2 are also in the experiment. The anomalous response of the PCB phosphorescence vibrational structure to the cryst. modifications of MCH is indicative of a large degree of distortability in its 3.pi..pi.* state. The distortability is interpreted as originating from vibrational-electronic interactions between the closely spaced 3.pi..pi.*-3n.pi.* states. Support for this view is found in the phosphorescence spectra of various deuterated derivs. of PCB in perprotonated and perdeuterated MCH. The apparent distortability of the emitting state varies with the extent of deuteration. .