Photochemistry of copper(II) macrocyclic complexes bound to poly(acrylic acid): Time-resolved observations in a picosecond-millisecond time domain and sequential biphotonic excitations

Journal Article · Wed Nov 14 00:00:00 EST 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00348a031· OSTI ID:5972000

Baumgartner, E; Ronco, S; Ferraudi, G ^[1]

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1. Univ. of Notre Dame, IN (USA)

Flash photolysis of Cu(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup 2+}-poly(acrylate) generates an intermediate, Cu{sup III}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4})-alkyl, in less than 20 ps. This intermediate decomposes into Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}) with a 20-{mu}s lifetime. We have followed, in a millisecond time scale, the disappearance of Cu(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup +}, a process that exhibits a kinetics expected for consecutive first- and second-order reactions. The reactions rates are dependent on the number of photochemically generated Cu(I) species per molecule of poly(acrylic acid) but are independent of the solutions' bulk viscosity. Flash irradiations of Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4})-poly(acrylate) complexes in aqueous solutions form metastable Cu{sup II}(ligand radical)-poly(acrylate) complexes. By contrast, Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup +} in methanol exhibits no photoreactivity. 17 refs., 5 figs., 3 tabs.

• OSTI ID: 5972000
• Journal Information: Inorganic Chemistry; (USA), Vol. 29:23; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACRYLIC ACID
PHOTOCHEMISTRY
COPPER COMPLEXES
POLYMERS
EXPERIMENTAL DATA
CARBOXYLIC ACIDS
CHEMISTRY
COMPLEXES
DATA
INFORMATION
MONOCARBOXYLIC ACIDS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties