Steric Effects in the Ground and Excited States of Cu(NN)2+ Systems

Autor:	Alexander J. Pallenberg, Michèle K. Eggleston, Kristina S. Koenig, David R. McMillin
Rok vydání:	1997
Předmět:	chemistry.chemical_classification Steric effects Ligand Substituent Photochemistry Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Excited state Emission spectrum Electron configuration Physical and Theoretical Chemistry Counterion Alkyl
Zdroj:	Inorganic Chemistry. 36:172-176
ISSN:	1520-510X 0020-1669
Popis:	This investigation focuses on a series of pseudotetrahedral complexes of the form Cu(NN)2+, where NN denotes a 1,10-phenanthroline ligand with alkyl substituents in the 2 and 9 positions and the counterion is PF6-. In these copper(I) systems, steric effects are of considerable interest because the electronic configuration predisposes the reactive charge-transfer excited state to undergo a flattening distortion or to add a fifth ligand. Both effects lead to emission quenching and a shorter excited-state lifetime. Bulky substituents inhibit these processes, but the spatial distribution of the atoms involved is more important than the total molecular volume in determining the influence of a substituent. According to the results of this study, the effective size decreases in the following order: sec-butyl > neopentyl > n-octyl ≈ n-butyl > methyl. In conjunction with the electrochemical data, the absorption and the emission spectra reveal three kinds of steric effects: (1) Clashes between substituents on opp...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::ec24a6cb996d9c011e6574ae337e6b34 https://doi.org/10.1021/ic960698a Zobrazit plný text záznamu