Issue 4, 1995

Luminescent nitridometal complexes. Photophysical and photochemical properties of the 3[(dxy)1(dπ*)1] excited state of nitridoosmium(VI) complexes with polypyridine ligands

Abstract

Nitridoosmium(VI) complexes of substituted 2,2′-bipyridines and 1,10-phenanthrolines have been prepared from [OsNCl4] and the appropriate chelating ligands in acetonitrile. Reaction of [Os(bipy)NCl3](bipy = 2,2′-bipyridine) and [Os(terpy)NCl2]Cl (terpy = 2,2′ : 6′,2″-terpyridine) with neat trifluoromethanesulfonic acid gave [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ respectively. The crystal structures of [Os(dmbipy)NCl3](dmbipy = 5,5′-dimethyl-2,2′-bipyridine), [Os(bipy)NCl2(H2O)]+ and [Os(terpy)N(Cl)(CF3SO3)]+ show that the Os[triple bond, length half m-dash]N distances are 1.68(1), 1.630(7) and 1.629(8)Å respectively. In the latter two complexes the Os[triple bond, length half m-dash]N moiety is perpendicular to the plane of the chelating ligand. The spectroscopic, photophysical and photochemical properties of the newly prepared complexes have been studied. All have long-lived and emissive 3[dxy,dπ.] excited states in the solid state and in fluid solution at room temperature. The complex mer-[Os(terpy)NCl2][ClO4] has the longest emission lifetime 4.64 µs (at infinite dilution) in degassed acetonitrile at room temperature. Based on quenching studies with aromatic hydrocarbons, this complex is a powerful photooxidant with E[OsVI*–OsV] being 2.12(30)V vs. the normal hydrogen electrode.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1995, 657-663

Luminescent nitridometal complexes. Photophysical and photochemical properties of the 3[(dxy)1(dπ*)1] excited state of nitridoosmium(VI) complexes with polypyridine ligands

K. Chin, K. Cheung, H. Yip, T. C. W. Mak and C. M. Che, J. Chem. Soc., Dalton Trans., 1995, 657 DOI: 10.1039/DT9950000657

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements