10.1021/ja990036v.s003
Diego J. Cárdenas
Diego J.
Cárdenas
Jean-Paul Collin
Jean-Paul
Collin
Pablo Gaviña
Pablo
Gaviña
Jean-Pierre Sauvage
Jean-Pierre
Sauvage
André De Cian
André
De Cian
Jean Fischer
Jean
Fischer
Nicola Armaroli
Nicola
Armaroli
Lucia Flamigni
Lucia
Flamigni
Veronica Vicinelli
Veronica
Vicinelli
Vincenzo Balzani
Vincenzo
Balzani
Synthesis, X-ray Structure, and Electrochemical and Excited-State
Properties of Multicomponent Complexes Made of a [Ru(Tpy)<sub>2</sub>]<sup>2+</sup>
Unit Covalently Linked to a [2]-Catenate Moiety. Controlling the
Energy-Transfer Direction by Changing the Catenate Metal Ion
American Chemical Society
1999
Ru
catenate
RuCu
tetrahedral coordination site
photoinduced intercomponent energy
photophysical properties
moiety
picosecond luminescence spectroscopy
Catenate Metal Ion New multicomponent species
RuAg
1999-05-27 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Synthesis_X-ray_Structure_and_Electrochemical_and_Excited-State_Properties_of_Multicomponent_Complexes_Made_of_a_Ru_Tpy_sub_2_sub_sup_2_sup_Unit_Covalently_Linked_to_a_2_-Catenate_Moiety_Controlling_the_Energy-Transfer_Direction_by_Changing_the_Catenate_M/3674013
New multicomponent species consisting of [2]-catenates incorporating the [Ru(tpy)<sub>2</sub>]<sup>2+</sup> moiety (tpy
= 2,2‘:6‘,2‘ ‘-terpyridine) within their framework have been prepared, and their electrochemical and photophysical
properties have been studied. The parent compound of the investigated species is a previously described Cu(I)
catenate (<b>RuCu</b>) containing a [Cu(dap)<sub>2</sub>]<sup>+</sup> fragment (dap = 2,9-dianisyl-1,10-phenanthroline) used as a template
and a [Ru(tpy)<sub>2</sub>]<sup>2+</sup> unit integrating one of the interlocked rings. Selective demetalation of the Cu(I) catenate
moiety of <b>RuCu</b> afforded a catenand (<b>Ru</b>) containing the [Ru(tpy)<sub>2</sub>]<sup>2+</sup>-type component and a free tetrahedral
coordination site. Reaction of this catenand with Ag<sup>+</sup> and Zn<sup>2+</sup> ions yielded two new bimetallic catenates
(<b>RuAg</b> and <b>RuZn</b>, respectively). The solid-state structure of complexes <b>RuCu</b> and <b>RuAg</b> has been determined
by X-ray diffraction. Electrochemical experiments have shown that the two moieties of the <b>RuCu</b> and <b>RuAg</b>
catenates undergo independent redox processes. The photophysical properties of <b>Ru</b>,<b> RuCu</b>,<b> RuZn</b>, and<b> RuAg
</b>have been investigated by steady-state and time-resolved techniques, and compared with those of appropriate
model compounds. The absorption spectra do not show any appreciable ground-state electronic interactions
between the [2]-catM (cat = catenand, catM = catenate) and [Ru(tpy)<sub>2</sub>]<sup>2+</sup>-type moieties, whereas luminescence
properties reveal the occurrence of efficient photoinduced intercomponent energy- and/or electron-transfer
processes, whose direction depends on the presence or on the nature of the metal ion in the [2]-cat-type moiety.
In <b>Ru, </b><b>RuZn</b>, and<b> RuAg</b> such a moiety is quenched by the [Ru(tpy)<sub>2</sub>]<sup>2+</sup> unit, whereas for <b>RuCu</b> the opposite
behavior is observed. The rate constant of intercomponent processes are determined via time-resolved nano-
and picosecond luminescence spectroscopy.