Photochemistry and Photophysics of Coordination Compounds

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Photochemistry and Photophysics of Coordination Compounds: Copper 79 has a strong tendency to bind phenanthroline-type ligands [27] originating a wealth of simple tetrahedral [Cu(NN)2] + complexeswithhighyields. The parent compound [Cu(phen)2] + (phen = 1,10-phenanthroline) has been scarcely studied, probably due to the lack of long-lived electronic excited states in solution, a problem that is partially avoided in the solid state, where some emission has been detected [28]. The most common [Cu(NN)2] + complexes are those 2,9 or 4,7 disubstituted phenanthrolines, due to an easier synthetic accessibility of the related ligands. The development of sophisticated synthetic strategies, which take advantage of this metal-ligand affinity, has afforded a number of complicated molecular architectures like catenanes [29–31], rotaxanes [7, 32, 33], Fig. 8 Selected examples of multicomponent arrays containing Cu(I)-bisphenanthroline centers: A catenane, B rotaxane (R=4-[tris-(4-tert-butyl-phenyl)-methyl]-phenolato), C grid, D dendrimer (R=C8H17)
80 N. Armaroli et al. pseudo-rotaxanes [34, 35], knots [36, 37], dendrimers [38, 39], helices [40– 42], polynuclear hosts [43] etc. as originally developed by Sauvage, Dietrich- Buchecker and coworkers [44]. Some of these fascinating structures are depicted in Fig. 8. Most notably, some suitably engineered supramolecular architectures based on [Cu(NN)2] + cores are able to carry out motion at the molecular level upon chemical [45], or electrochemical/photochemical stimulation [32, 46] behaving as molecular machine prototypes [47, 48]. For instance a [2]-catenate made of two different rings, one with a phenanthroline fragment the other bearing both a phenanthroline and a terpyridine unit, undergoes spontaneous and reversible molecular rearrangements (Fig. 9 steps (B) and (D)) upon oxidation (step A) and subsequent reduction (step C). Rearrangements are driven by the different preferential coordination geometries of Cu(I) and Cu(II), i.e. tetra- vs. pentacoordination [46]. Fig. 9 Electrochemically induced molecular motions in a catenane containing a [Cu(NN)2] + center and a free tpy ligand. The spontaneous motion is driven by the different preferential coordination geometry of Cu(I) vs. Cu(II) More recently, Schmittel and coworkers have made new supramolecular systems based on [Cu(NN)2] + -type building blocks such as racks [49], grids [50], boxes [51], and macrocycles [52]. Control of the sophisticated heteroleptic architectures has been achieved by exploiting the HETPHEN (HETeroleptic bisPHENanthroline) concept [53]. This approach is based on the kinetic control of the metal complexation equilibrium and, in the target complex, the Cu(I) ionturnsouttobeboundtoasimpleandabulky phenanthroline ligand; this concept is schematically illustrated in Fig. 10.
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280 Topics in Current Chemistry Edi
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Photochemistry and Photophysics of
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Volume Editors Prof. Vincenzo Balza
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Topics in Current Chemistry Also Av
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X Preface nation Compounds. The ven
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Contents Photochemistry and Photoph
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258 Author Index Volumes 251-280 Be
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Subject Index Alkyne bridges 148 An
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Subject Index 273 Rh(III) cyclometa
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Photochemistry and Photophysics of Coordination Compounds

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