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Structural Characterization and Lifetimes of Triple‐Stranded Helical Coinage Metal Complexes: Synthesis, Spectroscopy and Quantum Chemical Calculations

Wagner, Hanna E.; Di Martino‐Fumo, Patrick; Boden, Pit; Zimmer, Manuel; Klopper, Willem; Breher, Frank; Gerhards, Markus

Abstract:
This work reports on a series of polynuclear complexes containing a trinuclear Cu, Ag, or Au core in combination with the fac-isomer of the metalloligand [Ru(pypzH)$_{3}$](PF$_{6}$)$_{2}$ (pypzH=3-(pyridin-2-yl)pyrazole). These (in case of the Ag and Au containing species) newly synthesized compounds of the general formula [{Ru(pypz)$_{3}$}$_{2}$M$_{3}$](PF$_{6}$) (2: M=Cu; 3: M=Ag; 4: M=Au) contain triple-stranded helical structures in which two ruthenium moieties are connected by three N-M-N (M=Cu, Ag, Au) bridges. In order to obtain a detailed description of the structure both in the electronic ground and excited states, extensive spectroscopic and quantum chemical calculations are applied. The equilateral coinage metal core triangle in the electronic ground state of 2–4 is distorted in the triplet state. Furthermore, the analyses offer a detailed description of electronic excitations. By using time-resolved IR spectroscopy from the microsecond down to the nanosecond regime, both the vibrational spectra and the lifetime of the lowest lying electronically excited triplet state can be determined. The lifetimes of these almost only non-radiative triplet states of 2–4 show an unusual effect in a way that the Au-containing complex 4 has a lifetime which is by more than a factor of five longer than in case of the Cu complex 2. ... mehr

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Verlagsausgabe §
DOI: 10.5445/IR/1000124605
Veröffentlicht am 14.10.2020
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsmonat/-jahr 08.2020
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000124605
Erschienen in Chemistry - a European journal
Band 26
Heft 47
Seiten 10743–10751
Vorab online veröffentlicht am 28.07.2020
Nachgewiesen in Web of Science
Scopus
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