Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties.

Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties. Research Abstract Details 

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Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties. Abstract Text:

Claudio Garino,Roberto Gobetto,Carlo Nervi,Luca Salassa,Edward Rosenberg,J B Alexander Ross,Xi Chu,Kenneth I Hardcastle,Cristiana Sabatini,Claudio Garino,Roberto Gobetto,Carlo Nervi,Luca Salassa,Edward Rosenberg,J B Alexander Ross,Xi Chu,Kenneth I Hardcastle,Cristiana Sabatini,Claudio Garino,Roberto Gobetto,Carlo Nervi,Luca Salassa,Edward Rosenberg,J B Alexander Ross,Xi Chu,Kenneth I Hardcastle,Cristiana Sabatini,Claudio Garino,Roberto Gobetto,Carlo Nervi,Luca Salassa,Edward Rosenberg,J B Alexander Ross,Xi Chu,Kenneth I Hardcastle,Cristiana Sabatini,

The complex [Ru(tpy)(CO)(2)TFA]+[PF(6)]- (where tpy = 2,2':6',2' '-terpyridine and TFA = CF(3)CO(2)-) (1) has been synthesized and fully characterized spectroscopically. The X-ray structure of the complex has been determined. The photopysical properties of the ruthenium complex and the free ligand tpy have been investigated at room temperature and at 77 K in acetonitrile solution and in the solid state. Their electronic spectra are highly influenced by intermolecular stacking interactions, both in solution and in the solid state. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed to characterize the electronic structure and the excited states of [Ru(tpy)(CO)(2)TFA]+[PF(6)]- and tpy. TDDFT calculations on three different conformations of free ligand have been performed as well. Absorption and emission spectra of tpy have been studied at different temperatures and concentrations in order to have a better understanding of this ruthenium derivative's properties. The absorption spectrum of 1 is characterized by metal-perturbed ligand-centered (LC) bands in the UV region. No metal-to-ligand charge transfer (MLCT) bands are observed in the visible for the complex. Only at high concentrations (10(-4) M) does a very weak band appear at 470 nm. At 77 K and low concentrations, solutions of 1 exhibit a major 3LC emission band centered at 468 nm (21.4 x 10(-3) cm(-1)). When the concentration of the complex is increased, an unstructured narrow emission at 603 nm (16.6 x 10(-3) cm(-1)), with a lifetime of 10 micros, dominates the emission spectrum in glassy acetonitrile. This emission originates from a pi-pi stacked dimeric (or oligomeric) species. TDDFT calculations performed on a tail-to-tail dimer structure, similar to that seen in the solid state, ascribe the transition to a triplet excited state, where intermolecular metal (d) --> ligand (pi*, polypyridine) charge transfer occurs. A good estimate of the transition energy is also obtained (623 nm, 1.94 eV).

Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties. Publishing Authors By Initials

C Garino,R Gobetto,C Nervi,L Salassa,E Rosenberg,JB Ross,X Chu,KI Hardcastle,C Sabatini,C Garino,R Gobetto,C Nervi,L Salassa,E Rosenberg,JB Ross,X Chu,KI Hardcastle,C Sabatini,C Garino,R Gobetto,C Nervi,L Salassa,E Rosenberg,JB Ross,X Chu,KI Hardcastle,C Sabatini,C Garino,R Gobetto,C Nervi,L Salassa,E Rosenberg,JB Ross,X Chu,KI Hardcastle,C Sabatini,

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Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 8752-62

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ISSN: 0020-1669

DAY: 11

MONTH: 09

YEAR: 2007

Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties. Information

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LANGUAGE: eng

NlmUniqueID: 366543

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Grant and Affiliation Information for Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties.

AFFILIATION: Dipartimento di Chimica IFM, Università di Torino, Via P. Giuria 7, I-10125 Torino, Italy.

Country: United States

AGENCY: United States NCRR

GRANT: RR-15583

ACRONYM: RR

MEDLINETA: Inorg Chem

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