Long‐Lived, Emissive Excited States in Direct and Amide‐Linked Thienyl‐Substituted Ru<sup>II</sup> Complexes

Majewski, Marek B.; Smith, J. Graham; Wolf, Michael O.; Patrick, Brian O.

doi:10.1002/ejic.201501436

Cited by 4 publications

(3 citation statements)

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“…These results strongly indicate that the accessibility of the planar structure over the aryl substituted dmp enhances the π-conjugation over the dmp ligand. The similar phenomena about the long excited-state lifetime caused by the planarity between aryl substituents and α-diimine ligand has been discussed for emissive Ru complexes, in which the delocalization of negative charge over the substituted bpy (bpy = 2,2′-bipyridine) in the 3 MLCT excited state lowers their structural changes from the ground state, leading to decreasing k nr (Damrauer et al, 1997; Majewski et al, 2016). It is also reported that the Cu I (dmp) complex has the close-lying 3 π-π * state near the lowest 3 MLCT excited state as for Cu I (dmp)(PPh 3 )2+, which showed the vibronic emission spectrum at 77 K as a long-lifetime component as τ em ~ 10 ms (Rader et al, 1981).…”

Section: Resultsmentioning

confidence: 56%

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

et al. 2019

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The visible-light responsive Cu(I)-complex photosensitizers were developed by introducing various aromatic substituents at the 4,7-positions of a 2,9-dimethyl-1,10-phenanthroline (dmp) ligand in a heteroleptic Cu I (dmp)(DPEphos) + -type complexes (DPEphos = [2-(diphenylphosphino)phenyl]ether) for photocatalytic CO 2 reduction. Introducing biphenyl groups (Bp-) on the dmp ligand enhanced the molar extinction coefficient (ε) of the metal-to-ligand charge transfer (MLCT) band in the visible region (ε = 7,500 M −1 cm −1 ) compared to that of the phenyl (Ph-)-containing analog (ε = 5,700 M −1 cm −1 at λ max = 388 nm). However, introducing 4-R-Ph- groups (R = the electron-withdrawing groups NC-, or NO 2 -) led to a red shift in the band to λ max = 390, 400, and 401 nm, respectively. Single-crystal X-ray analysis showed the Ph- groups were twisted because of the steric repulsion between the 2,6-protons of the Ph- groups and 5,6-protons of the dmp ligand. The result strongly indicated that the π-conjugation effect of the 4-R-Ph- groups is so weak that the lowering of the energy of the dmp π * orbitals is small. However, when 4-R-ph- was substituted by a 5-membered heterorings, there was a larger red shift, leading to an increase in the ε value of the MLCT absorption band. Thus, the substitution to 2-benzofuranyl- groups resulted in visible-light absorption up to 500 nm and a shoulder peak at around 420 nm (ε = 12,300 M −1 cm −1 ) due to the expansion of π-conjugation over the substituted dmp ligand. The photocatalytic reaction for CO 2 reduction was tested using the obtained Cu I complexes as photosensitizers in the presence of a Fe(dmp) 2 (NCS) 2 catalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1 H -benzo[d]imidazole as a sacrificial reductant, which showed improved CO generation.

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Section: Resultsmentioning

confidence: 56%

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

et al. 2019

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“…Wolfs Gruppe interessiert sich für konjugierte Polymere und Materialien, die Photochemie und Photophysik von konjugierten Materialien und Koordinationskomplexen sowie die Synthese und den Einsatz modifizierter Nanomaterialien. Seine Veröffentlichung über das Verhalten von Ruthenium(II)‐Komplexen im angeregten Zustand wurde auf dem Titelbild des European Journal of Inorganic Chemistry vorgestellt …”

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Preise 2016 des Chemical Institute of Canada und der Canadian Society for Chemistry

2016

Angewandte Chemie

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“…His report on the excited-state behavior of ruthenium-(II) complexes was featured on the cover of the European Journal of Inorganic Chemistry. [9] Curtis P. He has reported in Angewandte Chemie on interfacial halogen bonding. [10] Tom Woo (University of Ottawa) has been recognized with the CSC Tom Ziegler Award, which is given for contributions to computational and theoretical chemistry.…”

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confidence: 99%

Chemical Institute of Canada and Canadian Society for Chemistry Awards 2016

2016

Angew Chem Int Ed

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TheC hemical Institute of Canada (CIC) and the Canadian Society for Chemistry (CSC) have honored several outstanding scientists in their 2016 awards program. We congratulate all the awardees including Mark Lautens (University of Toronto; CIC Catalysis Award), [1a] Stephen G. Withers (University of British Columbia;C IC Medal), [1b] Mark MacLachlan (University of British Columbia;CSC Award for Research Excellence in Materials Chemistry), [1a] and Federico Rosei (Institut National de la Recherche Scientifique,U niversitØ de QuØbec; CSC John C. Polyani Award), [1c] and feature those who have recently published in Angewandte Chemie and its sister journals. Kim M. Baines (Western University,Ontario) is the winner of the CIC MontrØal Medal/MØdaille de MontrØal, which is presented for distinguished contributions to the field of chemistry or chemical engineering.B aines studied at St. MarysU niversity,H alifax, and worked with Adrian G. Brook at the University of Toronto for her PhD (completed in 1987). From 1987-1988, she was ap ostdoctoral fellow with Wilhelm P. Neumann at the University of Dortmund (currently the Technische Universität Dortmund), and in 1988, she started her independent career at the University of Western Ontario (currently Western University). She was made professor in 2000 and is Vice-President of the CSC from June 2016 to May 2017. Baines and her research group are interested in the synthesis, reactivity,a nd spectroscopic characterization of low-valent main-group element compounds with novel bonding paradigms.S he has reported in Chemistry-A European Journal on cationic lowvalent gallium complexes of cryptand[2.2.2]. [2]Dennis G. Hall (University of Alberta) is the recipient of the Alfred Bader Award, which is given for excellent research in organic chemistry.H all carried out his PhD (completed in 1995

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Long‐Lived, Emissive Excited States in Direct and Amide‐Linked Thienyl‐Substituted Ru^II Complexes

Cited by 4 publications

References 78 publications

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

Preise 2016 des Chemical Institute of Canada und der Canadian Society for Chemistry

Chemical Institute of Canada and Canadian Society for Chemistry Awards 2016

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Long‐Lived, Emissive Excited States in Direct and Amide‐Linked Thienyl‐Substituted RuII Complexes

Cited by 4 publications

References 78 publications

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

Preise 2016 des Chemical Institute of Canada und der Canadian Society for Chemistry

Chemical Institute of Canada and Canadian Society for Chemistry Awards 2016

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Long‐Lived, Emissive Excited States in Direct and Amide‐Linked Thienyl‐Substituted Ru^II Complexes