TY  - JOUR
A1  - Rupp, Mira T.
A1  - Auvray, Thomas
A1  - Hanan, Garry S.
A1  - Kurth, Dirk G.
T1  - Electrochemical and photophysical study of homoleptic and heteroleptic methylated Ru(II) Bis-terpyridine complexes
JF  - European Journal of Inorganic Chemistry
N2  - In this study, we investigate the impact of N-methylation on the electronic and photophysical properties of both homoleptic and heteroleptic Ru(II) bis-terpyridine complexes based on the recently reported ligand 4’-(4-bromophenyl)-4,4’’’: 4’’,4’’’’-dipyr-idinyl-2,2’ : 6’,2’’-terpyridine (Bipytpy), with pyridine substituents in the 4- and 4’’-position. The first reduction of the methylated complexes takes place at the pyridinium site and is observed as multi-electron process. Following N-methylation, the complexes exhibit higher luminescence quantum yields and longer excited-state lifetimes. Interestingly, the photophysical properties of the heteroleptic and homoleptic complexes are rather similar. TD-DFT calculations support the experimental results. Furthermore, the complexes are tested as photosensitizers for photocatalytic hydrogen production, as the parent complex 1[Ru(Bipytpy)(Tolyltpy)](PF \(_6\))\(_2\) (Tolyltpy: 4’-tolyl-2,2’: 6’,2’’-terpyri-dine) was recently shown to be active and highly stable underphotocatalytic conditions. However, the methylated complexes reported herein are inactive as photosensitizers under the chosen conditions, presumably due to loss of the methyl groups, converting them to the non-methylated parent complexes.
KW  - Ruthenium
KW  - Luminescence
KW  - Electrochemistry
KW  - Ligand effects
KW  - Photocatalysis
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-248769
VL  - 2021
IS  - 28
SP  - 2822
EP  - 2829
ER  - 
TY  - JOUR
A1  - Lenczyk, Carsten
A1  - Roy, Dipak Kumar
A1  - Nitsch, Jörn
A1  - Radacki, Krzysztof
A1  - Rauch, Florian
A1  - Dewhurst, Rian D.
A1  - Bickelhaupt, F. Matthias
A1  - Marder, Todd B.
A1  - Braunschweig, Holger
T1  - Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes
JF  - Chemistry - A European Journal
N2  - The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH\(_3\)]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy\(_3\))\(_2\)HCl(H\(_2\))] (Cy: cyclohexyl) were studied, resulting in bis(σ)‐borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X‐ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho‐substitution of the aryl groups is necessary for the formation of terminal borylene complexes.
KW  - Arylborylene Complexes
KW  - Ruthenium
KW  - Dihydroboranes
KW  - boranes
KW  - borohydrides
KW  - borylenes
KW  - steric effects
KW  - sigma boranes
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-219537
SN  - 1521-3765
VL  - 25
IS  - 59
ER  -