About: Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)?

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About: Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)? Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	Replacement of 2,2''-bipyridine (bpy) by substituted 1,4-diazabutadiene (R-DAB) alpha;-diimine ligands N^N leads to a substantial hypsochromic shift of about 0.8 eV for the long-wavelength absorption band in compounds (N^N)Ir(C5Me5) but to a bathochromic absorption shift of about 0.4 eV for the complex ions [(N^N)IrCl(C5Me5)]+. DFT calculations on model complexes based on experimental (R-DAB compounds) and geometry-optimized structures (bpy systems) reveal that the low-energy transitions of the cationic chloro complexes are largely of ligandůto-ligand charge transfer character L''LCT (L = alpha-diimine, L'' = Cl) whereas the neutral compounds exhibit pí_pí* transitions between the considerably mixed metal d pí and alpha-diimine pí* orbitals. The much more pronounced metal-ligand orbital interaction for the R-DAB complexes causes the qualitatively different shifts on replacing the stronger basic bpy by the better pí-acceptors R-DAB. Replacement of 2,2''-bipyridine (bpy) by substituted 1,4-diazabutadiene (R-DAB) alpha;-diimine ligands N^N leads to a substantial hypsochromic shift of about 0.8 eV for the long-wavelength absorption band in compounds (N^N)Ir(C5Me5) but to a bathochromic absorption shift of about 0.4 eV for the complex ions [(N^N)IrCl(C5Me5)]+. DFT calculations on model complexes based on experimental (R-DAB compounds) and geometry-optimized structures (bpy systems) reveal that the low-energy transitions of the cationic chloro complexes are largely of ligandůto-ligand charge transfer character L''LCT (L = alpha-diimine, L'' = Cl) whereas the neutral compounds exhibit pí_pí* transitions between the considerably mixed metal d pí and alpha-diimine pí* orbitals. The much more pronounced metal-ligand orbital interaction for the R-DAB complexes causes the qualitatively different shifts on replacing the stronger basic bpy by the better pí-acceptors R-DAB. (en)
Title	Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)? Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)? (en)
skos:prefLabel	Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)? Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)? (en)
skos:notation	RIV/61388955:_____/03:54030171!RIV/2004/AV0/A54004/N
http://linked.open.../vavai/riv/strany	5185;5191
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(OC D14.20), P(OC D15.10), Z(AV0Z4040901)
http://linked.open...iv/cisloPeriodika	N/A
http://linked.open...vai/riv/dodaniDat	2004
http://linked.open...aciTvurceVysledku	Záliš, Stanislav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	625299
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/03:54030171
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	bipyridine; 1,4-diazabutadiene; transition metal complexes (en)
http://linked.open.../riv/klicoveSlovo	1 4-diazabutadiene transition metal complexes bipyridine
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[397AB8853282]
http://linked.open...i/riv/nazevZdroje	Inorganic Chemistry
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	1 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...ocetUcastnikuAkce	0 (xsd:int)
http://linked.open...nichUcastnikuAkce	0 (xsd:int)
http://linked.open...vavai/riv/projekt	http://linked.opendata.cz/resource/domain/vavai/projekt/OC%20D14.20 http://linked.opendata.cz/resource/domain/vavai/projekt/OC%20D15.10
http://linked.open...UplatneniVysledku	2003
http://linked.open...v/svazekPeriodika	42
http://linked.open...iv/tvurceVysledku	Kaim, W. Sieger, M. Záliš, Stanislav Greulich, S. Stoll, H.
http://linked.open...n/vavai/riv/zamer	Objasňování zákonitostí vztahů struktury a vlastností - zejména dynamiky a chemické reaktivity - látek a molekulárních systémů
issn	0020-1669
number of pages	7 (xsd:int)

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