Effect of Chelate Ring Expansion on Jahn-Teller Distortion and Jahn Teller Dynamics in Copper(II) Complexes

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Katharina Mack
  • Anica Wuensche von Leupoldt
  • Christoph Foerster
  • Maria Ezhevskaya
  • Dariush Hinderberger
  • Karl W Klinkhammer
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000306381800056&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/ic300929g
eISSN
1520-510X
Externe Identifier
  • Clarivate Analytics Document Solution ID: 973TD
  • PubMed Identifier: 22747572
ISSN
0020-1669
Ausgabe der Veröffentlichung
14
Zeitschrift
INORGANIC CHEMISTRY
Paginierung
7851 - 7858
Datum der Veröffentlichung
2012
Status
Published
Titel
Effect of Chelate Ring Expansion on Jahn-Teller Distortion and Jahn Teller Dynamics in Copper(II) Complexes
Sub types
  • Article
Ausgabe der Zeitschrift
51

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Autoren
  • Katharina Mack
  • Anica Wünsche von Leupoldt
  • Christoph Förster
  • Maria Ezhevskaya
  • Dariush Hinderberger
  • Karl W Klinkhammer
  • Katja Heinze
DOI
10.1021/ic300929g
eISSN
1520-510X
ISSN
0020-1669
Ausgabe der Veröffentlichung
14
Zeitschrift
Inorganic Chemistry
Sprache
en
Online publication date
2012
Paginierung
7851 - 7858
Datum der Veröffentlichung
2012
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/ic300929g
Datum der Datenerfassung
2023
Titel
Effect of Chelate Ring Expansion on Jahn–Teller Distortion and Jahn–Teller Dynamics in Copper(II) Complexes
Ausgabe der Zeitschrift
51

Datenquelle: Crossref

Abstract
The expanded ligand N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridin-2,6-diamine (ddpd) coordinates to copper(II) ions in a meridional fashion giving the dicationic complex mer-[Cu(ddpd)(2)](BF(4))(2) (1). In the solid state at temperatures below 100 K the cations of 1 localize in Jahn-Teller elongated CuN(6) polyhedra with the longest Cu-N bond pointing in the molecular x or y directions while the z axis is constrained by the tridentate ddpd ligand. The elongated polyhedra are ordered in an antiferrodistortive way giving an idealized zincblende structure. At higher temperature dynamically averaged (fluxional) polyhedra in the molecular x/y directions are observed by multifrequency variable temperature electron paramagnetic resonance (EPR) and by variable temperature X-ray diffraction studies. Compared to [Cu(tpy)(2)](2+) (tpy = 2,2';6',2″-terpyridine) the Jahn-Teller splitting 4δ(1) of 1 is larger. This is very probably caused by the much more favorable orbital overlap in the Cu-N bonds in 1 which results from the larger bite angle of ddpd as compared to tpy. The "freezing-in" of the Jahn-Teller dynamics of 1 (T ≈ 100 K) occurs at higher temperature than observed for [Cu(tpy)(2)](2+) (T < 77 K) which is also probably due to the larger Jahn-Teller distortion of 1 resulting in a larger activation barrier.
Addresses
  • Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
Autoren
  • Katharina Mack
  • Anica Wünsche von Leupoldt
  • Christoph Förster
  • Maria Ezhevskaya
  • Dariush Hinderberger
  • Karl W Klinkhammer
  • Katja Heinze
DOI
10.1021/ic300929g
eISSN
1520-510X
Externe Identifier
  • PubMed Identifier: 22747572
Open access
false
ISSN
0020-1669
Ausgabe der Veröffentlichung
14
Zeitschrift
Inorganic chemistry
Sprache
eng
Medium
Print-Electronic
Online publication date
2012
Paginierung
7851 - 7858
Datum der Veröffentlichung
2012
Status
Published
Datum der Datenerfassung
2012
Titel
Effect of chelate ring expansion on Jahn-Teller distortion and Jahn-Teller dynamics in copper(II) complexes.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
51

Datenquelle: Europe PubMed Central

Abstract
The expanded ligand N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridin-2,6-diamine (ddpd) coordinates to copper(II) ions in a meridional fashion giving the dicationic complex mer-[Cu(ddpd)(2)](BF(4))(2) (1). In the solid state at temperatures below 100 K the cations of 1 localize in Jahn-Teller elongated CuN(6) polyhedra with the longest Cu-N bond pointing in the molecular x or y directions while the z axis is constrained by the tridentate ddpd ligand. The elongated polyhedra are ordered in an antiferrodistortive way giving an idealized zincblende structure. At higher temperature dynamically averaged (fluxional) polyhedra in the molecular x/y directions are observed by multifrequency variable temperature electron paramagnetic resonance (EPR) and by variable temperature X-ray diffraction studies. Compared to [Cu(tpy)(2)](2+) (tpy = 2,2';6',2″-terpyridine) the Jahn-Teller splitting 4δ(1) of 1 is larger. This is very probably caused by the much more favorable orbital overlap in the Cu-N bonds in 1 which results from the larger bite angle of ddpd as compared to tpy. The "freezing-in" of the Jahn-Teller dynamics of 1 (T ≈ 100 K) occurs at higher temperature than observed for [Cu(tpy)(2)](2+) (T < 77 K) which is also probably due to the larger Jahn-Teller distortion of 1 resulting in a larger activation barrier.
Autoren
  • Katharina Mack
  • Anica Wünsche von Leupoldt
  • Christoph Förster
  • Maria Ezhevskaya
  • Dariush Hinderberger
  • Karl W Klinkhammer
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/22747572
DOI
10.1021/ic300929g
eISSN
1520-510X
Ausgabe der Veröffentlichung
14
Zeitschrift
Inorg Chem
Sprache
eng
Country
United States
Paginierung
7851 - 7858
Datum der Veröffentlichung
2012
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2012
Titel
Effect of chelate ring expansion on Jahn-Teller distortion and Jahn-Teller dynamics in copper(II) complexes.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
51

Datenquelle: PubMed

Beziehungen:
Eigentum von

Werkzeuge