The University of Southampton
University of Southampton Institutional Repository

Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors

Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors
Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors
We have prepared a number of new dipolar complexes containing ethynyl or buta-1,3-diynyl units linking electron-rich {Ru-11(NH3)(5)}(2+), trans-{Ru-11(NH3)(4)L}(+) (L = pyridine or N-methylimidazole), or trans-{(RuCl)-Cl-11 (pdma)(2)}(+) [pdma = 1,2-phenylenebis(dimethylarsine)] centers to pyridinium electron acceptors. In acetonitrile solutions at 295 K, the new complexes display unusual blue-shifting of their metal-to-ligand charge-transfer (MLCT) bands as the conjugation is extended, in a fashion similar to that of the corresponding ethenyl systems. Hyper-Rayleigh scattering (HRS) and Stark spectroscopic measurements provide direct and indirect estimates of static first hyperpolarizabilities beta(0), and both the linear and nonlinear optical (NLO) properties are temperature- and medium-dependent. Thus, at 77 K in butyronitrile glasses, the MLCT bands display more normal red shifts upon conjugation extension. While the Stark-derived beta(0) values generally increase as n (the number of ethynyl units) increases from 0 to 2, the HRS data show maximization at n = 1 for two of the ammine series but an increase upon moving from n = 1 to 2 for the pdma complexes. Comparisons with the analogous ethenyl chromophores show that the latter generally display larger beta(0) values, whether determined via HRS or Stark data, and the inferiority of the ethynyl systems in terms of NLO response is more pronounced when n = 2. This differing behavior is attributable primarily to larger increases in the transition dipole moment 02 (and, hence, donor-acceptor pi-electronic coupling) on elongation in the ethenyl chromophores.
transition-metal complexes, hyper-rayleigh scattering, organometallic complexes, cubic hyperpolarizabilities, ammine complexes, trans-tetraammineruthenium(ii) complexes, 1st hyperpolarizabilities, sigma-arylacetylides, crystal-structure, excited-states
0020-1669
1215-1227
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harries, Josephine L.
ee93b1df-53b6-4eba-87d0-a26c0721a7db
Helliwell, Madeleine
974b9c73-cb00-4d9c-87c7-0a2119a95dfc
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Asselberghs, Inge
91f37820-e68b-4257-b9b1-82bb02933558
Hung, Sheng-Ting
9b8b4aaf-346b-40a4-a213-887a442af3c9
Clays, Koen
f13fe1bc-8c4d-463a-97e3-423523cf4f75
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harries, Josephine L.
ee93b1df-53b6-4eba-87d0-a26c0721a7db
Helliwell, Madeleine
974b9c73-cb00-4d9c-87c7-0a2119a95dfc
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Asselberghs, Inge
91f37820-e68b-4257-b9b1-82bb02933558
Hung, Sheng-Ting
9b8b4aaf-346b-40a4-a213-887a442af3c9
Clays, Koen
f13fe1bc-8c4d-463a-97e3-423523cf4f75
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Coe, Benjamin J., Harries, Josephine L., Helliwell, Madeleine, Brunschwig, Bruce S., Harris, James A., Asselberghs, Inge, Hung, Sheng-Ting, Clays, Koen, Horton, Peter N. and Hursthouse, Michael B. (2006) Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors. Inorganic Chemistry, 45 (3), 1215-1227. (doi:10.1021/ic051816+).

Record type: Article

Abstract

We have prepared a number of new dipolar complexes containing ethynyl or buta-1,3-diynyl units linking electron-rich {Ru-11(NH3)(5)}(2+), trans-{Ru-11(NH3)(4)L}(+) (L = pyridine or N-methylimidazole), or trans-{(RuCl)-Cl-11 (pdma)(2)}(+) [pdma = 1,2-phenylenebis(dimethylarsine)] centers to pyridinium electron acceptors. In acetonitrile solutions at 295 K, the new complexes display unusual blue-shifting of their metal-to-ligand charge-transfer (MLCT) bands as the conjugation is extended, in a fashion similar to that of the corresponding ethenyl systems. Hyper-Rayleigh scattering (HRS) and Stark spectroscopic measurements provide direct and indirect estimates of static first hyperpolarizabilities beta(0), and both the linear and nonlinear optical (NLO) properties are temperature- and medium-dependent. Thus, at 77 K in butyronitrile glasses, the MLCT bands display more normal red shifts upon conjugation extension. While the Stark-derived beta(0) values generally increase as n (the number of ethynyl units) increases from 0 to 2, the HRS data show maximization at n = 1 for two of the ammine series but an increase upon moving from n = 1 to 2 for the pdma complexes. Comparisons with the analogous ethenyl chromophores show that the latter generally display larger beta(0) values, whether determined via HRS or Stark data, and the inferiority of the ethynyl systems in terms of NLO response is more pronounced when n = 2. This differing behavior is attributable primarily to larger increases in the transition dipole moment 02 (and, hence, donor-acceptor pi-electronic coupling) on elongation in the ethenyl chromophores.

Full text not available from this repository.

More information

Published date: 2006
Keywords: transition-metal complexes, hyper-rayleigh scattering, organometallic complexes, cubic hyperpolarizabilities, ammine complexes, trans-tetraammineruthenium(ii) complexes, 1st hyperpolarizabilities, sigma-arylacetylides, crystal-structure, excited-states

Identifiers

Local EPrints ID: 44407
URI: http://eprints.soton.ac.uk/id/eprint/44407
ISSN: 0020-1669
PURE UUID: e014ee55-8b07-422d-aea5-88942f6c42e9
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

Catalogue record

Date deposited: 05 Mar 2007
Last modified: 29 Aug 2019 00:47

Export record

Altmetrics

Contributors

Author: Benjamin J. Coe
Author: Josephine L. Harries
Author: Madeleine Helliwell
Author: Bruce S. Brunschwig
Author: James A. Harris
Author: Inge Asselberghs
Author: Sheng-Ting Hung
Author: Koen Clays
Author: Peter N. Horton ORCID iD

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×