Details
| Original language | English |
|---|---|
| Article number | 122998 |
| Number of pages | 9 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 1006 |
| Early online date | 22 Dec 2023 |
| Publication status | Published - 15 Feb 2024 |
Abstract
Symmetrical and unsymmetrical donor-acceptor (D–A) based chromophores were designed and synthesized by the Pd–catalyzed Sonogashira cross–coupling reaction of 1,1′-diiodoferrocene with (4-N,N-dimethylaminophenyl)ethyne followed by [2+2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). Ferrocene was used as a central donor unit and 4-(N,N-dimethylamino)phenyl group as the end-capping donor. Herein, we report the cycloaddition-retrocyclization reaction of TCNE/TCNQ groups on the disubstituted ferrocene containing more than one triple bond to get disubstituted tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD products. The effect of the conjugation length and different π–acceptor linkers were investigated by photophysical, redox and computational studies. The redox study reveals multiple oxidation waves corresponding to donor moieties (ferrocene and 4-(N,N-dimethylamino)phenyl group) and reduction waves corresponding to acceptor units (TCBD / cyclohexa-2,5- diene-1,4-diylidene-expanded TCBD). The thermogravimetric analysis data shows that the compounds exhibit high thermal stability. The computational studies reveal HOMO-LUMO gaps consistent with the experimentally obtained data.
Keywords
- Charge transfer, Cyclic voltammetry, Cycloaddition, Donor-acceptor, Ferrocene, Sonogashira cross-coupling
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Biochemistry
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
- Chemistry(all)
- Inorganic Chemistry
- Materials Science(all)
- Materials Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Journal of Organometallic Chemistry, Vol. 1006, 122998, 15.02.2024.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - NIR-absorbing TCBD and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD bridged derivatives of 1,1′-bis(N,N-dimethylaniline)-substituted ferrocene
AU - Popli, Charu
AU - Misra, Rajneesh
AU - Butenschön, Holger
N1 - Funding Information: C. P. thank CSIR, New Delhi for fellowship. R.M. thanks to the Science and Engineering Research Board (SERB) Project No. CRG /2022/000023 and STR/2022/000001, New Delhi We also thank the Sophisticated Instrumentation Centre (SIC), Indian Institute of Technology (IIT) Indore. R. M. is indebted to the Alexander von Humboldt Foundation for a research fellowship. Support by DAAD (Passage to India) is gratefully acknowledged.
PY - 2024/2/15
Y1 - 2024/2/15
N2 - Symmetrical and unsymmetrical donor-acceptor (D–A) based chromophores were designed and synthesized by the Pd–catalyzed Sonogashira cross–coupling reaction of 1,1′-diiodoferrocene with (4-N,N-dimethylaminophenyl)ethyne followed by [2+2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). Ferrocene was used as a central donor unit and 4-(N,N-dimethylamino)phenyl group as the end-capping donor. Herein, we report the cycloaddition-retrocyclization reaction of TCNE/TCNQ groups on the disubstituted ferrocene containing more than one triple bond to get disubstituted tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD products. The effect of the conjugation length and different π–acceptor linkers were investigated by photophysical, redox and computational studies. The redox study reveals multiple oxidation waves corresponding to donor moieties (ferrocene and 4-(N,N-dimethylamino)phenyl group) and reduction waves corresponding to acceptor units (TCBD / cyclohexa-2,5- diene-1,4-diylidene-expanded TCBD). The thermogravimetric analysis data shows that the compounds exhibit high thermal stability. The computational studies reveal HOMO-LUMO gaps consistent with the experimentally obtained data.
AB - Symmetrical and unsymmetrical donor-acceptor (D–A) based chromophores were designed and synthesized by the Pd–catalyzed Sonogashira cross–coupling reaction of 1,1′-diiodoferrocene with (4-N,N-dimethylaminophenyl)ethyne followed by [2+2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). Ferrocene was used as a central donor unit and 4-(N,N-dimethylamino)phenyl group as the end-capping donor. Herein, we report the cycloaddition-retrocyclization reaction of TCNE/TCNQ groups on the disubstituted ferrocene containing more than one triple bond to get disubstituted tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD products. The effect of the conjugation length and different π–acceptor linkers were investigated by photophysical, redox and computational studies. The redox study reveals multiple oxidation waves corresponding to donor moieties (ferrocene and 4-(N,N-dimethylamino)phenyl group) and reduction waves corresponding to acceptor units (TCBD / cyclohexa-2,5- diene-1,4-diylidene-expanded TCBD). The thermogravimetric analysis data shows that the compounds exhibit high thermal stability. The computational studies reveal HOMO-LUMO gaps consistent with the experimentally obtained data.
KW - Charge transfer
KW - Cyclic voltammetry
KW - Cycloaddition
KW - Donor-acceptor
KW - Ferrocene
KW - Sonogashira cross-coupling
UR - http://www.scopus.com/inward/record.url?scp=85181079857&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2023.122998
DO - 10.1016/j.jorganchem.2023.122998
M3 - Article
AN - SCOPUS:85181079857
VL - 1006
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
M1 - 122998
ER -