Modulation of electronics and thermal stabilities of photochromic phosphino-aminoazobenzene derivatives in weak-link approach coordination complexes

Jung Su Park, Alejo M. Lifschitz, Ryan M. Young, Jose Mendez-Arroyo, Michael R Wasielewski, Charlotte L. Stern, Chad A. Mirkin

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

A series of d8 transition-metal (Pt(II) and Pd(II)) coordination complexes incorporating phosphine-functionalized aminoazobenzene derivatives as hemilabile phosphino-amine (P,N) ligands were synthesized and studied as model weak-link approach (WLA) photoresponsive constructs. The optical and photochemical properties of these complexes were found to be highly influenced by various tunable parameters in WLA systems, which include type of metal, coordination mode, type of ancillary ligand, solvent, and outer-sphere counteranions. In dichloromethane, reversible chelation and partial displacement of the P,N coordinating moieties allow for toggling between aminoazobenzene- or pseudostilbene- and azobenzene-type derivatives. The reversible switching between electronic states of azobenzene can be controlled through either addition or extraction of chloride counterions and is readily visualized in the separation between π-π* and n-π* bands in the complexes' electronic spectra. In acetonitrile solution, the WLA variables inherent to semiopen complexes have a significant impact on the half-lives of the corresponding cis isomers, allowing one to tune their half-lives from 20 to 21000 s, while maintaining photoisomerization behaviors with visible light. Therefore, one can significantly increase the thermal stability of a cis-aminoazobenzene derivative to the extent that single crystals for X-ray diffraction analysis can be grown for the first time, uncovering an unprecedented edge-to-face arrangement of the phenyl rings in the cis isomer. Overall, the azobenzene-functionalized model complexes shed light on the design parameters relevant for photocontrolled WLA molecular switches, as well as offer new ways of tuning the properties of azobenzene-based, photoresponsive materials.

Original languageEnglish
Pages (from-to)16988-16996
Number of pages9
JournalJournal of the American Chemical Society
Volume135
Issue number45
DOIs
Publication statusPublished - Nov 13 2013

Fingerprint

Azobenzene
Coordination Complexes
Thermodynamic stability
Electronic equipment
Hot Temperature
Modulation
Derivatives
phosphine
Isomers
Amines
Metals
Ligands
Photoisomerization
Methylene Chloride
Dichloromethane
Electronic states
Chelation
Acetonitrile
X-Ray Diffraction
X ray diffraction analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Modulation of electronics and thermal stabilities of photochromic phosphino-aminoazobenzene derivatives in weak-link approach coordination complexes. / Park, Jung Su; Lifschitz, Alejo M.; Young, Ryan M.; Mendez-Arroyo, Jose; Wasielewski, Michael R; Stern, Charlotte L.; Mirkin, Chad A.

In: Journal of the American Chemical Society, Vol. 135, No. 45, 13.11.2013, p. 16988-16996.

Research output: Contribution to journalArticle

Park, Jung Su ; Lifschitz, Alejo M. ; Young, Ryan M. ; Mendez-Arroyo, Jose ; Wasielewski, Michael R ; Stern, Charlotte L. ; Mirkin, Chad A. / Modulation of electronics and thermal stabilities of photochromic phosphino-aminoazobenzene derivatives in weak-link approach coordination complexes. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 45. pp. 16988-16996.
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abstract = "A series of d8 transition-metal (Pt(II) and Pd(II)) coordination complexes incorporating phosphine-functionalized aminoazobenzene derivatives as hemilabile phosphino-amine (P,N) ligands were synthesized and studied as model weak-link approach (WLA) photoresponsive constructs. The optical and photochemical properties of these complexes were found to be highly influenced by various tunable parameters in WLA systems, which include type of metal, coordination mode, type of ancillary ligand, solvent, and outer-sphere counteranions. In dichloromethane, reversible chelation and partial displacement of the P,N coordinating moieties allow for toggling between aminoazobenzene- or pseudostilbene- and azobenzene-type derivatives. The reversible switching between electronic states of azobenzene can be controlled through either addition or extraction of chloride counterions and is readily visualized in the separation between π-π* and n-π* bands in the complexes' electronic spectra. In acetonitrile solution, the WLA variables inherent to semiopen complexes have a significant impact on the half-lives of the corresponding cis isomers, allowing one to tune their half-lives from 20 to 21000 s, while maintaining photoisomerization behaviors with visible light. Therefore, one can significantly increase the thermal stability of a cis-aminoazobenzene derivative to the extent that single crystals for X-ray diffraction analysis can be grown for the first time, uncovering an unprecedented edge-to-face arrangement of the phenyl rings in the cis isomer. Overall, the azobenzene-functionalized model complexes shed light on the design parameters relevant for photocontrolled WLA molecular switches, as well as offer new ways of tuning the properties of azobenzene-based, photoresponsive materials.",
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