A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties

Jia, Chunyang; Ding, J.; Liu, Shi-Xia; Labat, G.; Neels, A.; Hauser, A.; Decurtins, Silvio (2013). A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties. Polyhedron, 55, pp. 87-91. Elsevier 10.1016/j.poly.2013.02.064

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The reaction of 4,5-bis(2'-cyanoethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with Pt(phen)Cl-2 (phen = 1,10-phenanthroline) with CsOH as base in CH3OH-THE affords the target complex I in 44% yield. This complex crystallizes in the monoclinic space group P2(1)/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) angstrom, beta = 107.693(12)degrees, V = 2672.4(5) angstrom(3) and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm(-1) (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm(-1) (640 nm) in glassy solution below 150K results in emission from the (LLCT)-L-3 excited state. GRAPHICS (C) 2013 Elsevier Ltd. All rights reserved.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Jia, Chunyang; Liu, Shi-Xia and Decurtins, Silvio

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0277-5387

Publisher:

Elsevier

Language:

English

Submitter:

Gabriela Claudia Frei

Date Deposited:

25 Jul 2014 16:24

Last Modified:

02 Sep 2015 11:38

Publisher DOI:

10.1016/j.poly.2013.02.064

Uncontrolled Keywords:

Tetrathiafulvalene, Intramolecular charge-transfer, Spectroelectrochemistry

BORIS DOI:

10.7892/boris.46365

URI:

https://boris.unibe.ch/id/eprint/46365

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