Synthesis of Cyclometallated Platinum Complexes with Substituted Thienylpyridines and Detailed Characterization of Their Luminescence Properties / Kozhevnikov Dmitry N.,Kozhevnikov Valery N.,Ustinova Maria M.,Santoro Amedeo,Bruce Duncan W.,Koenig Burkhard,Czerwieniec Rafal,Fischer Tobias,Zabel Manfred,Yersin Hartmut // INORGANIC CHEMISTRY. - 2009. - V. 48, l. 9. - P. 4179-4189.

ISSN/EISSN:

0020-1669 / нет данных

Type:

Article

Abstract:

Synthesis of various derivatives of 2-(2-thienyl)pyridine via substituted 3-thienyl-1,2,4-triazines is reported. The final step of the synthesis is a transformation of the triazine ring to pyridine in an aza-Diels-Alder-type reaction. The resulting 5-aryl-2-(2-thienyl)pyridines (HL1-HL4) and 5-aryl-2-(2-thienyl)cyclopenteno{[}c]pyridines (HL5-HL8) (with aryl = phenyl, 4-methoxyphenyl, 2-naphtyl, and 2-thienyl) were used as cyclometallating ligands to prepare a series of eight luminescent platinum complexes of the type {[}Pt(L)(acac)] (L = cyclometallating ligand, acac = acetylacetonato). X-ray single crystal structures of three complexes of that series, {[}Pt(L5)(acac)] = {[}Pt(5-phenyl-2-(2-thienyl)cyclopenteno{[}c]pyridine)(acac)], {[}Pt(L6)(acac)] = {[}Pt(5-(4-methoxy)-2-(2-thienyl)cyclopenteno{[}c]pyridine)(acac)], and {[}Pt(L7)(acac)] = {[}Pt(5-(2-naphtyl)-2-(2-thienyl) cyclopenteno{[}c]pyridine)(acac)] were determined. Photoluminescence and electronic absorption spectra of the new {[}Pt(L)(acac)] complexes are reported. For two representative compounds of that series, {[}Pt(L4)(acac)] and {[}Pt(L5)(acac)], a detailed photophysical characterization based on highly resolved emission and excitation spectra, as well as on emission decay properties, was carried out. The studies down to low temperature (T = 1.2 K) and up to high magnetic fields (B = 10 T) allowed us to characterize the three individual substates of the emitting triplet state. In particular, it is shown that the lowest triplet states of {[}Pt(L4)(acac)] and {[}Pt(L5)(acac)] are largely ligand-centered (LC) of (3)pi-pi{*}character, which experience only weak spin-orbit couplings to higher lying singlet states.

Author keywords:

SIMPLE LEGO SYSTEM; DEMAND DIELS-ALDER; IRIDIUM(III) DIIMINE COMPLEXES; DETECTED MAGNETIC-RESONANCE; INTRALIGAND CHARGE-TRANSFER; SENSITIZED SOLAR-CELLS; ONE-POT SYNTHESIS; ENERGY-GAP LAW; PHOTOPHYSICAL PROPERTIES; HIGH-RESOLUTION

DOI:

10.1021/ic802401j

Web of Science ID:

ISI:000265749000035

Соавторы в МНС:

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Другие поля

Поле	Значение
Month	MAY 4
Publisher	AMER CHEMICAL SOC
Address	1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Language	English
Keywords-Plus	SIMPLE LEGO SYSTEM; DEMAND DIELS-ALDER; IRIDIUM(III) DIIMINE COMPLEXES; DETECTED MAGNETIC-RESONANCE; INTRALIGAND CHARGE-TRANSFER; SENSITIZED SOLAR-CELLS; ONE-POT SYNTHESIS; ENERGY-GAP LAW; PHOTOPHYSICAL PROPERTIES; HIGH-RESOLUTION
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Inorganic \& Nuclear
Author-Email	dnk@ios.uran.ru db519@york.ac.uk hartmut.yersin@chemie.uni-regens-burg.de
ResearcherID-Numbers	Kozhevnikov, Valery/B-1178-2010 Koenig, Burkhard/A-1362-2009 Czerwieniec, Rafal/K-7644-2012
ORCID-Numbers	Kozhevnikov, Valery/0000-0001-7032-8886 Koenig, Burkhard/0000-0002-6131-4850 Czerwieniec, Rafal/0000-0003-4789-6273 Bruce, Duncan/0000-0002-1365-2222
Funding-Acknowledgement	Bundesministerium fur Bildung and Forschung, BMBF; Russian Foundation for Basic Research, RFBR; University of York; Royal Society; EU; EPSRC
Funding-Text	The authors thank the Bundesministerium fur Bildung and Forschung, BMBF (R.C., T.F., and H.Y.), the Russian Foundation for Basic Research, RFBR, the University of York (M.M.U and A.S.), the Royal Society (D.N.K), the EU and the EPSRC (V.N.K.) for the funding and Johnson Matthey for generous loans of platinum metal salts.
Number-of-Cited-References	70
Usage-Count-Last-180-days	3
Usage-Count-Since-2013	24
Journal-ISO	Inorg. Chem.
Doc-Delivery-Number	441DH