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Title: Platinum diimine bis(acetylide) complexes: Synthesis, characterization, and luminescence properties

Abstract

A new set of luminescent platinum(II) diimine complexes has been synthesized and characterized. The anionic ligands in these complexes are arylacetylides. The complexes are brightly emissive in fluid solution with relative emission quantum yields {phi}{sub em} ranging from 3 x 10{sup {minus}3} to 10{sup {minus}1}. Two series of complexes have been investigated. The first has the formula Pt(Rphen)(C{equivalent{underscore}to}CC{sub 6}H{sub 5}){sub 2} where Rphen is 1,10-phenanthroline substituted in the 5-position with R = H, Me, Cl, Br, NO{sub 2}, or C{equivalent{underscore}to}CC{sub 6}H{sub 5}, while the second has the formula Pt(dbbpy)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}X){sub 2} where dbbpy = 4,4{prime}-di(tert-butyl)bipyridine and X = H, Me, F, or NO{sub 2}. From NMR, IR, and electronic spectroscopies, all of the complexes are assigned a square planar coordination geometry with cis-alkynyl ligands. The crystal structure of Pt(phen)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}CH{sub 3}){sub 2} confirms this assignment. All of the complexes exhibit an absorption band at ca. 400 nm that corresponds to a Pt d {r{underscore}arrow} {pi}{asterisk}{sub diimine} charge-transfer transition. The variation of {lambda}{sub max} for this band with substituent variation supports this assignment. From similar changes in the energy of the solution luminescence as a function of substituents R and X, the emissive excited state is also of MLCTmore » origin, but with spin-forbidden character on the basis of excited-state lifetime measurements (0.01--5.6 {mu}s). The complexes undergo electron-transfer quenching, showing good Stern-Volmer behavior using 10-methylphenothiazine and N,N,N{prime},N{prime}-tetramethylbenzidine as reductive quenchers. Excited-state reduction potentials are estimated on the basis of a simple thermochemical analysis. Crystal data for Pt(phen)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}CH{sub 3}){sub 2}: monoclinic, space group C2/c, a = 19.0961(1){angstrom}, b = 10,4498(1){angstrom}, c = 11.8124(2){angstrom}, {beta} = 108.413(1){degree}, V = 2236.49{angstrom}{sup 3}, number of reflections 1614, number of variables 150, R1 = 0.0163, wR2 (I > 2{sigma}) = 0.0410.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Rochester, NY (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20017280
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 3; Other Information: PBD: 7 Feb 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; PLATINUM COMPLEXES; IMINES; SYNTHESIS; LUMINESCENCE; CRYSTAL STRUCTURE; PHENANTHROLINES; BIPYRIDINES; SPECTRA

Citation Formats

Hissler, M, Connick, W B, Geiger, D K, McGarrah, J E, Lipa, D, Lachicotte, R J, and Eisenberg, R. Platinum diimine bis(acetylide) complexes: Synthesis, characterization, and luminescence properties. United States: N. p., 2000. Web. doi:10.1021/ic991250n.
Hissler, M, Connick, W B, Geiger, D K, McGarrah, J E, Lipa, D, Lachicotte, R J, & Eisenberg, R. Platinum diimine bis(acetylide) complexes: Synthesis, characterization, and luminescence properties. United States. https://doi.org/10.1021/ic991250n
Hissler, M, Connick, W B, Geiger, D K, McGarrah, J E, Lipa, D, Lachicotte, R J, and Eisenberg, R. 2000. "Platinum diimine bis(acetylide) complexes: Synthesis, characterization, and luminescence properties". United States. https://doi.org/10.1021/ic991250n.
@article{osti_20017280,
title = {Platinum diimine bis(acetylide) complexes: Synthesis, characterization, and luminescence properties},
author = {Hissler, M and Connick, W B and Geiger, D K and McGarrah, J E and Lipa, D and Lachicotte, R J and Eisenberg, R},
abstractNote = {A new set of luminescent platinum(II) diimine complexes has been synthesized and characterized. The anionic ligands in these complexes are arylacetylides. The complexes are brightly emissive in fluid solution with relative emission quantum yields {phi}{sub em} ranging from 3 x 10{sup {minus}3} to 10{sup {minus}1}. Two series of complexes have been investigated. The first has the formula Pt(Rphen)(C{equivalent{underscore}to}CC{sub 6}H{sub 5}){sub 2} where Rphen is 1,10-phenanthroline substituted in the 5-position with R = H, Me, Cl, Br, NO{sub 2}, or C{equivalent{underscore}to}CC{sub 6}H{sub 5}, while the second has the formula Pt(dbbpy)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}X){sub 2} where dbbpy = 4,4{prime}-di(tert-butyl)bipyridine and X = H, Me, F, or NO{sub 2}. From NMR, IR, and electronic spectroscopies, all of the complexes are assigned a square planar coordination geometry with cis-alkynyl ligands. The crystal structure of Pt(phen)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}CH{sub 3}){sub 2} confirms this assignment. All of the complexes exhibit an absorption band at ca. 400 nm that corresponds to a Pt d {r{underscore}arrow} {pi}{asterisk}{sub diimine} charge-transfer transition. The variation of {lambda}{sub max} for this band with substituent variation supports this assignment. From similar changes in the energy of the solution luminescence as a function of substituents R and X, the emissive excited state is also of MLCT origin, but with spin-forbidden character on the basis of excited-state lifetime measurements (0.01--5.6 {mu}s). The complexes undergo electron-transfer quenching, showing good Stern-Volmer behavior using 10-methylphenothiazine and N,N,N{prime},N{prime}-tetramethylbenzidine as reductive quenchers. Excited-state reduction potentials are estimated on the basis of a simple thermochemical analysis. Crystal data for Pt(phen)(C{equivalent{underscore}to}CC{sub 6}H{sub 4}CH{sub 3}){sub 2}: monoclinic, space group C2/c, a = 19.0961(1){angstrom}, b = 10,4498(1){angstrom}, c = 11.8124(2){angstrom}, {beta} = 108.413(1){degree}, V = 2236.49{angstrom}{sup 3}, number of reflections 1614, number of variables 150, R1 = 0.0163, wR2 (I > 2{sigma}) = 0.0410.},
doi = {10.1021/ic991250n},
url = {https://www.osti.gov/biblio/20017280}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 3,
volume = 39,
place = {United States},
year = {Mon Feb 07 00:00:00 EST 2000},
month = {Mon Feb 07 00:00:00 EST 2000}
}