A polymorphic platinum(II) complex: Yellow, red, and green polymorphs and X-ray crystallography of [Pt(fdpb)Cl] [Hfdpb = 1,3-Bis(5-trifluoromethyl-2- pyridyl)benzene]

Yuta Nishiuchi, Asuka Takayama, Takayoshi Suzuki, Kazuteru Shinozaki

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

We investigated polymorphism in [Pt(fdpb)Cl] [Hfdpb = 1,3-bis(5- trifluoromethyl-2-pyridyl)benzene]. The following polymorphs of the complex were crystallized: yellow [Form Y; orthorhombic, Pca21, a = 23.4336(14) Å, b = 4.6377(2) Å, c = 15.7845(9) Å, Z = 4], red [Form R; monoclinic, C2/c, a = 21.3619(12) Å, b = 13.5629(7) Å, c = 13.6974(6) Å, β = 122.301(2)°, Z = 8], and dark green [Form G; monoclinic,P21/a, a = 6.7953(4) Å, b = 18.2519(12) Å, c = 13.5199(8) Å, β = 96.039(2)°, Z = 4]. The yellow color of Form Y was due to the influence of stacking on the π,π* absorption of the Pt molecule; the red color of Form R originated from a MMLCT absorption due to Pt-Pt interactions in a closely stacked dimer; and the dark green of Form G was attributed to the absorption of a linear array of PtII complexes. The polymorphs emitted luminescence at around 550 (Form Y), 670 (Form R), and 750 nm (Form G). Mechanical grinding of the crystals changed the polymorphs from the crystalline to the amorphous phase; the emission spectra of ground samples of Forms Y and R, observed at 750 nm, were identical. When the amorphous solid was heated to around 500 K, the emission spectrum was blueshifted to 670 nm due to a phase transition from amorphous to crystalline. Heating also caused a crystal-crystal transformation; phase transitions from Form G to Form R and Form R to Form Y proceeded at 430-470 and 540-560 K, respectively. Polymorphs of a platinum(II) complex were prepared, and their crystal structures were clarified by X-ray crystallography. Mechanical grinding changed the polymorphs from the crystalline to the amorphous phase. Heating caused the transition between the amorphous and the crystal phase and the crystal-crystal transformations of the green form to the red from and of the red form to the yellow form.

Original languageEnglish
Pages (from-to)1815-1823
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number11
DOIs
Publication statusPublished - Apr 2011

Fingerprint

X ray crystallography
Benzene
Platinum
Polymorphism
Crystals
Crystallization
Phase transitions
Color
Heating
Dimers
Luminescence
Crystal structure
Crystalline materials
Molecules

Keywords

  • Crystal engineering
  • Luminescence
  • Phase transitions
  • Polymorphism
  • Stacking interactions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{1bf9fede0120480f90d683fb3373dbe3,
title = "A polymorphic platinum(II) complex: Yellow, red, and green polymorphs and X-ray crystallography of [Pt(fdpb)Cl] [Hfdpb = 1,3-Bis(5-trifluoromethyl-2- pyridyl)benzene]",
abstract = "We investigated polymorphism in [Pt(fdpb)Cl] [Hfdpb = 1,3-bis(5- trifluoromethyl-2-pyridyl)benzene]. The following polymorphs of the complex were crystallized: yellow [Form Y; orthorhombic, Pca21, a = 23.4336(14) {\AA}, b = 4.6377(2) {\AA}, c = 15.7845(9) {\AA}, Z = 4], red [Form R; monoclinic, C2/c, a = 21.3619(12) {\AA}, b = 13.5629(7) {\AA}, c = 13.6974(6) {\AA}, β = 122.301(2)°, Z = 8], and dark green [Form G; monoclinic,P21/a, a = 6.7953(4) {\AA}, b = 18.2519(12) {\AA}, c = 13.5199(8) {\AA}, β = 96.039(2)°, Z = 4]. The yellow color of Form Y was due to the influence of stacking on the π,π* absorption of the Pt molecule; the red color of Form R originated from a MMLCT absorption due to Pt-Pt interactions in a closely stacked dimer; and the dark green of Form G was attributed to the absorption of a linear array of PtII complexes. The polymorphs emitted luminescence at around 550 (Form Y), 670 (Form R), and 750 nm (Form G). Mechanical grinding of the crystals changed the polymorphs from the crystalline to the amorphous phase; the emission spectra of ground samples of Forms Y and R, observed at 750 nm, were identical. When the amorphous solid was heated to around 500 K, the emission spectrum was blueshifted to 670 nm due to a phase transition from amorphous to crystalline. Heating also caused a crystal-crystal transformation; phase transitions from Form G to Form R and Form R to Form Y proceeded at 430-470 and 540-560 K, respectively. Polymorphs of a platinum(II) complex were prepared, and their crystal structures were clarified by X-ray crystallography. Mechanical grinding changed the polymorphs from the crystalline to the amorphous phase. Heating caused the transition between the amorphous and the crystal phase and the crystal-crystal transformations of the green form to the red from and of the red form to the yellow form.",
keywords = "Crystal engineering, Luminescence, Phase transitions, Polymorphism, Stacking interactions",
author = "Yuta Nishiuchi and Asuka Takayama and Takayoshi Suzuki and Kazuteru Shinozaki",
year = "2011",
month = "4",
doi = "10.1002/ejic.201001359",
language = "English",
pages = "1815--1823",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "11",

}

TY - JOUR

T1 - A polymorphic platinum(II) complex

T2 - Yellow, red, and green polymorphs and X-ray crystallography of [Pt(fdpb)Cl] [Hfdpb = 1,3-Bis(5-trifluoromethyl-2- pyridyl)benzene]

AU - Nishiuchi, Yuta

AU - Takayama, Asuka

AU - Suzuki, Takayoshi

AU - Shinozaki, Kazuteru

PY - 2011/4

Y1 - 2011/4

N2 - We investigated polymorphism in [Pt(fdpb)Cl] [Hfdpb = 1,3-bis(5- trifluoromethyl-2-pyridyl)benzene]. The following polymorphs of the complex were crystallized: yellow [Form Y; orthorhombic, Pca21, a = 23.4336(14) Å, b = 4.6377(2) Å, c = 15.7845(9) Å, Z = 4], red [Form R; monoclinic, C2/c, a = 21.3619(12) Å, b = 13.5629(7) Å, c = 13.6974(6) Å, β = 122.301(2)°, Z = 8], and dark green [Form G; monoclinic,P21/a, a = 6.7953(4) Å, b = 18.2519(12) Å, c = 13.5199(8) Å, β = 96.039(2)°, Z = 4]. The yellow color of Form Y was due to the influence of stacking on the π,π* absorption of the Pt molecule; the red color of Form R originated from a MMLCT absorption due to Pt-Pt interactions in a closely stacked dimer; and the dark green of Form G was attributed to the absorption of a linear array of PtII complexes. The polymorphs emitted luminescence at around 550 (Form Y), 670 (Form R), and 750 nm (Form G). Mechanical grinding of the crystals changed the polymorphs from the crystalline to the amorphous phase; the emission spectra of ground samples of Forms Y and R, observed at 750 nm, were identical. When the amorphous solid was heated to around 500 K, the emission spectrum was blueshifted to 670 nm due to a phase transition from amorphous to crystalline. Heating also caused a crystal-crystal transformation; phase transitions from Form G to Form R and Form R to Form Y proceeded at 430-470 and 540-560 K, respectively. Polymorphs of a platinum(II) complex were prepared, and their crystal structures were clarified by X-ray crystallography. Mechanical grinding changed the polymorphs from the crystalline to the amorphous phase. Heating caused the transition between the amorphous and the crystal phase and the crystal-crystal transformations of the green form to the red from and of the red form to the yellow form.

AB - We investigated polymorphism in [Pt(fdpb)Cl] [Hfdpb = 1,3-bis(5- trifluoromethyl-2-pyridyl)benzene]. The following polymorphs of the complex were crystallized: yellow [Form Y; orthorhombic, Pca21, a = 23.4336(14) Å, b = 4.6377(2) Å, c = 15.7845(9) Å, Z = 4], red [Form R; monoclinic, C2/c, a = 21.3619(12) Å, b = 13.5629(7) Å, c = 13.6974(6) Å, β = 122.301(2)°, Z = 8], and dark green [Form G; monoclinic,P21/a, a = 6.7953(4) Å, b = 18.2519(12) Å, c = 13.5199(8) Å, β = 96.039(2)°, Z = 4]. The yellow color of Form Y was due to the influence of stacking on the π,π* absorption of the Pt molecule; the red color of Form R originated from a MMLCT absorption due to Pt-Pt interactions in a closely stacked dimer; and the dark green of Form G was attributed to the absorption of a linear array of PtII complexes. The polymorphs emitted luminescence at around 550 (Form Y), 670 (Form R), and 750 nm (Form G). Mechanical grinding of the crystals changed the polymorphs from the crystalline to the amorphous phase; the emission spectra of ground samples of Forms Y and R, observed at 750 nm, were identical. When the amorphous solid was heated to around 500 K, the emission spectrum was blueshifted to 670 nm due to a phase transition from amorphous to crystalline. Heating also caused a crystal-crystal transformation; phase transitions from Form G to Form R and Form R to Form Y proceeded at 430-470 and 540-560 K, respectively. Polymorphs of a platinum(II) complex were prepared, and their crystal structures were clarified by X-ray crystallography. Mechanical grinding changed the polymorphs from the crystalline to the amorphous phase. Heating caused the transition between the amorphous and the crystal phase and the crystal-crystal transformations of the green form to the red from and of the red form to the yellow form.

KW - Crystal engineering

KW - Luminescence

KW - Phase transitions

KW - Polymorphism

KW - Stacking interactions

UR - http://www.scopus.com/inward/record.url?scp=79953693948&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79953693948&partnerID=8YFLogxK

U2 - 10.1002/ejic.201001359

DO - 10.1002/ejic.201001359

M3 - Article

AN - SCOPUS:79953693948

SP - 1815

EP - 1823

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

IS - 11

ER -