Transformation of a Cu II thiazolo-1,2,4-triazine derivative from a metastable coordination network to a monomer in solution and vapor conditions

Akiko Hori, Takahiro Kikuchi, Kumiko Miyamoto, Takashi Okano, Chihiro Kachi-Terajima, Hiroshi Sakaguchi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Although mononuclear complexes were mainly obtained from Cu 2+ ion and phenyl-, ethyl- or benzyl-substituted thiazolo-1,2,4-triazine derivatives, unique metastable orange-yellow crystals [CuCl 2(3a)] n (5a; Cu/3a = 1:1) with the phenyl-substituted derivative 3a were obtained as a 1D coordination polymer through bis(μ-chloro) linkages in a 2-propanol solution. The crystals show dynamic and irreversible structural transformation into blue crystals of [CuCl 2(3a) 2] (6a; Cu/3a = 1:2) not only in solution but also in vapor conditions. As 5a and 6a are ferromagnetic and paramagnetic, respectively, the transformation of 5a was monitored by magnetic susceptibility measurements in the solid state, and πT of 5a decreased according to the color change. The XRD pattern of 5a also changed to a new aggregation state, ascribed to the disproportionation of the 1D network to form a mononuclear complex and a solvated metal ion in the crystalline state. This unusual 1D network is stabilized by intermolecular π-π stacking between the phenyl and the triazine moieties, and comparative studies of the ethyl and benzyl-substituted complexes show no polymeric structures. The coordination site of all the thiazolo-1,2,4-triazine derivatives in this work was found to be the imino nitrogen as a monodentate coordination site by X-ray crystallographic studies and DFT calculations.

Original languageEnglish
Pages (from-to)3059-3066
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number20
DOIs
Publication statusPublished - 2011 Jul
Externally publishedYes

Fingerprint

Monomers
Vapors
Derivatives
Crystals
Triazines
2-Propanol
Magnetic susceptibility
Discrete Fourier transforms
Metal ions
Polymers
Nitrogen
Agglomeration
Ions
Crystalline materials
Color
X rays
1,2,4-triazine

Keywords

  • Coordination modes
  • Copper
  • Magnetic properties
  • Metastable compounds
  • Solvatochromism

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Transformation of a Cu II thiazolo-1,2,4-triazine derivative from a metastable coordination network to a monomer in solution and vapor conditions. / Hori, Akiko; Kikuchi, Takahiro; Miyamoto, Kumiko; Okano, Takashi; Kachi-Terajima, Chihiro; Sakaguchi, Hiroshi.

In: European Journal of Inorganic Chemistry, No. 20, 07.2011, p. 3059-3066.

Research output: Contribution to journalArticle

Hori, Akiko ; Kikuchi, Takahiro ; Miyamoto, Kumiko ; Okano, Takashi ; Kachi-Terajima, Chihiro ; Sakaguchi, Hiroshi. / Transformation of a Cu II thiazolo-1,2,4-triazine derivative from a metastable coordination network to a monomer in solution and vapor conditions. In: European Journal of Inorganic Chemistry. 2011 ; No. 20. pp. 3059-3066.
@article{226321b896c14f55ac43f7b9d3d5df8f,
title = "Transformation of a Cu II thiazolo-1,2,4-triazine derivative from a metastable coordination network to a monomer in solution and vapor conditions",
abstract = "Although mononuclear complexes were mainly obtained from Cu 2+ ion and phenyl-, ethyl- or benzyl-substituted thiazolo-1,2,4-triazine derivatives, unique metastable orange-yellow crystals [CuCl 2(3a)] n (5a; Cu/3a = 1:1) with the phenyl-substituted derivative 3a were obtained as a 1D coordination polymer through bis(μ-chloro) linkages in a 2-propanol solution. The crystals show dynamic and irreversible structural transformation into blue crystals of [CuCl 2(3a) 2] (6a; Cu/3a = 1:2) not only in solution but also in vapor conditions. As 5a and 6a are ferromagnetic and paramagnetic, respectively, the transformation of 5a was monitored by magnetic susceptibility measurements in the solid state, and πT of 5a decreased according to the color change. The XRD pattern of 5a also changed to a new aggregation state, ascribed to the disproportionation of the 1D network to form a mononuclear complex and a solvated metal ion in the crystalline state. This unusual 1D network is stabilized by intermolecular π-π stacking between the phenyl and the triazine moieties, and comparative studies of the ethyl and benzyl-substituted complexes show no polymeric structures. The coordination site of all the thiazolo-1,2,4-triazine derivatives in this work was found to be the imino nitrogen as a monodentate coordination site by X-ray crystallographic studies and DFT calculations.",
keywords = "Coordination modes, Copper, Magnetic properties, Metastable compounds, Solvatochromism",
author = "Akiko Hori and Takahiro Kikuchi and Kumiko Miyamoto and Takashi Okano and Chihiro Kachi-Terajima and Hiroshi Sakaguchi",
year = "2011",
month = "7",
doi = "10.1002/ejic.201100119",
language = "English",
pages = "3059--3066",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "20",

}

TY - JOUR

T1 - Transformation of a Cu II thiazolo-1,2,4-triazine derivative from a metastable coordination network to a monomer in solution and vapor conditions

AU - Hori, Akiko

AU - Kikuchi, Takahiro

AU - Miyamoto, Kumiko

AU - Okano, Takashi

AU - Kachi-Terajima, Chihiro

AU - Sakaguchi, Hiroshi

PY - 2011/7

Y1 - 2011/7

N2 - Although mononuclear complexes were mainly obtained from Cu 2+ ion and phenyl-, ethyl- or benzyl-substituted thiazolo-1,2,4-triazine derivatives, unique metastable orange-yellow crystals [CuCl 2(3a)] n (5a; Cu/3a = 1:1) with the phenyl-substituted derivative 3a were obtained as a 1D coordination polymer through bis(μ-chloro) linkages in a 2-propanol solution. The crystals show dynamic and irreversible structural transformation into blue crystals of [CuCl 2(3a) 2] (6a; Cu/3a = 1:2) not only in solution but also in vapor conditions. As 5a and 6a are ferromagnetic and paramagnetic, respectively, the transformation of 5a was monitored by magnetic susceptibility measurements in the solid state, and πT of 5a decreased according to the color change. The XRD pattern of 5a also changed to a new aggregation state, ascribed to the disproportionation of the 1D network to form a mononuclear complex and a solvated metal ion in the crystalline state. This unusual 1D network is stabilized by intermolecular π-π stacking between the phenyl and the triazine moieties, and comparative studies of the ethyl and benzyl-substituted complexes show no polymeric structures. The coordination site of all the thiazolo-1,2,4-triazine derivatives in this work was found to be the imino nitrogen as a monodentate coordination site by X-ray crystallographic studies and DFT calculations.

AB - Although mononuclear complexes were mainly obtained from Cu 2+ ion and phenyl-, ethyl- or benzyl-substituted thiazolo-1,2,4-triazine derivatives, unique metastable orange-yellow crystals [CuCl 2(3a)] n (5a; Cu/3a = 1:1) with the phenyl-substituted derivative 3a were obtained as a 1D coordination polymer through bis(μ-chloro) linkages in a 2-propanol solution. The crystals show dynamic and irreversible structural transformation into blue crystals of [CuCl 2(3a) 2] (6a; Cu/3a = 1:2) not only in solution but also in vapor conditions. As 5a and 6a are ferromagnetic and paramagnetic, respectively, the transformation of 5a was monitored by magnetic susceptibility measurements in the solid state, and πT of 5a decreased according to the color change. The XRD pattern of 5a also changed to a new aggregation state, ascribed to the disproportionation of the 1D network to form a mononuclear complex and a solvated metal ion in the crystalline state. This unusual 1D network is stabilized by intermolecular π-π stacking between the phenyl and the triazine moieties, and comparative studies of the ethyl and benzyl-substituted complexes show no polymeric structures. The coordination site of all the thiazolo-1,2,4-triazine derivatives in this work was found to be the imino nitrogen as a monodentate coordination site by X-ray crystallographic studies and DFT calculations.

KW - Coordination modes

KW - Copper

KW - Magnetic properties

KW - Metastable compounds

KW - Solvatochromism

UR - http://www.scopus.com/inward/record.url?scp=79959816052&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79959816052&partnerID=8YFLogxK

U2 - 10.1002/ejic.201100119

DO - 10.1002/ejic.201100119

M3 - Article

SP - 3059

EP - 3066

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

IS - 20

ER -