Single crystal X-ray and optical studies on bis(1,5-diazacyclooctane)-copper(II) nitrate, a thermochromic copper(II) complex involving hydrogen bonds between the ligand and the counter ion.
スポンサーリンク
概要
- 論文の詳細を見る
A thermochromic copper(II) complex of 1,5-diazacyclooctane (daco), [Cu(daco)<SUB>2</SUB>](NO<SUB>3</SUB>)<SUB>2</SUB>, has been subjected to single-crystal X-ray and optical studies. This complex is orange as isolated, but it turns violet discontinuously when heated above 90 °C and returns to orange on cooling. Crystal structure of the low-temperature form has been determined at room temperature; the complex crystallizes in the monoclinic space group <I>P</I>2<SUB>1</SUB>⁄<I>n</I> with <I>a</I>=7.9040(7), <I>b</I>=15.694(1), <I>c</I>=7.0886(7) Å, β=95.36(1)°; <I>V</I>=875.5(1) Å<SUP>3</SUP>, and <I>Z</I>=2. The CuN<SUB>4</SUB> chelate plane is planar and Cu–N coordination bonds are rather short. The structure has revealed the presence of weak hydrogen bonds bridging imino groups of the ligands with the nitrate ions and forming a macrocycle-like ring system, which results in enhancement of the ligand field strength. Single-crystal visible and infrared spectra for both low- and high-temperature forms have heen obtained and compared. A high-energy d–d transition band(s) causing the orange color at room temperature is in contrast to an extremely flattened broad band(s) for the violet form. The IR spectra of the two forms clearly differ in the intensity of ν<SUB>NH</SUB> stretching peak, implying that the thermochromic phase transition involves a change in the nature of the hydrogen bonds of the imine ligands. On the basis of these observations and comparison to reported studies on a similarly thermochromic copper(II) complex, a mechanism is suggested involving dynamic fluctuation of the ligand field and geometry due to thermal motion of the anion/ligand hydrogen bond system.
- 公益社団法人 日本化学会の論文
著者
-
MARUMO Fumiyuki
Research Laboratory of Engineering Materials, Tokyo Institute of Technology
-
Sone Kozo
Department Of Chemistry Faculty Of Science Josai University
-
Fukuda Yutaka
Department Of Chemistry Faculty Of Science Ochanomizu Univeity
-
Hoshino Naomi
Department of Chemistry, Faculty of Science, Ochanomizu University
-
Tanaka Kiyoaki
Research Laboratory of Engineering Materials, Tokyo Institute of Technology
関連論文
- Survival-promoting effect of electrical stimulation on axotomized retinal ganglion cells
- Thermodynamic Activity of Liquid Zn-Cd Alloys Studied by EMF Method with Zirconia Solid Electrolyte
- Syntheses and Structure of New Dinuclear Palladium(II)Complexes with 1, 1, 2, 2-Tetraacetylethanate and β-Diketonate
- d-f Metal Ion Interaction through Fe-C≡N-Ln Bridge between Dicyanobis(1,10-phenanthroline)iron(II) Complex and LnCl_3
- X-Ray Diffraction Study on Phase Relation of BaZnGeO_4
- Formation and Structure of Mixed Quaternary Chelates with Late-Lanthanide Metal Ions
- Alcohol Brine Freezing of Japanese Horse Mackerel (Trachurus japonicus) for Raw Consumption
- Structure and Enantio-Differentiating Behaviors of Nickel(II) Complexes with Chiral Schiff Base Ligands Derived from 1,1'-Binaphthyl-2,2'-diamine
- Agmatine Suppresses Mesangial Cell Proliferation by Modulating Polyamine Metabolism
- Hemispheric differences in color detection : a comparison of visual reaction times in human subjects
- Observation of the New κ^2C,O:κ^2C',O' Coordination Mode of 1,1,2,2-Tetraacetylethanato Ligand in a Dinuclear 1,1,1,5,5,5-Hexafluoroacetylacetonato Palladium(II) Complex
- Effect of Freezing Rate on the Denaturation of Myofibrillar Protein in Fish Muscle (特集 次世代の高品質凍結食品を目指す新技術)
- Alkyl-Substitution Effect of the Diamine on Coordination Geometry and Ligand-Field Strength of Nickel(II) Mixed-Ligand Complexes Containing N-Alkylethylenediamine, Acetylacetonate, and Nitrate Ligands
- Synthesis, Crystal Structure, and Chromotropic Properties of Mixed-Ligand Nickel(II) Complexes with 1,3-Diketonate and P-N Bidentate Ligands
- Syntheses, Structures, Spectroscopic Properties, and Thermal Behavior of Nickel(II) Mixed-Ligand Complexes with N, N, N', N'-Tetramethylethylenediamine, Benzoylacetonate, and a Halide Anion
- Synthesis of New Cationic Schiff Base Complexes of Copper(II) and Their Selective Binding with DNA
- Apoptotic death of beta cells induced by optic nerve transection in adult cat retinas
- Synthesis, Characterization and Spin-Crossover Behaviors of [Co(hydroxycarboxylato)(triphos)] Complexes
- Structures and Magnetic Properties of Dinuclear Copper(II) Complexes Containing a Bulky Diamine Ligand, 1,2-Dipiperidinoethane
- Different Magnetic Properties for Diastereomers of Alkoxide-bridged (β-Diketonato)ruthenium(III) Binuclear Complexes
- Substituent and Solvent Effects on Square-Planar-Tetrahedral Equilibria of Bis[4-(arylimino)pentan-2-onato]nickel(II) and Bis[1-aryl-3-(phenylimino)butan-1-onato]nickel(II) Complexes
- Copper(II) Mixed Ligand Complex with an N-Alkylated Diamine and a New β-Diketonate
- Theoretical Study on the Disproportionation Reaction of Nickel(II) Mixed-Ligand Complexes Containing N,N,N',N'-Tetramethylethylenediamine, Benzoylacetonate, and a Halide Anion
- Raman Spectra of Hydroxo Complexes of Tin (II) and Lead (II) in Strongly Alkaline Solutions, and of Antimony (III) Fluoride in Various Solvents
- Steric Crowding Effect of 1,3-Diketonates on the Structures and the Solution Behaviors of Nickel(II) Mixed-Ligand Complexes
- Solvatochromism and Structure of Acetylacetonatocoper(II) Complexes with N,N'-Dipropyl-,N,N,N',N'-Tetraproplyl-, and N,N- and N,N'-Diisopropylethylenediamines
- Anion-Sensing Electrodes Based on Nickel(II) Mixed Ligand Complexes
- Studies on mixed chelates. XIX. 5-coordinate nickel(II) complexes with N,N,N'N",N"-pentamethyldiethylenetriamine and .BETA.-diketonates.
- A Ruptured Basilar Tip Aneurysm Showing Repeated Perianeurysmal Edema after Endovascular Coil Embolization: Case Report
- Studies on mixed chelates. XIII. Formation and electronic spectra of 5-coordinated mixed copper(II) chelates containing N-alkylated ethylenediamine, acetylacetonate, and halide anions.
- On Liquefaction Caused by the Trituration of Pairs of Solid Compounds
- Preparation and thermal square planar-octahedral transformation of nickel(II) complexes containing 1,2-butanediamine or 3,3-dimethyl-1,2-butanediamine in solid phase.
- The Structures and Thermal Behaviors of Bivalent Metal Succinates in the Solid State
- Influences of the lanthanoid contraction on the thermal dehydration reactions of lanthanoid(III) malonate hydrates.
- Studies on mixed chelates. VI. Mixed copper(II) chelates with N,N,N',N'-tetraethylethylenediamine and various .BETA.-diketones.
- On the assignment of band II in the electronic spectrum of (Ni(H2O)6)2+.
- Studies on mixed chelates. VII. Mixed nickel(II) chelates containing N,N'- or N,N-dialkylethylenediamines and acetylacetone.
- Single crystal X-ray and optical studies on bis(1,5-diazacyclooctane)-copper(II) nitrate, a thermochromic copper(II) complex involving hydrogen bonds between the ligand and the counter ion.
- Studies on mixed chelates. XVI. Mixed copper(II) chelates with 1,2-dipiperidinoethane and .BETA.-diketonates.
- Studies on mixed chelates. XV. An ESR investigation of solvaochromic copper(II) complexes with various N-alkylated ethylenediamines and .BETA.-diketonates.
- On some mixed chelates of nickel(II) which are highly volatile,fusible,and soluble in nonpolar solvents.
- Studies on Mixed Chelates. I. Mixed Copper(II) Chelates with N,N,N′,N′-Tetramethylenediamine and a Bidentate Ligand
- (Acetylacetonato)(N,N,N',N'-tetramethylethylenediamine)copper(II) tetraphenylborate as a solvent basicity indicator.
- Solvent and Temperature Effects on the Electronic Spectra of Mixed Nickel(II) Chelates with N,N,N′,N′-Tetramethylethylenediamine and Acetylacetone
- Studies on mixed chelates. XII. Formation and electronic spectra of 5-coordinated mixed copper(II) chelates containing N-alkylated ethylenediamine, acetylacetonate, and pseudohalide anions.
- Solvent effect on the Raman spectra of mercury(II) halides.
- Synthesis and Thermochromic Properties of New Five-coordinate Copper Chelates
- Thermal dehydration reactions of bivalent transition metal malonate dihydrates in solid state.
- Imaging Δρwith the Photon Factory BL-14A Four Circle Diffractometer
- Studies on mixed chelates. XI. Syntheses and comparative study of a new series of mixed nickel(II) chelates with halide and pseudohalide ligands.
- Syntheses and thermal properties of some bivalent transition metal complexes with 1,4-diazabicyclo[2.2.2]octane.
- Effect of solvent on the electrochemical properties of chromotropic copper(II) mixed chelates.