Syntheses and accumulation of novel hydrogen-bonded electron-donor molecules including a nitrogen-heterocycle

• Project/Area Number: 16350074
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Osaka University
• Principal Investigator: MORITA Yasushi Osaka University, Graduate School of Science, Associate Professor, 理学研究科, 助教授 (70230133)
• Project Period (FY): 2004 – 2005
• Project Status: Completed (Fiscal Year 2005)
• Budget Amount: ¥16,000,000 (Direct Cost: ¥16,000,000); Fiscal Year 2005: ¥4,600,000 (Direct Cost: ¥4,600,000); Fiscal Year 2004: ¥11,400,000 (Direct Cost: ¥11,400,000)
• Keywords: hydrogen bond / charge transfer / electrical conductivity / benzoquinone / tetrathiafulvalene / metal

Research Abstract

In order to explore novel molecular conductors based on hydrogen-bonding (H-bonding) interaction, we have been much interested in an imidazole-ring system as redox-active molecule and as an intriguing functionality of H-bond. In addition to the strong and directional feature of H-bond to accumulate and order molecular aggregation, we focus on realization of an exotic electronic modulation effect of H-bond in purely organic charge-transfer (CT) complexes and salts. We designed and synthesized novel H-bonded CT salts of TCNQ with mono- and di-protonated 4,4'-biimidazolium, and demonstrated high potential of 4,4'-biimidazole system in molecular conductors from the viewpoint of crystal engineering and electronic modulation. Crystal structure analyses of these CT salts unambiguously turned out an an importance of H-bonding modes depending on the protpnated states for stacking partially ionized TCNQ molecules to gain high electrical conductivity. Recently, we designed a TTF-imidazole (TTF-Im) dyad as a simple modification of TTF with H-bonding functionality. The p-chloranil CT complex of TTF-Im was obtained as black needle-like crystals and possessed a H-bonded D-A-D triad, realizing a control of D-A ratio and a partially ionized state of TTF-Im molecule. Together with these structural and electronic properties, side-by-side S…S contacts on TTF moiety gives a three-dimensional network of intermolecular interactions. The static paramagnetic susceptibility of the polycrystalline sample and temperature dependence of electrical conductivity for single crystal along the π-stacking direction confirms the metallic behavior down to 180 K with room temperature conductivity of 124 Scm^<-1>, demonstrating the first disclosure of a purely organic molecular metal based on the H-bonded CT complex.

Research Products

• [Journal Article] Phenalenyl-based Highly Conductive Molecular Systems with Hydrogen-Bonded Networks : Synthesis, Physical Properties and Crystal Structures of 1,3- and 1,6-Diazaphenalenes, and Their Protonated Salts and Charge-Transfer Complexes with TCNQ (2006)
  • Author(s): Murata, T.
  • Journal Title: Bull.Chem.Soc.Jpn. (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Multi-Dimensional Networks of π-Conjugated Oligomer : Crystal Structures of 4,4':2',2'':4'',4'''-Quaterimidazole in Hydrate, Protonated Salt and Dinucleic Copper Complex (2006)
  • Author(s): Murata, T.
  • Journal Title: Cryst.Growth Des. (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Aromaticity on the Pancake-Bonded Dimer of Neutral Phenalenyl Radical as Studied by MS and NMR Spectroscopies and NICS Analysis (2006)
  • Author(s): Suzuki, S.
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 2530-2530
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Second Hyperpolarizabilities of Polycyclic Aromatic Hydrocarbons Involving Phenalenyl Radical Units (2006)
  • Author(s): Nakano.M.
  • Journal Title: Chem.Phys.Lett. 418 Pages: 142-142
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Second Hyperpolarizability of Phenalenyl Radical System Involving Acetylene π-Conjugated Bridge (2006)
  • Author(s): Ohta, S.
  • Journal Title: Chem.Phys.Lett. 420 Pages: 432-432
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Hydrogen-Bonded Structure of 2:1 TCNQ Salt of 2-Methyl-5-phenyl-7,9-dichloro-1,6-diazaphenalene (2006)
  • Author(s): Murata, T.
  • Journal Title: J.Low Temp.Phys. (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Ethylenedithio-TTF-Imidazole : Construction of Pluri-Dimensional Network by Hydrogen-Bonding and S・・・S Interactions (2006)
  • Author(s): Murata, T.
  • Journal Title: Multifunctional Conducting Molecular Materials(Saito, G., Wudl, F., Haddon, R.C., Tanigaki, K., Enoki, T., Katz, H.E., Eds)(Royal Society of Chemistry), London, U.K. (in press)(印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Multi-Dimensional Networks of π-Conjugated Oligomer : Crystal Structures of 4,4':2',2'':4'',4'''-Quaterimidazole in Hydrate, Protonated Salt and Dinucleic Copper Complex (2006)
  • Author(s): Murata T.
  • Journal Title: Cryst.Growth Des. 6 Pages: 1043-1047
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Second Hyperpolarizabilities of Polycyclic Aromatic Hydrocarbons Involving Phenalenyl Radical Units (2006)
  • Author(s): Nakano, M.
  • Journal Title: Chem.Phys.Lett. 418 Pages: 142-147
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Phenalenyl-based Highly Conductive Molecular Systems with Hydrogen-Bonded Networks : Synthesis, Physical Properties and Crystal structures of 1,3- and 1,6-Diazaphenalenes, and Their Protonated Salts and Charge-Transfer Complexes with TCNQ (2006)
  • Author(s): Murata, T.
  • Journal Title: Bull.Chem.Soc.Jpn. (印刷中)
• [Journal Article] Multi-Dimensional Networks of π-Conjugated Oligomer. Crystal Structures of 4,4':2,2'':4'',4'''-Quatenmidazole in Hydrate, Protonated Salt and Dinucleic Copper Complex (2006)
  • Author(s): Murata, T.
  • Journal Title: Cryst.Growth Des. (印刷中)
• [Journal Article] Second Hyperpolarizabilities of Polycyclic Aromatic hydrocarbons Involving Phenalenyl Radical Units (2006)
  • Author(s): Nakano, M.
  • Journal Title: Chem.Phys.Lett. 418 Pages: 142-142
• [Journal Article] Hydrogen-Bonded Structure of 2:1 TCNQ Salt of 2-Methyl-5-phenyl-7,9-dichloro-1,6-diazaphenalene (2006)
  • Author(s): Murata, T.
  • Journal Title: J.Low Temp.Phys (印刷中)
• [Journal Article] Hexaazaphenalenyl Anion Revisited : A Highly Symmetric Planar π System with Multiple-Networking Ability for Self-Assembled Metal Complexation (2005)
  • Author(s): Suzuki, S.
  • Journal Title: Inorg.Chem.(Communication) 44 Pages: 8197-8197
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Spin Transfer and Solvato-/Thermochromism Induced by Intramolecular Electron Transfer in A Purely Organic Open-Shell System (2005)
  • Author(s): Nishida, S.
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 7277-7277
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Introduction of Amino Groups into the Dibenzo-TTF π-System : Enhanced Electron-Donating Ability and Intermolecular Hydrogen Bonding (2005)
  • Author(s): Morita, Y.
  • Journal Title: Bull.Chem.Soc.Jpn. 78 Pages: 2014-2014
  • NAID: 10016845250
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] 2-Iodo-1,6-dithiapyrene : Syntheses, Crystal Structures and Physical Properties of CT Complexes and Salts (2005)
  • Author(s): Miyazaki, E.
  • Journal Title: Polyhedron 24 Pages: 2632-2632
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Hydrogen-Bonded Networks of 2,2'-Substituted-4,4'-biimidazoles : New Ligands for The Assembled Metal Complexes (2005)
  • Author(s): Murata, T.
  • Journal Title: Polyhedron 24 Pages: 2625-2625
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Effect of Methoxy Groups in a 1,3-Diazaphenalenyl π-System : Electronic-Spin Structure of 4,9-Dimethoxy-1,3-Diazaphenalenyl (2005)
  • Author(s): Suzuki, S.
  • Journal Title: Polyhedron 24 Pages: 2618-2618
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Deflected Spin Transmission from Radical Substituent to Corannulene's Curved Surface : Density Functional Theory Calculations (2005)
  • Author(s): Fukui, K.
  • Journal Title: Polyhedron 24 Pages: 2326-2326
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Spin Delocalization on Curved Surface π-System : Corannulene with Iminonitroxide (2005)
  • Author(s): Nishida, S.
  • Journal Title: Polyhedron 24 Pages: 2200-2200
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] 2-Aryl Substituted 3-Oxophenalenoxyl Radicals : π-Spin Structures and Properties Evaluated by Dimer Structure (2005)
  • Author(s): Nishida, S.
  • Journal Title: Polyhedron 24 Pages: 2194-2194
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis, Intermolecular Interaction, and Semiconductive Behavior of a Delocalized Singlet Biradical Hydrocarbon (2005)
  • Author(s): Kubo, T.
  • Journal Title: Angew.Cher.Int.Ed. 44 Pages: 6564-6564
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Transformation of Double Hydrogen-bonding Motifs of TTF-Uracil System by Redox Change (2005)
  • Author(s): Miyazaki, E.
  • Journal Title: Chem.Lett. 34 Pages: 1326-1326
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Dibenzotetrathiafulvalene with Amino Groups : New Electron-Donor Molecule with Hydrogen-Bonding Functionalities (2005)
  • Author(s): Morita, Y.
  • Journal Title: Synth.Met. 152 Pages: 433-433
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Pluri-Dimensional Hydrogen-Bonded Networks of Novel Thiophene-Introduced Oligo(imidazole)s and Physical Properties of Their Charge-Transfer Complexes with TCNQ (2005)
  • Author(s): Murata, T.
  • Journal Title: Tetrahedron 61 Pages: 6056-6056
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Hydrogen-Bonded Networks in Organic Conductors : Crystal Structures and Electronic Properties of Charge-Transfer Salts of Tetracyanoquinodimethane with 4,4'-Biimidazolium having Multi Protonated States (2005)
  • Author(s): Morita, Y.
  • Journal Title: J.Org.Chem. 70 Pages: 2739-2739
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Spin Transfer and Solvato/Thermochromism Inducede by Intramolecular Electron Transfer in A Purely Organic Open-Shell System (2005)
  • Author(s): Nishida, S.
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 7277-7280
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis, Intermolecular Interaction, and Semiconductive Behavior of a Delocalized Singlet Biradical Hydrocarbon (2005)
  • Author(s): Kubo, T.
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 6564-6568
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Hexaazaphenalenyl Anion Revisited : A Highly-Symmetric Planar π-System with Multiple-Networking Ability for Self-Assembled Metal Complexation (2005)
  • Author(s): Suzuki, S.
  • Journal Title: Inorg.Chem.(Communication) 44 Pages: 8197-8197
• [Journal Article] Spin Transfer and Solvato-/Themochromism Induced by Intramolecular Electron Transfer in A Purely Organic Open-Shell System (2005)
  • Author(s): Nishida, S.
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 7277-7277
• [Journal Article] Synthesis, Intermolecular Interaction, and Semiconductive behavior of a Delocalized Singlet Biradical Hydrocarbon (2005)
  • Author(s): Kubo, T.
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 6564-6564
• [Journal Article] Pluri-Dimensional Hydrogen-Bonded Networks of Novel Thiophene-Introduced Oligo(Imidazole)s and Physical Properties of Their Charge-Transfer Complexes with TCNQ (2005)
  • Author(s): Murata, T.
  • Journal Title: Tetrahedron 61 Pages: 6056-6056
• [Journal Article] Hydrogen-Bonded Networks in Organic Conductors : Crystal Sructures and Electronic Properteis of Charge-transfer Salts of Tetracyanoquinodimethane with 4,4'-Biimidazolium having Multi Protonated States (2005)
  • Author(s): Morita, Y.
  • Journal Title: J.Org.Chem. 70 Pages: 2739-2739
• [Journal Article] Hydrogen-Bonded Networks in Organic Conductors : Crystal Structures and Electronic Properties of Charge-Transfer Salts of Tetracyanoquinodimethane with 4,4'-Biimidazolium having Multi Protonated States (2005)
  • Author(s): Morita, Y
  • Journal Title: J.Org.Chem. 印刷中
• [Journal Article] 2-Aryl Substituted 3-Oxophenalenoxyl Radicals : π-Spin Structures and Properties Evaluated by Dimer Structure (2005)
  • Author(s): Nishida, S.
  • Journal Title: Polyhedron 印刷中
• [Journal Article] Dibenzotetrathiafulvalene with Amino Groups : New Electron-Donor Molecule with Hydrogen-Bonding Functionalities (2005)
  • Author(s): Morita, Y.
  • Journal Title: Synth.Met. 印刷中
• [Journal Article] Deflected Spin Transmission from Radical Substituent to Corannulene's Curved Surface : Density Functional Theory Calculations (2005)
  • Author(s): Fukui, K.
  • Journal Title: Polyhedron 印刷中
• [Journal Article] Spin Delocalization on Curved Surface π-System : Corannulene with Iminonitroxide (2005)
  • Author(s): Nishida, S.
  • Journal Title: Polyhedron 印刷中
• [Journal Article] Effect of Methoxy Groups in a 1,3-Diazaphenalenyl π-System : Electronic-Spin Structure of 4,9-Dimethoxy-1,3-Diazaphenalenyl (2005)
  • Author(s): Suzuki, S.
  • Journal Title: Polyhedron 印刷中
• [Journal Article] A Purely Organic Molecular Metal Based on a Hydrogen-Bonded Charge-Transfer Complex : Crystal Structure and Electronic Properties of TTF-Imidazole-p-Chloranil (2004)
  • Author(s): Murata, T.
  • Journal Title: Angew.Chem.Int.Ed. 43 Pages: 6343-6343
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] The First Bowl-Shaped Stable Neutral Radical with a Corannulene System : Synthesis and Characterization of the Electronic Structure (2004)
  • Author(s): Morita, Y.
  • Journal Title: Org.Lett. 6 Pages: 1397-1397
• [Journal Article] The First Metal Complexes of 4,4'-Biimidazole and 4,4'-Biimidazolate with Hydrogen-Bonding Networks on the Cu(II) Complexes : 1-D Structures by N-H…X…H-N Hydrogen-Bonding (2004)
  • Author(s): Morita, Y.
  • Journal Title: Chem.Lett. 33 Pages: 188-188
  • NAID: 10012042920
• [Journal Article] Hydrogen-Bonded Charge-transfer Complexes of TTFs Containing Nucleobase or Imidazole Moiety (2004)
  • Author(s): Morita, Y.
  • Journal Title: J.Phys.IV 114 Pages: 471-471
• [Journal Article] Phenalenyl-based Highly Conductive Molecular Systems with Hydrogen-Bonded Networks : Synthesis, Physical Properties and Crystal Structures of 1,3- and 1,6-Diazaphenalenes, and Their Protonated Salts and Charge-Transfer Complexes with TCNQ
  • Author(s): Murata, T.
  • Journal Title: Bull.Chem.Soc.Jpn. (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Ethylenedithio-TTF-Imidazole : Construction of Pluri-Dimensional Network by Hydrogen-Bonding and S…S Interactions
  • Author(s): Murata, T.
  • Journal Title: Multifunctional Conducting Molecular Materials (Saito, G., Wudl, F., Haddon, R.C., Tanigaki, K., Enoki, T., Katz, H.E., Eds.) (Royal Society of Chemistry, London, U.K.) (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Hydrogen-Bonded Structure of 2:1 TCNQ Salt of 2-Methyl-5-phenyl-7,9-dichloro-1,6-diazaphenalene
  • Author(s): Murata, T.
  • Journal Title: J.Low Temp.Phys. (in press)
  • Description: 「研究成果報告書概要(欧文)」より