Development of Novel Functional Organic Crystals by Utilizing Proton- and π-Electron-Donating/Accepting Abilities

Crystalline materials that comprise π-electron organic molecules exhibit various interesting physical properties and functionalities, related to electrical conductivity, magnetism, optical properties, etc. Conventionally, such properties and functionalities are determined or controlled by the intermolecular π-electron interactions in the crystal. Recently, however, the switching or control of the electronic structure and physical properties based on hydrogen dynamics was realized in a series of purely organic conductors. In this account article, the structure, properties, and switching phenomenon of this new type of organic conductors developed by utilizing proton- and π-electron-donating/accepting abilities are summarized. In addition, a highly polarized π-electron donor-acceptor type semiconductor molecule obtained in connection with the above conductors is also described.

[1]  I. Sivaev,et al.  New Fulvalenium Salts of Cobalt Bis(dicarbollide): Crystal Structures and Electrical Conductivities , 2012 .

[2]  Kaoru Yamamoto,et al.  Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal. , 2014, Journal of the American Chemical Society.

[3]  P. Batail.  Introduction: Molecular Conductors , 2004 .

[4]  H. Nakao,et al.  Charge-order driven proton arrangement in a hydrogen-bonded charge-transfer complex based on a pyridyl-substituted TTF derivative. , 2012, Chemical communications.

[5]  Yamada,et al.  Negative evidence for a proton-tunneling mechanism in the phase transition of KH2PO4-type crystals. , 1987, Physical review. B, Condensed matter.

[6]  H. Nakao,et al.  Protonation of pyridyl-substituted TTF derivatives: substituent effects in solution and in the proton-electron correlated charge-transfer complexes. , 2014, Chemistry.

[7]  S. Ishibashi,et al.  Structure-property relationship of supramolecular ferroelectric [H-66dmbp][Hca] accompanied by high polarization, competing structural phases, and polymorphs. , 2014, Chemistry.

[8]  H. Mori,et al.  Gapless quantum spin liquid in an organic spin-1/2 triangular-lattice κ-H3(Cat-EDT-TTF)2. , 2014, Physical review letters.

[9]  R. Kato.  Development of π-Electron Systems Based on [M(dmit)2] (M = Ni and Pd; dmit: 1,3-dithiole-2-thione-4,5-dithiolate) Anion Radicals , 2014 .

[10]  U. Nagashima,et al.  Multicomponent DFT study of geometrical H/D isotope effect on hydrogen-bonded organic conductor, κ-H 3 (Cat EDT-ST) 2 , 2017 .

[11]  H. Mori,et al.  Thermodynamics of the quantum spin liquid state of the single-component dimer Mott system κ − H 3 ( Cat − EDT − TTF ) 2 , 2017 .

[12]  Y. Morita,et al.  Cooperation of Hydrogen-Bond and Charge-Transfer Interactions in Molecular Complexes in the Solid State , 2013 .

[13]  S. Ishibashi,et al.  A single-component molecular superconductor. , 2014, Journal of the American Chemical Society.

[14]  G. A. Jeffrey,et al.  An Introduction to Hydrogen Bonding , 1997 .

[15]  Marc Fourmigué,et al.  Activation of hydrogen- and halogen-bonding interactions in tetrathiafulvalene-based crystalline molecular conductors. , 2004, Chemical reviews.

[16]  H. Okamoto,et al.  Exploration of new cooperative proton-electron transfer (PET) systems: first example of extended conjugated quinhydrones, 1,5-dihalo-2,6-naphthoquinhydrones , 1991 .

[17]  Jesse J. Bergkamp,et al.  Current advances in fused tetrathiafulvalene donor-acceptor systems. , 2015, Chemical Society reviews.

[18]  H. Nakao,et al.  Solid-solid phase interconversion in an organic conductor crystal: hydrogen-bond-mediated dynamic changes in π-stacked molecular arrangement and physical properties. , 2014, Chemical communications.

[19]  Yukihiro Yoshida,et al.  Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials , 2007 .

[20]  Y Okano,et al.  A three-dimensional synthetic metallic crystal composed of single-component molecules. , 2001, Science.

[21]  Joel S. Miller,et al.  Magnetism: Molecules to Materials V , 2001 .

[22]  Takehiko Mori.  Structural Genealogy of BEDT-TTF-Based Organic Conductors III. Twisted Molecules: δ and α′ Phases , 1999 .

[23]  O. Sato,et al.  Control of magnetic properties through external stimuli. , 2007, Angewandte Chemie.

[24]  U. Nagashima,et al.  Theoretical study of the H/D isotope effect on phase transition of hydrogen-bonded organic conductor κ-H3(Cat-EDT-TTF)2. , 2016, Physical chemistry chemical physics : PCCP.

[25]  H. Inokuchi,et al.  Electrical Conductivity of the Perylene–Bromine Complex , 1954, Nature.

[26]  O. Sato.  Dynamic molecular crystals with switchable physical properties. , 2016, Nature chemistry.

[27]  N. Avarvari,et al.  Electrical magnetochiral anisotropy in a bulk chiral molecular conductor , 2014, Nature Communications.

[28]  H. Mori.  Materials viewpoint of organic superconductors , 2006 .

[29]  H. Mori,et al.  Synthesis and properties of catechol-fused tetrathiafulvalene derivatives and their hydrogen-bonded conductive charge-transfer salts , 2012 .

[30]  H. Mori,et al.  Improved stability of a metallic state in benzothienobenzothiophene-based molecular conductors: an effective increase of dimensionality with hydrogen bonds. , 2017, Chemical communications.

[31]  R. Hicks.  Stable radicals : fundamentals and applied aspects of odd-electron compounds , 2010 .

[32]  H. Nakao,et al.  Hydrogen bond-promoted metallic state in a purely organic single-component conductor under pressure , 2013, Nature Communications.

[33]  T. Gustafsson,et al.  Linear relation between transition temperature and H-bond distance in M3H(SeO4)2-type crystals (M = K, Rb, Cs) with 0-dimensional H-bond network , 1993 .

[34]  H. Mori,et al.  Unexpected Formation of ortho-Benzoquinone-fused Tetraselenafulvalene (TSF): Synthesis, Structures, and Properties of a Novel TSF-based Donor–Acceptor Dyad , 2015 .

[35]  M. Enomoto,et al.  Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism. , 2015, Chemistry.

[36]  Takehiko Mori.  Structural Genealogy of BEDT-TTF-Based Organic Conductors I. Parallel Molecules: .BETA. and .BETA." Phases. , 1998 .

[37]  S. J. Grabowski.  Theoretical studies of strong hydrogen bonds , 2006 .

[38]  H. Mori,et al.  Anion substitution in hydrogen-bonded organic conductors: the chemical pressure effect on hydrogen-bond-mediated phase transition , 2017 .

[39]  Mitani,et al.  Cooperative phenomena associated with electron and proton transfer in quinhydrone charge-transfer crystal. , 1988, Physical review letters.

[40]  N. Avarvari,et al.  Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM‐BEDT‐TTF) with the Hexachlororhenate(IV) Anion , 2014 .

[41]  Takehiko Mori,et al.  Structural Genealogy of BEDT-TTF-Based Organic Conductors II. Inclined Molecules: θ, α, and κ Phases , 1999 .

[42]  H. Mori,et al.  Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes , 2015, Beilstein journal of organic chemistry.

[43]  L. Ouahab.  Multifunctional molecular materials , 2013 .

[44]  N. Avarvari,et al.  Anion size control of the packing in the metallic versus semiconducting chiral radical cation salts (DM-EDT-TTF)2XF6 (X = P, As, Sb). , 2016, Chemical communications.

[45]  N. Avarvari,et al.  Strategies towards chiral molecular conductors , 2009 .

[46]  A. Kobayashi,et al.  Single-component molecular metals with extended-TTF dithiolate ligands. , 2004, Chemical reviews.

[47]  N. Avarvari,et al.  Covalent non-fused tetrathiafulvalene-acceptor systems. , 2016, Chemical communications.