Striking Increase in Hole Mobility upon Metal Coordination to Triphenylene Schiff Base Semiconducting Multicolumnar Mesophases.

This paper reports the synthesis, liquid-crystal behavior, and charge-transport properties in the mesophase of triphenylene Schiff bases and their copper(II), nickel(II), and oxovanadium(IV) complexes. The thermal and electronic properties of the Schiff bases are modulated by coordination to the corresponding metal moieties, which have the ability to self-assemble into linear structures and help the alignment of the triphenylene columns. This produces two kinds of electronically nonconnected columnar regions, one purely organic and one more inorganic. The most remarkable effect is a striking charge mobility enhancement in the metal-containing mesophases, due to the contribution of the more inorganic columns: in comparison to values of hole mobility along the columnar stacking for the purely organic columnar mesophases, on the order of 10-7 cm2 V-1 s-1, these values jump to 1-10 cm2 V-1 s-1 in these hybrid inorganic/organic columnar materials.

[1]  T. Akutagawa,et al.  C 3 Symmetric Hexaphenyltriphenylenehexamide: Molecular Design of Fluorescent Ferroelectrics , 2018, ChemistrySelect.

[2]  S. Coco,et al.  Triphenylene-Imidazolium Salts and Their NHC Metal Complexes, Materials with Segregated Multicolumnar Mesophases. , 2018, Inorganic chemistry.

[3]  Sandeep Kumar,et al.  Recent Advances in Discotic Liquid Crystal-Assisted Nanoparticles , 2018, Materials.

[4]  A. Golemme,et al.  High One-Dimensional Charge Mobility in Semiconducting Columnar Mesophases of Isocyano-Triphenylene Metal Complexes , 2017 .

[5]  Monika Gupta,et al.  Highly Resolved Morphology of Room‐Temperature Columnar Liquid Crystals Derived from Triphenylene and Multialkynylbenzene Using Reconstructed Electron Density Maps , 2017 .

[6]  A. Golemme,et al.  Not Only Columns: High Hole Mobility in a Discotic Nematic Mesophase Formed by Metal-Containing Porphyrin-Core Dendrimers. , 2017, Angewandte Chemie.

[7]  S. Coco,et al.  Isocyano-Triphenylene Complexes of Gold, Copper, Silver, and Platinum. Coordination Features and Mesomorphic Behavior , 2016 .

[8]  A. Golemme,et al.  H-Bonded Donor-Acceptor Units Segregated in Coaxial Columnar Assemblies: Toward High Mobility Ambipolar Organic Semiconductors. , 2016, Journal of the American Chemical Society.

[9]  Jianchuang Wang,et al.  A systematic study on the influences of linkage length on phase behaviours and charge carrier mobilities of discotic dimers , 2016 .

[10]  Sabine Laschat,et al.  Discotic Liquid Crystals. , 2016, Chemical reviews.

[11]  Monika Gupta,et al.  Triphenylene-Based Room-Temperature Discotic Liquid Crystals: A New Class of Blue-Light-Emitting Materials with Long-Range Columnar Self-Assembly. , 2016, Langmuir : the ACS journal of surfaces and colloids.

[12]  B. Heinrich,et al.  Highly Segregated Lamello-Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor-Acceptor Triads. , 2015, Chemistry.

[13]  Manjun Xiao,et al.  Luminescent metallomesogens based on platinum complex containing triphenylene unit , 2015 .

[14]  A. Ourari,et al.  Synthesis and characterization of a new Schiff base derived from 2,3-diaminopyridine and 5-methoxysalicylaldehyde and its Ni(II), Cu(II) and Zn(II) complexes. Electrochemical and electrocatalytical studies , 2015 .

[15]  W. Greenbank,et al.  Photophysical behaviour of 4-hexyloxysalicylaldimies and their copper(II) complexes , 2014 .

[16]  S. Coco,et al.  Alignment of palladium complexes into columnar liquid crystals driven by peripheral triphenylene substituents. , 2014, Inorganic chemistry.

[17]  Sandeep Kumar,et al.  Triphenylene-based discotic liquid crystals: recent advances , 2013 .

[18]  Fafu Yang,et al.  Ion complexation-induced mesomorphic conversion between two columnar phases of novel symmetrical triads of triphenylene-calix[4]arene-triphenylenes , 2013 .

[19]  J. Pflaum,et al.  Triphenylene silanes for direct surface anchoring in binary mixed self-assembled monolayers. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[20]  A. Cammidge,et al.  Discotic triphenylene twins linked through thiophene bridges: controlling nematic behavior in an intriguing class of functional organic materials. , 2012, The Journal of organic chemistry.

[21]  Manoj Kumar,et al.  Triazole-modified triphenylene derivative: self-assembly and sensing applications. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[22]  T. Umeyama,et al.  Segregated donor-acceptor columns in liquid crystals that exhibit highly efficient ambipolar charge transport. , 2011, Journal of the American Chemical Society.

[23]  K. Hirao,et al.  Carbon nanotube wiring of donor-acceptor nanograins by self-assembly and efficient charge transport. , 2011, Angewandte Chemie.

[24]  Yong Cao,et al.  Metallomesogens based on platinum(II) complexes: synthesis, luminescence and polarized emission. , 2011, Dalton transactions.

[25]  M. G. Hutchings,et al.  Nickel(II) and palladium(II) complexes of azobenzene-containing ligands as dichroic dyes. , 2010, Inorganic chemistry.

[26]  M. Orio,et al.  X-ray structures of copper(II) and nickel(II) radical salen complexes: the preference of galactose oxidase for copper(II). , 2010, Angewandte Chemie.

[27]  Mohamed M. Ahmida,et al.  Measurements and Prediction of Electronic Properties of Discotic Liquid Crystalline Triphenylenes and Phthalocyanines , 2010 .

[28]  A. Bezaatpour,et al.  Synthesis, characterization and studies of mechanochemical, electrochemical, and thermal behavior of electronegative oxovanadium(IV) Schiff-base complexes , 2009 .

[29]  Jong Kang Park,et al.  Supramolecular donor-acceptor heterojunctions by vectorial stepwise assembly of porphyrins and coordination-bonded fullerene arrays for photocurrent generation. , 2009, Journal of the American Chemical Society.

[30]  M. Lutz,et al.  Ni(salen): a System That Forms Many Solvates with Interacting Ni Atoms , 2009 .

[31]  J. Prakash,et al.  Coordination of a mesogenic Schiff-base with Mn II , Co II , Ni II , Cu II and Zn II : Synthesis, spectral studies and crystal structures , 2008 .

[32]  D. Bruce,et al.  Phosphorescent, terdentate, liquid-crystalline complexes of platinum(II): stimulus-dependent emission. , 2008, Angewandte Chemie.

[33]  M. Miyake,et al.  Control of stripelike and hexagonal self-assembly of gold nanoparticles by the tuning of interactions between triphenylene ligands. , 2007, Journal of the American Chemical Society.

[34]  S. Coco,et al.  Dinuclear gold(I) isocyanide complexes with luminescent properties, and displaying thermotropic liquid crystalline behavior. , 2006, Inorganic chemistry.

[35]  J. Etxebarria,et al.  Achiral Bent-Core Liquid Crystals with Azo and Azoxy Linkages: Structural and Nonlinear Optical Properties and Photoisomerization , 2006 .

[36]  Sandeep Kumar,et al.  Triphenylene‐based discotic liquid crystal dimers, oligomers and polymers , 2005 .

[37]  Sandeep Kumar,et al.  Recent developments in the chemistry of triphenylene-based discotic liquid crystals , 2004 .

[38]  S. Diele,et al.  Molecular design at the calamitic/discotic cross-over point. Mononuclear ortho-metallated mesogens based on the combination of rod-like phenylpyrimidines and -pyridines with bent or half-disc-shaped diketonates , 2003 .

[39]  N. Boden,et al.  Helical geometry and liquid crystalline properties of 2,3,6,7,10,11-hexaalkoxy-1-nitrotriphenylenes , 2003 .

[40]  A. Cammidge,et al.  Macrodiscotic triphenylenophthalocyanines. , 2002, Chemical communications.

[41]  S. Fetics,et al.  The structural and functional equivalence of aurophilic and hydrogen bonding: evidence for the first examples of rotator phases induced by aurophilic bonding. , 2001, Journal of the American Chemical Society.

[42]  Sandeep Kumar,et al.  A new form of discotic metallomesogens: the synthesis of metal-bridged triphenylene discotic dimers , 2001 .

[43]  S. K. Prasad,et al.  Novel heptasubstituted triphenylene discotic liquid crystals , 2000 .

[44]  Sandeep Kumar,et al.  Electrophilic aromatic substitution in triphenylene discotics: Synthesis of alkoxynitrotriphenylenes , 1999 .

[45]  N. Boden,et al.  Cyano substituted triphenylene-based discotic mesogens , 1999 .

[46]  J. Serrano,et al.  Photopolymerization of reactive mesogenic schiff bases and related metallomesogens , 1999 .

[47]  Sandeep Kumar,et al.  INFLUENCE OF DISORDER ON ELECTRONIC EXCITED STATES : AN EXPERIMENTAL AND NUMERICAL STUDY OF ALKYLTHIOTRIPHENYLENE COLUMNAR PHASES , 1998 .

[48]  Dirk Blunk,et al.  CORE-HALOGENATED, HELICAL-CHIRAL TRIPHENYLENE-BASED COLUMNAR LIQUID CRYSTALS , 1997 .

[49]  Richard J. Bushby,et al.  α-Halogenation of triphenylene-based discotic liquid crystals : towards a chiral nucleus , 1997 .

[50]  N. Boden,et al.  Preliminary Communications Functionalization of discotic liquid crystals by direct substitution into the discogen ring α-Nitration of triphenylene-based discogens , 1995 .

[51]  A. Tol,et al.  Effect of the Orientation of the Ester Bonds on the Properties of Three Isomeric Liquid Crystal Diacrylates before and after Polymerization , 1995 .

[52]  N. Boden,et al.  Versatile Synthesis of Unsymmetrically Substituted Triphenylenes , 1995 .

[53]  G. Wegner,et al.  SYNTHESIS OF TRIPHENYLENE-BASED PORPHYRAZINATO METAL(II) COMPLEXES WHICH DISPLAY DISCOTIC COLUMNAR MESOMORPHISM , 1995 .

[54]  N. Boden,et al.  Novel discotic liquid crystals created by electrophilic aromatic substitution , 1995 .

[55]  L. Gallos,et al.  Triphenylene Columnar Liquid Crystals: Excited States and Energy Transfer , 1995 .

[56]  T. Swager,et al.  Polar Superstructures Stabilized by Polymeric Oxometal Units: Columnar Liquid Crystals Based on Tapered Dioxomolybdenum Complexes† , 1994 .

[57]  P. Schuhmacher,et al.  Fast photoconduction in the highly ordered columnar phase of a discotic liquid crystal , 1994, Nature.

[58]  T. Swager,et al.  Transition Metals in Highly Correlated Discotic Phases: Designing Metallomesogens with Selected Intermolecular Organizations , 1994 .

[59]  T. Swager,et al.  Controlling intermolecular associations with molecular superstructure : polar discotic linear chain phases , 1993 .

[60]  T. Swager,et al.  Tuning the intermolecular dative interactions in vanadium-oxo linear chain compounds : formation of a new type of liquid crystalline polymer , 1992 .

[61]  N. Ruiz,et al.  Metallo-mesogens based on ortho-palladated polar imines: III. Influence of the polar group position , 1991 .