Electron-phonon interactions in the monocations of polyacetylenes

Electron-phonon interactions in the monocations of trans-polyacetylenes such as C2H4 (2tpa), C4H6 (2tpa), C6H8 (6tpa), and C8H10 (8tpa) are studied. The C-C stretching Ag modes around 1700 cm(-1) afford the largest electron-phonon coupling constants in the monocations of polyacetylenes. However, the C-C bending Ag modes around 1200 cm(-1) afford much smaller electron-phonon coupling constants than the C-C stretching Ag modes around 1700 cm(-1) in the monocations of polyacetylenes. The total electron-phonon coupling constants for the monocations (l HOMO) are estimated to be 0.357, 0.285, 0.281, and 0.279 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. The l HOMO values for polyacetylenes with C 2h geometry hardly change with an increase in molecular size while those for polyacenes with D 2h geometry significantly decrease with an increase in molecular size. The l HOMO values for polyacetylenes are larger than those for polyacenes. The calculated results are rationalized in terms of the phase patterns of the molecular orbitals in detail. The electron transfer in the positively charged polyacetylenes is also discussed. Intramolecular electron mobility (sigma(intra,monocation)) in the positively charged polyacetylenes is estimated to be smaller than those for the positively charged polyacenes. The reorganization energies for the positively charged polyacetylenes are estimated to be larger than those for the positively charged polyacenes. Thus, the larger overlap integrals between two neighboring molecules are needed for the positively charged polyacetylenes to become good conductor than those for positively charged polyacenes. On the other hand, the conditions under which the electron-electron interactions are attractive are more easily realized in the monocations of polyacetylenes than in the monocations of polyacenes. The quality as conducting materials would not significantly depend on the molecular size in the positively charged polyacetylenes, compared with that in the positively charged polyacenes. Multimode problem is also treated in order to investigate how consideration of multimode problem is closely related to the characteristics of the electron-phonon interactions.     

The effect of atomic substitution on electron-phonon interactions in negatively charged B, N-substituted acenes

Electron-phonon interactions in the monoanions of B, N-substituted acenes such as B(3)N(3)F(6) (1f) and B(5)N(5)F(8) (2f) are studied, and compared with those in the monoanions of B(3)N(3)H(6) (1h) and B(5)N(5)H(8) (2h), and B(3)N(3)D(6) (1d) and B(5)N(5)D(8) (2d). The low frequency modes around 500 cm(-1) as well as the frequency modes higher than 1000 cm(-1) strongly couple to the lowest unoccupied molecular orbitals (LUMO) in 1f and 2f. The total electron-phonon coupling constants (l(LUMO)) are estimated to be 2.710 and 2.054 eV for 1f and 2f, respectively, and those are estimated to be 0.342 and 0.235 eV for 1d and 2d, respectively, while those were estimated to be 0.340 and 0.237 eV for 1h and 2h, respectively. That is, the l(LUMO) value increases much more significantly by H-F substitution than by H-D substitution in B, N-substituted acenes. The larger displacements of B and N atoms in the vibronic active modes in 1f and 2f than those in 1d and 2d due to larger atomic mass of fluorine than that of deuterium, and the phase patterns difference between the LUMO in 1f and 2f, in which the atomic orbitals between N and its neighboring F atoms form strong sigma-antibonding interactions, and that in 1d and 2d, in which the atomic orbitals between two neighboring B and N atoms form weak pi-bonding and pi-antibonding interactions, are the main reason why the l(LUMO) value increases much more significantly by H-F substitution than by H-D substitution. The reorganization energies between the neutral molecules and the corresponding monoanions are estimated to be 0.122, 0.063, 0.733, and 0.830 eV for 1h, 2h, 1f, and 2f, respectively. Therefore, the estimated reorganization energies between the neutral molecules and the corresponding monoanions for 1f and 2f are much larger than those for 1h and 2h.     

Inverse isotope effects and electron-phonon coupling in the positively charged deutero- and fluoroacenes

Electron-phonon interactions in the monocations of deutero- and fluoroacenes are studied and compared with those in the monocations of acenes and those in the monoanions of fluoroacenes. Because of the significant phase pattern difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO), the frequency modes lower than 500 cm(-1) and the high-frequency modes around 1400 cm(-1) couple more strongly to the LUMO than to the HOMO, while the frequency modes around 500 cm(-1) and the frequency modes around 1600 cm(-1) couple more strongly to the HOMO than to the LUMO in fluoroacenes with D2h geometry. The total electron-phonon coupling constants for the monocations (l(HOMO)) are estimated and compared with those for the monoanions (l(LUMO)) in deutero- and fluoroacenes. The l(HOMO) values are estimated to be 0.418, 0.399, 0.301, 0.255, and 0.222 eV for C6F6 (1f), C10F8 (2f), C14F10 (3f), C18F12 (4f), and C22F14 (5f), respectively. The l(HOMO) values are smaller than the l(LUMO) values in small fluoroacenes. But the l(HOMO) value decreases with an increase in molecular size less rapidly than the l(LUMO) value in fluoroacenes, and the l(HOMO) value of 0.074 eV is much larger than the l(LUMO) value of 0.009 eV in polyfluoroacene. The logarithmically averaged phonon frequencies for the monocations (omega(ln,HOMO)) are estimated to be larger than those for the monoanions (omega(ln,LUMO)) in fluoroacenes. This is because the C-C stretching modes around 1600 cm(-1) couple most strongly to the HOMO, and those around 1400 cm(-1) couple the most strongly to the LUMO in fluoroacenes. The significant phase pattern difference between the HOMO and the LUMO is the main reason for the calculational results. The l(HOMO) values increase much more significantly by H-F substitution than by H-D substitution in acenes. The possible inverse isotope effects in the electron-phonon interactions as a consequence of deuteration in the monocations of nanosized molecules are suggested.     

The essential role of H-F substitution in the electron-phonon interactions and electron transfer in the negatively charged acenes

The single charge transfer through acenes, partially H-F substituted acenes, and fluoroacenes is discussed. The reorganization energies between the neutral molecules and the corresponding monoanions for partially H-F substituted acenes lie between those for acenes and fluoroacenes. The delocalization of the lowest unoccupied molecular orbitals (LUMO) by substituting hydrogen atoms by fluorine atoms with the highest electronegativity in every element is the main reason why the reorganization energy between the neutral molecule and the monoanion for partially H-F substituted acenes lies between those for acenes and fluoroacenes. This result implies that the negatively charged partially H-F substituted acenes would be better conductors with rapid electron transfer than the negatively charged fluoroacenes if we assume that the overlap of the LUMO between partially H-F substituted acenes is not significantly different from that between two neighboring fluoroacenes. The structures of the monoanions of acenes, fluoroacenes, and partially H-F substituted acenes are optimized under D2h geometry, and the Jahn-Teller effects in the monoanions of benzene and fluorobenzene are discussed. The vibration effect onto the charge transfer problem is also discussed. The C-C stretching modes around 1500 cm(-1) are the main modes converting the neutral molecules to the monoanions in acenes, fluoroacenes, and partially H-F substituted acenes. It can be confirmed from the calculational results that the C-C stretching modes around 1500 cm(-1) the most strongly couple to the LUMO in these molecules. The main reason why the total electron-phonon coupling constants (lLUMO) for the monoanions of acenes in which four outer hydrogen atoms are substituted by fluorine atoms are larger than those for the monoanions of acenes in which several inner hydrogen atoms are substituted by fluorine atoms is suggested. The relationships between the electron transfer and the electron-phonon interactions are discussed. The plot of the reorganization energies against the lLUMO values is found to be nearly linear. In view of these results, the relationships between the normal and superconducting states are briefly discussed.     

Vibronic interactions and possible electron pairing in the photoinduced excited electronic States in molecular systems: a theoretical study

Electron-phonon interactions in the photoinduced excited electronic states in molecular systems such as phenanthrene-edge-type hydrocarbons are discussed and compared with those in the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) (the atomic orbitals between two neighboring carbon atoms combined in phase (out of phase) in the HOMO are combined out of phase (in phase) in the LUMO) are the main reason that the C-C stretching modes around 1500 cm(-1) afford much larger electron-phonon coupling constants in the excited electronic states than in the charged electronic states. The frequencies of the vibrational modes that play an essential role in the electron-phonon interactions for the excited electronic states are similar to those for the monoanions and cations in phenanthrene-edge-type hydrocarbons. Possible electron pairing and Bose-Einstein condensation in the photoinduced excited electronic states as well as those in the monoanions and cations in molecular systems such as phenanthrene-edge-type hydrocarbons are also discussed.     

Electron-phonon interactions in photoinduced excited electronic states in fluoroacenes

The electron-phonon coupling constants [l(B1u(HOMO-->LUMO))] in the photoinduced excited electronic states in fluoroacenes are estimated and compared with those in the monoanions (l(LUMO)) and cations (l(HOMO)). The l(B1u(HOMO-->LUMO)) values are much larger than the l(LUMO) and l(HOMO) values in fluoroacenes. Furthermore, the Coulomb pseudopotential mu* values for the excited electronic states are estimated to be smaller than those for the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) is the main reason why the electron-phonon coupling constants and the mu* values are larger and smaller, respectively, in the photoinduced excited electronic states than in the monoanions and cations. The possible electron pairing and Bose-Einstein condensation in the excited electronic states of fluoroacenes are discussed. Because of larger electron-phonon coupling constants and smaller mu* values in the excited electronic states than in the charged states, the conditions under which the electron-electron interactions become attractive can be more easily realized, in principle, in the excited electronic states than in the charged states in fluoroacenes. The l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution, even though the l(LUMO) and l(HOMO) values significantly increase by H-F substitution in acenes. Antibonding interactions between carbon and fluorine atoms in the HOMO and LUMO are the main reason why the l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution in acenes.     

Vibronic interactions and possible electron pairing in positively charged cyanodienes

The conditions under which the attractive electron-electron interactions are realized in the monocations of sigma-conjugated cyanodienes such as C(6)N(4)H(4), C(8)N(6)H(4), and C(10)N(8)H(4) and of pi-conjugated acenes are discussed. The total electron-phonon coupling constants for the monocations l(HOMO) of cyanodienes are much larger than those for the monocations of acenes. The strong sigma orbital interactions between two neighboring atoms in the highest occupied molecular orbitals (HOMO) of sigma-conjugated cyanodienes are the main reason for the calculated results. Furthermore, we discuss how the conditions under which the monocation crystals become good conductor are related to the molecular size. Both the l(HOMO) values and the reorganization energies between the neutral molecules and the monocations decrease with an increase in molecular size in cyanodienes. The calculated results for the sigma-conjugated cyanodienes are compared with those for the pi-conjugated acenes in order to investigate how the CH-N substitutions in cyanodienes are closely related to the l(HOMO) values and the reorganization energies. Both the l(HOMO) and the reorganization energies in the positively charged sigma-conjugated cyanodienes are much larger than those in the positively charged pi-conjugated acenes. This means that in order to become good conductors, the positively charged sigma-conjugated cyanodienes need larger overlap integral between two adjacent molecules than the positively charged pi-conjugated acenes. On the other hand, since the l(HOMO) values for cyanodienes are much larger than those for acenes, the condition of attractive electron-electron interactions is more easily to be realized in the monocations of cyanodienes than in the monocations of acenes. It is suggested that the positively charged sigma-conjugated cyanodienes cannot easily become good conductors, but the conditions under which the electron-electron interactions become attractive are realized more easily in the positively charged sigma-conjugated cyanodienes than in the positively charged pi-conjugated acenes.     

Electron-intramolecular-vibration interactions in positively charged phenanthrene-edge-type hydrocarbons

Electron-phonon interactions in positively charged phenanthrene-edge-type hydrocarbons such as phenanthrene, chrysene, and picene are studied. The C-C stretching modes around 1500 cm(-1) and the low-frequency modes around 500 cm(-1) strongly couple to the highest occupied molecular orbitals (HOMO) in phenanthrene-edge-type hydrocarbons. The total electron-phonon coupling constants for the monocations (lHOMO) of 0.251, 0.135, and 0.149 eV for phenanthrene, chrysene, and picene, respectively, are estimated to be larger than those of 0.130, 0.107, and 0.094 eV for anthracene, tetracene, and pentacene, respectively. The phase patterns difference between the HOMO localized on carbon atoms which are located at the molecular edge in acene-edge-type hydrocarbons and the delocalized HOMO in phenanthrene-edge-type hydrocarbons is the main reason for the result. Strengths of orbital interactions between two neighboring carbon atoms in the HOMO become weaker with an increase in molecular size because the electron density on each carbon atom in the HOMO becomes smaller with an increase in molecular size in phenanthrene-edge-type hydrocarbons. On the other hand, the frontier orbitals of acene-edge-type hydrocarbons have somewhat nonbonding characters and thus cannot strongly couple to the totally symmetric vibrational modes compared with the frontier orbitals of phenanthrene-edge-type hydrocarbons. This is the reason why the lHOMO value for phenanthrene-edge-type hydrocarbons decreases with an increase in molecular size more significantly than that for acene-edge-type hydrocarbons, and the reason why the lHOMO value for polyphenanthrene with C2v geometry (0.033 eV) is estimated to be similar to that for polyacene (0.036 eV). The reorganization energies between the neutral molecules and the corresponding monocations for phenanthrene-edge-type hydrocarbons with large molecular size are estimated to be larger than those for acene-edge-type hydrocarbons with large molecular size.     

Two-photon photoemission spectroscopy study of 1,3-butadiene on Cu(111): electronic structures and excitation mechanism

The characteristics of 1,3-butadiene (C(4)H(6)) adsorbed on Cu(111) were investigated with temperature-programmed desorption (TPD) and two-photon photoemission spectroscopy (2PPE). Dosed at 90 K, the work function drops by 0.4 eV and TPD provides no evidence for dissociation, but there are four coverage-dependent local maxima located at 195, 135, 121, and 115 K. From the 2PPE spectra, three unoccupied electronic states of the C(4)H(6)-Cu(111) system were identified: the LUMO (pi(1)*, 2a(u)), LUMO + 1 (pi(2)*, 2b(g)), and LUMO + 2 (sigma*, 7b(u)), lying 1.3, 3.4, and 4.8 eV above the Fermi level, respectively. Although the excitation mechanisms for the LUMO and LUMO + 1 are substrate mediated, the excitation of the LUMO + 2 is attributed to intramolecular excitation.     

A DFT Investigation on Hydrogen Adsorption Based on Alkali-metal Organic Complexes

Using density functional theory calculation based on the B3LYP method,we have studied the interactions of H2 molecules with alkali-metal organic complexes C6H6-nLin(n = 1～3),C6H5Na and C6H5K.A significant part of the electronic charge of M s orbital(Li 2s,Na 3s,K 4s) is donated to phenyl and is accommodated by H2 bonding orbital.For all the complexes considered,each bonded alkali-metal atom can adsorb up to five H2 in molecular form with the mean binding energy of 0.59,0.55 and 0.56 eV/H2 molecule for C6H6-nLin(n = 1～3),C6H5Na and C6H5K,respectively.The kinetic stability of these hydrogen-covered organometallic complexes is discussed in terms of energy gap between HOMO and LUMO.It is remarkable that these alkali-metal organic complexes can store up to 23.80 wt% hydrogen.Therefore,the complexes studied may be used as hydrogen storage materials.     

Cyclic perfluorocarbon radicals and anions having high global warming potentials (GWPs): structures, electron affinities, and vibrational frequencies

Adiabatic electron affinities, optimized molecular geometries, and IR-active vibrational frequencies have been predicted for small cyclic hydrocarbon radicals C(n)H(2)(n)(-)(1) (n = 3-6) and their perfluoro counterparts C(n)F(2)(n)(-)(1) (n = 3-6). Total energies and optimized geometries of the radicals and corresponding anions have been obtained using carefully calibrated (Chem. Rev. 2002, 102, 231) density functional methods, namely, the B3LYP, BLYP, and BP86 functionals in conjunction with the DZP++ basis set. The predicted electron affinities show that only the cyclopropyl radical tends to bind electrons among the hydrocarbon radicals studied. The trend for the perfluorocarbon (PFC) radicals is quite different. The electron affinities increase with expanding ring size until n = 5 and then slightly decrease at n = 6. Predicted electron affinities of the hydrocarbon radicals using the B3LYP hybrid functional are 0.24 eV (C(3)H(5)/C(3)H(5)(-)), -0.19 eV (C(4)H(7)/C(4)H(7)(-)), -0.15 eV (C(5)H(9)/C(5)H(9)(-)), and -0.11 eV (C(6)H(11)/C(6)H(11)(-)). Analogous electron affinities of the perflurocarbon radicals are 2.81 eV (C(3)F(5)/C(3)F(5)(-)), 3.18 eV (C(4)F(7)/C(4)F(7)(-)), 3.34 eV (C(5)F(9)/C(5)F(9)(-)), and 3.21 eV (C(6)F(11)/C(6)F(11)(-)).     

Optical properties of (Z)‐2‐(2‐phenylhydrazinylidene)acenaphthen‐1(2H)‐one: a potential electron donor in organic solar cells

Electron‐donating molecules play an important role in the development of organic solar cells. (Z )‐2‐(2‐Phenylhydrazinylidene)acenaphthen‐1(2H )‐one (PDAK), C₁₈H₁₂N₂O, was synthesized by a Schiff base reaction. The crystal structure shows that the molecules are planar and are linked together forming `face‐to‐face' assemblies held together by intermolecular C—H…O, π–π and C—H…π interactions. PDAK exhibits a broadband UV–Vis absorption (200–648 nm) and a low HOMO–LUMO energy gap (1.91 eV; HOMO is the highest occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital), while fluorescence quenching experiments provide evidence for electron transfer from the excited state of PDAK to C₆₀. This suggests that the title molecule may be a suitable donor for use in organic solar cells.     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.     

Hydrogen Adsorption on Ti Decorating Benzene Grafted Tetrahydrido-silsequioxanes

A novel type of Ti decorating benzene grafted tetrahydrido-silsequioxane struc-tures was designed and investigated using density functional theory(DFT).The hydrogen adsorption properties of this new material were investigated at the same level of theory.The results reveal that up to four hydrogen molecules(with the restrict of 18 electrons rule) can be adsorbed on each Ti atom of(TiC6H5)m-H4-mSi4O6(m = 1-4) molecular systems with the average binding energies of 0.691,0.692,0.693 and 0.695 eV for m = 1-4,respectively.The variations of HOMO- LUMO energy gaps verify that the host structures with four H2 molecules adsorbed own the best kinetics stability.The interaction mechanism of H2 molecules with the host materials mainly attributes to the well-known "kubas interactions".All the results indicate that the complex structures designed here may be used as hydrogen storage materials at ambient conditions.     

Controlled hydrolysis of lanthanide complexes of the N-donor tripod tris(2-pyridylmethyl)amine versus bisligand complex formation

The reaction of the lanthanide salts LnI3(thf)4 and Ln(OTf)3 with tris(2-pyridylmethyl)amine (tpa) was studied in rigorously anhydrous conditions and in the presence of water. Under rigorously anhydrous conditions the successive formation of mono- and bis(tpa) complexes was observed on addition of 1 and 2 equiv of ligand, respectively. Addition of a third ligand equivalent did not yield additional complexes. The mono(tpa) complex [Ce(tpa)I3] (1) and the bis(tpa) complexes [Ln(tpa)2]X3 (X = I, Ln = La(III) (2), Ln = Ce(III) (3), Ln = Nd(III) (4), Ln = Lu(III) (5); X = OTf, Ln = Eu(III) (6)) were isolated under rigorously anhydrous conditions and their solid-state and solution structures determined. In the presence of water, 1H NMR spectroscopy and ES-MS show that the successive addition of 1-3 equiv of tpa to triflate or iodide salts of the lanthanides results in the formation of mono(tpa) aqua complexes followed by formation of protonated tpa and hydroxo complexes. The solid-state structures of the complexes [Eu(tpa)(H2O)2(OTf)3] (7), [Eu(tpa)(mu-OH)(OTf)2]2 (8), and [Ce(tpa)(mu-OH)(MeCN)(H2O)]2I4 (9) have been determined. The reaction of the bis(tpa) lanthanide complexes with stoichiometric amounts of water yields a facile synthetic route to a family of discrete dimeric hydroxide-bridged lanthanide complexes prepared in a controlled manner. The suggested mechanism for this reaction involves the displacement of one tpa ligand by two water molecules to form the mono(tpa) complex, which subsequently reacts with the noncoordinated tpa to form the dimeric hydroxo species.     

Electron-phonon interactions and Jahn-Teller effects in the monocation of corannulene

Electron-phonon interactions in the monocation of corannulene are studied by using the hybrid Hartree-Fock (HF)/density-functional-theory (DFT) method in the Gaussian 98 program package. The C-C stretching mode of 1498 cm(-1) most strongly couples to the e1 highest occupied molecular orbitals (HOMO) in corannulene. The total electron-phonon coupling constant for the monocation (l(HOMO)) of corannulene is estimated to be 0.165 eV. The l(HOMO) value for corannulene is much larger than those for coronene and acenes with similar numbers of carbon atoms. The delocalized electronic structures and the intermediate characteristics between the strong sigma-orbital interactions and weak pi-orbital interactions originating from a bowl-shaped C(5v) geometry are the main reason that the l(HOMO) value for corannulene is much larger than those for planar D(6h) symmetric pi-conjugated coronene and D(2h) symmetric pi-conjugated acenes with similar numbers of carbon atoms. The electron transfer in the positively charged corannulene is also discussed. Intramolecular electron mobility (sigma(intra,monocation)) in the positively charged corannulene is estimated to be smaller than those for the positively charged pi-conjugated acenes and coronene. The reorganization energy for the positively charged corannulene (0.060 eV) is estimated to be larger than those for the positively charged acenes and coronene. The strong orbital interactions between two neighboring carbon atoms in the HOMO of corannulene with the bowl-shaped structure are the main reasons for the calculated results. Thus, the larger overlap integral between two neighboring molecules is needed for the positively charged corannulene to become a better conductor than those for positively charged coronene and acenes. The smaller density of states at the Fermi level n(0) values are enough for the conditions of the attractive electron-electron interactions to be realized in the monocation of corannulene than in the monocations of coronene and acenes with similar numbers of carbon atoms. The multimode problem is also treated in order to investigate how consideration of the multimode problem is closely related to the characteristics of the electron-phonon interactions.     

Preparation and properties of oxadiazole‐containing polyacetylenes as electron transport materials

A series of functional polyacetylenes (PAs) bearing diphenyl oxadiazole pendant groups ( P1 – P4 ) were prepared, and the resultant polymers are completely soluble in common organic solvents. Their structures and properties were characterized and evaluated by DSC, TGA, UV, PL, CV, and EL analyses. The results show that all the resulting polymers possesses low LUMO energy level and high thermal stability, and the resultant functional polyacetylenes without spacer group between the polyacetylene conjugated main chain and oxadiazole pendant groups ( P1 – P3 ) show lower LUMO energy level (～?3.87 eV) and higher thermal properties (T_g) than that ( P4 ) with a flexible spacer. The resultant polymer ( P2 ) was applied as an ETM in bilayer electroluminescent devices and effectively enhances external quantum efficiency and the brightness of device, and decreases turn‐on voltages of devices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1406–1414, 2010     

Electrochemical, computational, and photophysical characterization of new luminescent dirhenium-pyridazine complexes containing bridging OR or SR anions

A series of [Re(2)(μ-ER)(2)(CO)(6)(μ-pydz)] complexes have been synthesized (E = S, R = C(6)H(5), 2; E = O, R = C(6)F(5), 3; C(6)H(5), 4; CH(3), and 5; H, 6), starting either from [Re(CO)(5)O(3)SCF(3)] (for 2 and 4), [Re(2)(μ-OR)(3)(CO)(6)](-) (for 3 and 5), or [Re(4)(μ(3)-OH)(4)(CO)(12)] (for 6). Single-crystal diffractometric analysis showed that the two μ-phenolato derivatives (3 and 4) possess an idealized C(2) symmetry, while the μ-benzenethiolato derivative (2) is asymmetrical, because of the different conformation adopted by the phenyl groups. A combined density functional and time-dependent density functional study of the geometry and electronic structure of the complexes showed that the lowest unoccupied molecular orbital (LUMO) and LUMO+1 are the two lowest-lying π* orbitals of pyridazine, whereas the highest occupied molecular orbitals (HOMOs) are mainly constituted by the "t(2g)" set of the Re atoms, with a strong Re-(μ-E) π* character. The absorption spectra have been satisfactorily simulated, by computing the lowest singlet excitation energies. All the complexes exhibit one reversible monoelectronic reduction centered on the pyridazine ligand (ranging from -1.35 V to -1.53 V vs Fc(+)|Fc). The benzenethiolato derivative 2 exhibits one reversible two-electron oxidation (at 0.47 V), whereas the OR derivatives show two close monoelectronic oxidation peaks (ranging from 0.85 V to 1.35 V for the first peak). The thioderivative 2 exhibits a very small electrochemical energy gap (1.9 eV, vs 2.38-2.70 eV for the OR derivatives), and it does not show any photoluminescence. The complexes containing OR ligands show from moderate to poor photoluminescence, in the range of 608-708 nm, with quantum yields decreasing (ranging from 5.5% to 0.07%) and lifetimes decreasing (ranging from 550 ns to 9 ns) (3 > 4 > 6 ≈ 5) with increasing emission wavelength. The best emitting properties, which are closely comparable to those of the dichloro complex (1), are exhibited by the pentafluorophenolato derivative (3).     

Synthesis and group 4 complexes of tris(pyrrolyl-alpha-methyl)amine

The tetradentate, trianionic ligand tris(pyrrolyl-alpha-methyl)amine (H(3)tpa) is available in 84% yield in a single step by a triple Mannich reaction involving 3 equiv of pyrrole, 3 equiv of formaldehyde, and ammonium chloride. The new ligand is readily placed on titanium by transamination on Ti(NMe(2))(4), which generates Ti(NMe(2))(tpa) (1) in 73% yield. Treating 1 with 1 equiv of 1,3-dimethyl-2-iminoimidazolidine (H-imd) in toluene provided a rare example of a titanium 2-iminoimidazolidinide, which displays some interesting structural features. Of note is the Ti-N(imd) distance of 1.768(2) A, a typical Ti-N double to triple bond distance. Reaction of Zr(NMe(2))(4) with H(3)tpa gave a complex of variable composition, probably varying in the amount of labile dimethylamine retained. However, stable discreet compounds were available by addition of THF, pyridine, or 4,4'-di-tert-butyl-2,2'-bipyridine (Bu(t)bpy) to in situ generated Zr(NMe(2))(NHMe(2))(x)(tpa). Three chloro zirconium complexes were generated using three different strategies. Treating Zr(tpa)(NMe(2))(Bu(t)bpy) (5) with ClSiMe(3) afforded Zr(tpa)(Cl)(Bu(t)bpy) (6) in 92% yield. Reaction of Li(3)tpa with ZrCl(4)(THF)(2) in THF gave a 72% yield of ZrCl(tpa)(THF)(2) (7). In addition, treatment of ZrCl(NMe(2))(3) with H(3)tpa cleanly generated ZrCl(NHMe(2))(2)(tpa) (8) in 95% yield. An organometallic zirconium complex was generated on treatment of 6 with LiCtbd1;CPh; alkynyl Zr(Ctbd1;CPh)(tpa)(Bu(t)bpy) (9) was isolated in 62% yield. 1, Ti(imd)(tpa) (2), 6, and 9 were characterized by X-ray diffraction.