・電荷移動相互作用 ・水素結合 - Kyoto U

1 (donor) (acceptor) (D A) (D+ A- ) Donor: n-donor -donor Acceptor: -acceptor (X2) R X -acceptor * * n- *, n- *, - *, - * Charge-Transfer Complexes Molecular Complexes Low ionization potential Large electron affinity Non-bonding state Charge-transfer state Resonating stabilization Lone-pair electrons Unsaturated carbons, aromatics with electron donating groups Halogen molecules Anti-bonding * orbital Unsaturated carbons, aromatics with electron accepting groups Anti-bonding * orbital Possible 4 types of combinations <n- * complex> (CH3)3N-I2 N H3C H3C H3C I I n-electron *-orbital cf.

2 N I van der Waals cf. free I2 CT interaction <n- * complex> Fig. 17. 1:2 complex of hexamethyleneteramine and bromine. Fig. 18. 2:1 complex of methanol and bromine. N Br: Br Br: O Br: Br Br: cf. N Br van der Waals free Br2 cf. O Br van der Waals < - * complex> Fig. 20. 1:1 complex of p-xylene and carbontetrabromide. Fig. 19. 1:1 complex of benzene and bromine. Br Br: cf. -ring Br van der Waals free Br2 <n- * complex> < - * complex> Fig. 21. 1:1 complex of dinitrogen-tetroxide and 1,4-dioxane. Fig. 22. 1:1 complex of perylene and pyromellitic dianhydride. O N: cf. O N van der Waals - * complex A A A A D D D D A A A A D D D D A A A A D D D D HOMO -orbital LUMO *-orbital HOMO LUMO d d 0 HOMO -orbital overlaps with LUMO *-orbital so that the sign of the coefficients coincides Assuming no change in the distance Overlap integral LUMO1 LUMO2 HOMO1 HOMO2 CNCNNCNCTCNB LUMO NH2NH2 PDA HOMO Benzene-type molecules Maximum overlap integral For the eclipsed overlap 0 Overlap integral ~0 NH2NH2 PDA HOMO p-benzoquinone-type acceptor OOLUMO 85 % Maximum overlap integral overlap integral ~85% TCNQ-type acceptor CNNCNCCNLUMO NH2NH2 PDA HOMO ring-over-bond type overlap Maximum overlap integral A- A- A- A- D+ D+ D+ D+

3 D + D D+ + D- A + A A+ + A- A A A A D D D D A1/2- D1/2+ A A D D D+ D+ A- A- D1/2+ D1/2+ D1/2+ A1/2- A1/2- A1/2- D+ + D+ D2+ + D0 A- + A- A0 + A2- donor acceptor D0 + D+ D+ + D0 A- + A0 A0 + A- donor acceptor The complex with a neutral ground state does not take this structure Segregated stacked CT complexes full ionization partial charge transfer CT interaction CT interaction Organic conductors O1 H O2 O1 O2 distance O1 H distance H O2 distance O1 H distance Hydrogen bonds X H Y + - - Occurrence frequency s / cm-1 Stronger hydrogen bonds Nakamoto diagram NNHHNEtOHHNNNOPhPhHNNNNHHNOEtHNNRONHHNHO NOHNHHHHPrOPhPrONNNPhPh(a) (b) (c) D D D A A A D D D A A A D D D A A A - G0 = kJ mol-1 - G0 = 23 kJ mol-1 - G0 > 29 kJ mol-1 repulsive attractive attractive NHHNPhOPhNHHNPhOPhNHHNXOXNHHNXOXOOOOHOHO OHOHNHHNXOXNHHNXOXOOOOHOHOOHOHNHHNHOHCNC NNHHNHOH urea Hydrogen bonds and Crystal design Two-dimensional extension by introducing functional groups Two-dimensional extension by combining other components One-dimensional chain structure of urea M.

4 Etter NC-C5-CN NC-C4-CN NC-C3-CN Dipole moment NNHNHR2R1 NNR1 HHNNHOOHOR3R3 NNHNHR2R1 NNR1 HHmelamine derivative barbituric acid derivative R1, R2, R3 One-dimensional tape structure is preferentially formed relatively irrelevant with R1, R2, and R3 Lehn, whitesides C12 + biphenyl C12 + naphthyl C8 + naphthyl Hamilton Crystals for non-linear optics E P P = E + E2 + E3 + Polarization (P) induced by electric field (E) polarizability Second-order hyper-polarizability = 0 Molecule (substance) with inversion center D A E E Electrons can move easily Electrons move less easily If the molecule has no inversion center NH2CH3NO2P NOONHHH3 CNOONHHH3 CNOONHHH3 Cnitroanilines D A 2 SHG Nakanishi, Marder N+CH3 NCH3H3 CCH3SO3-N+CH3 OHCH3SO3-HO packing layer