Electron Spin Polarization and Rectification Driven by Chiral Perylene Diimide-Based Nanodonuts.

The chirality-induced spin selectivity (CISS) effect allows thin-film layers of chiral conjugated molecules to function as spin filters at ambient temperature. Through solvent-modulated dropcasting of chiral l- and d-perylene diimide (PDI) monomeric building blocks, two types of aggregate morphologies, nanofibers and nanodonuts, may be realized. Spin-diode behavior is evidenced in the nanodonut structures. Stacked PDI units, which form the conjugated core of these nanostructures, dominate the nanodonut-Au electrode contact; in contrast, the AFM tip contacts largely the high-resistance solubilizing alkyl chains of the chiral monomers that form these nanodonuts. Current-voltage responses of the nanodonuts, measured by magnetic conductive AFM (mC-AFM), demonstrate substantial spin polarizations as well as spin current rectification ratios (>10) that exceed the magnitudes of those determined to date for other chiral nanoscale systems. These results underscore the potential for chiral nanostructures, featuring asymmetric molecular junctions, to enable CISS-based nanoscale spin current rectifiers.

Trimethylsilanolate-Promoted Activation of Alkynyl Trimethylsilanes: Hiyama-Type Sonogashira Cross-Coupling for the Synthesis of Arylene-Ethynylene-Linked Porphyrin Arrays.

To synthesize meso-ethynylene-conjugated porphyrin arrays, the Sonogashira cross-coupling reaction is straightforward to construct the C(sp)-C(sp2) bonds, but the reaction is often accompanied by side reactions such as the Glaser homocoupling. The rate-determining oxidative addition step results in the unexpected kinetic competition with the Glaser homocoupling, which is desired to be circumvented. We here propose two sets of improved strategies for the synthesis of arylene-ethynylene-linked porphyrin arrays from the meso-brominated porphyrin and alkynes. First, we explored the solvent-modulated approach employing dichloromethane as the reaction solvent to minimize the formation of the copper acetylide dimer as the intermediate for the Glaser homocoupling, while the scope of the approach is limited. Subsequently, we have developed the trimethylsilanolate-promoted Hiyama-type approach that activates alkynyl trimethylsilanes (TMSs) by use of potassium trimethylsilanolate under amine-free conditions. The latter approach is advantageous not only in skipping the preprotodesilylation of the TMS group but also in achieving an excellent isolated yield.

Preferential solvation of meso-methyl BODIPYs with pyridine via pseudo-hydrogen-bonds.

This study explored unexpected pseudo-hydrogen bond interactions between meso-methyl BODIPYs and pyridine or acridine. NMR spectral evidence indicated that the meso-methyl group and BF2 core of BODIPYs formed C-H⋯N and C-H⋯F-B pseudo-hydrogen bonds with pyridine, respectively. The weak binding strength was attributed to the preferential solvation of pyridine in the vicinity of meso-methyl BODIPYs in cyclohexane. The observations were explained by the formation of pseudo-hydrogen bonds based on the quantum theory of atoms in molecules (QTAIM) formalism. In contrast, acridine binds to BODIPY with a moderate binding strength. QTAIM formalism suggested the existence of the complementary pseudo-hydrogen bonds, which superficially seemed to rationalise the experimental observations. However, extensive NMR experiments have found no discrete geometry for the complex, indicating considerable geometric freedom. This discrepancy suggests that the static pictures based on the QTAIM analyses conflict with the enthalpy-entropy compensation principle in essential thermodynamics.

Evidence of C-F···H-C Attractive Interaction: Enforced Coplanarity of a Tetrafluorophenylene-Ethynylene-Linked Porphyrin Dimer.

The formation of C-F···H-C "hydrogen bonds" has been a controversial subject because, in principle, fluorine is hardly an acceptor for less acidic protons contrasting to the C-F···H-O and C-F···H-N hydrogen bonds. Nevertheless, the interaction is emerging as a powerful implement for confining the torsional rotation in the design of fully coplanar π-conjugated polymers. Heretofore, no evidence of the C-F···H-C interaction has been observed in solutions. We herein disclose comprehensive evidence that the C-F···H-C interaction produces an attractive force. A 19F-1H heteronuclear Overhauser effect experiment elucidated the close proximity of the F and H atoms in the doubly edge-facing C-F···H-C interactions of a meso-tetrafluorophenylene-ethynylene-conjugated porphyrin dimer (1). Extensive electronic and photophysical property investigations confirmed that all the aromatic units were torsionally restricted by the C-F···H-C interactions. Moreover, the enforced coplanarity invoked a markedly high π-staking propensity. Thus, we have firmly established the formation of a C-F···H-C interaction that produces a hydrogen-bond-like attractive force in solution.

Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.

Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.

Perfluorophenyl-Directed Giant Porphyrin J-Aggregates.

Quadrupolar interactions of porphyrin bearing two pentafluorophenylethynyl terminals (1) drove the formation of a successive one-dimensional staircase structure, i.e., J-aggregates, to yield millimeter-length needles with a single-crystalline character in methylcyclohexane solution. In contrast, π-stacked interactions of porphyrin bearing two nonfluorinated phenyl terminals (2) formed no aggregates in solution. A spin-cast film of 1 also showed bathochromic shift of the Soret and Q bands, indicating the formation of J-aggregates. The molecular arrangement of the J-aggregates was revealed by microbeam glazing-incidence wide-angle X-ray diffraction (GIWAXD), and was in good agreement with the optimized structure generated by density functional theory (DFT) calculations.

Fully Conjugated Porphyrin Glass: Collective Light-Harvesting Antenna for Near-Infrared Fluorescence beyond 1 µm.

Expanded π-systems with a narrow highest occupied molecular orbital-lowest unoccupied molecular orbital band gap encounter deactivation of excitons due to the "energy gap law" and undesired aggregation. This dilemma generally thwarts the near-infrared (NIR) luminescence of organic π-systems. A sophisticated cofacially stacked π-system is known to involve exponentially tailed disorder, which displays exceptionally red-shifted fluorescence even as only a marginal emission component. Enhancement of the tail-state fluorescence might be advantageous to achieve NIR photoluminescence with an expected collective light-harvesting antenna effect as follows: (i) efficient light-harvesting capacity due to intense electronic absorption, (ii) a long-distance exciton migration into the tail state based on a high spatial density of the chromophore site, and (iii) substantial transmission of NIR emission to circumvent the inner filter effect. Suppression of aggregation-induced quenching of fluorescence could realize collective light-harvesting antenna for NIR-luminescence materials. This study discloses an enhanced tail-state NIR fluorescence of a self-standing porphyrin film at 1138 nm with a moderate quantum efficiency based on a fully π-conjugated porphyrin that adopts an amorphous form, called "porphyrin glass".

Preferential Solvation Unveiled by Anomalous Conformational Equilibration of Porphyrin Dimers: Nucleation Growth of Solvent-Solvent Segregation.

Preferential solvation was explored using ethynylene- or butadiynylene-linked porphyrin dimers bearing 3,4,5-tri(( S)-3,7-dimethyloctyloxy)phenyl groups at the meso positions in binary hexafluorobenzene (C6F6) and cyclohexane (C6H12) mixture, expecting contrasting solvent affinity of the porphyrin core and the alkyl side chains toward the individual solvent component. Although the solvent polarity remained nearly constant along with the continuous variation of the solvent composition, the porphyrin dimer showed dramatic change in spectroscopic signatures, indicating the occurrence of preferential solvation. Because of small rotational barrier around the ethynylene and butadiynylene linkage, the torsional conformations of the porphyrin dimers varied from orthogonal to planar due to continuous variation of molar fraction of C6H12-C6F6 mixture. Thorough thermodynamic analyses inferred that nucleation as the enthalpic component and phase segregation as the entropic component operated preferential solvation. The porphyrin dimer nucleated the C6H12-C6F6 segregation, and the torsional conformation was diagnostic of the inversion of the interfacial curvature of the solvent segregation along with the continuous variation.

An antiparallel double-stranded BODIPY-porphyrin dyad assembled via a self-complementary B-FZn interaction.

An antiparallel double-strand of a BODIPY-zinc-porphyrin dyad was assembled via geometrical complementarity of an unusual B-FZn coordination bonding interaction.

A metal-lustrous porphyrin foil.

A metal-lustrous self-standing film, named "porphyrin foil", was formed from a glass-forming polymeric porphyrin. The amorphous glass nature of the porphyrin foil played a key role in spontaneously producing a smooth surface. Its sharp contrast in intense absorption and specular reflection of light at each wavelength provided a brilliant metallic lustre.

A Tightly Stretched Ultralong Supramolecular Multiporphyrin Array Propagated by Double-Strand Formation.

A shape-programmed linearity through supramolecular polymerization is demonstrated by a step-growth double-strand formation of a telechelic oligomeric porphyrin array in which two alternating pyridyl-porphyrin sequenced units are held together by self-complementary ligand-to-metal coordination. The stiff rod-like structure and sufficiently large binding constant of the double-strand unit considerably extended a supramolecular array in the one dimension, which produced a tightly stretched string with a length that exceeded several micrometers.

Group 14 Dithienometallole-Linked Ethynylene-Conjugated Porphyrin Dimers.

The considerably conjugated π systems of the group 14 dithienometallole-linked ethynylene-conjugated porphyrin dimers (1Ms) were described based on comprehensive experimental and theoretical studies. The electronic absorption spectra of 1M displayed a large splitting in the Soret band and a red-shifted Q-band, indicating that the dithienometallole spacer was effective in facilitating the porphyrin-porphyrin electronic coupling. Torsional planarization behaviors of 1M were observed in the time-resolved fluorescence spectra. Density functional theory (DFT) calculations revealed that the dithienometallole spacer is an ideal partner for the ethynylene-conjugated porphyrin to produce fully delocalized highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels due to their similar HOMO and LUMO levels. Finally, 1M exhibited a strong propensity for the quinoidal-cummulenic conjugation in the dithienometallole spacer when in a photoexcited state.

Oligoamylose-entwined porphyrin: excited-state induced-fit for chirality induction.

An oligoamylose-strapped porphyrin displayed circularly polarized luminescence (CPL) in the S1 state despite being silent in circular dichroism (CD) in the ground state, suggesting chirality induction in the photoexcited porphyrin moiety from the oligoamylose-strap in the photoexcited state.

Self-complementary double-stranded porphyrin arrays assembled from an alternating pyridyl-porphyrin sequence.

Oligomeric porphyrin arrays with an alternating pyridyl-porphyrin sequence were synthesized to explore double-strand formation through self-complementary pyridyl-to-zinc axial coordination bonds. Competitive titration experiments revealed the thermodynamic aspects involved in the zipper effect within double-strand formation. Multiple axial coordination bonds defined the stacked conformation, despite a marginal contribution to the stability of the double-strands. Thus, the zipper cooperativity was the dominant factor for the remarkable stability. Moreover, the dimeric and trimeric porphyrin arrays were independently assembled into double-strands by self-sorting from a binary mixture. Double-strand formation engineered discretely stacked π-systems. Successive slipped-cofacial stacks of the porphyrin rings progressively extended the π-system via exciton coupling over the double-strand while keeping a relatively high fluorescence quantum yield.

Highly fluorescent slipped-cofacial phthalocyanine dimer as a shallow inclusion complex with α-cyclodextrin.

Supramolecular control of the π-stacked configuration of aqueous phthalocyanine (Zn[Pc(SO(3))(4)]) was achieved, allowing organization of a J-type slipped-cofacial dimer with per-O-methylated α-cyclodextrin (TMe-α-CDx) by the aid of host-guest interactions. Pristine Zn[Pc(SO(3))(4)] forms nonfluorescent face-to-face aggregates in water. The π-stacked configuration was controlled in the slipped-cofacial dimer, which was formed as a shallow inclusion complex with TMe-α-CDx, giving remarkably enhanced fluorescence with a very small Stokes shift. Organization of the J-type slipped-cofacial dimer as a 2:2 Zn[Pc(SO(3))(4)]-TMe-α-CDx complex was achieved through π-stacking of the unencapsulated segment of Zn[Pc(SO(3))(4)] shallowly encapsulated by a small TMe-α-CDx cavity.

Hexameric subphthalocyanine rosette.

A highly congested hexameric subphthalocyanine array was synthesized by axial chlorine-to-phenoxy substitution of a hexakis(4-hydroxyphenyl)benzene based subphthalocyanine, and photoinduced symmetry-breaking charge separation was demonstrated in polar solvent.

Ligand-assisted J-type aggregates of zinc porphyrin: anticooperative molecular organization in self-assembled bolaamphiphile.

Bolaamphiphilic zinc porphyrins bearing a 2-pyridylethynyl or 4-methoxyphenylethynyl group, Zn(PyPor) or Zn(ArPor), respectively, were newly synthesized in order to explore the molecular organizing behaviours within the interior hydrophobic layer of aqueous self-assemblies. Well-ordered J-type aggregates of Zn(PyPor) were formed in aqueous self-assembled bolaamphiphile, whereas J-type aggregates of Zn(ArPor) were disordered. The titration experiments suggest that axial coordination bond improves the structural uniformity of the J-type aggregates of Zn(PyPor). In a homogeneous isotropic media, on the other hand, Zn(PyPor) formed an antiparallel dimer through self-complementary coordination. Unprecedented molecular organization of ligand-assisted J-type aggregates is described in the term of anticooperative effect under the bulk conditions.

Strong two-photon and three-photon absorptions in the antiparallel dimer of a porphyrin-phthalocyanine tandem.

Imidazolyl-appended phthalocyaninatozinc(II) containing an ethynylporphyrin linkage was stacked by complementary coordination into an antiparallel dimer that displayed strong nonlinear optical properties involving two-photon and three-photon absorptions.

Tandem cofacial stacks of porphyrin-phthalocyanine dyads through complementary coordination.

A novel straightforward methodology to organize discrete heterogeneous stacks of porphyrin and phthalocyanine employed an imidazolyl-to-zinc complementary coordination protocol for a Zn(II) phthalocyanine that contains an imidazolyl terminal with an ethynylporphyrin as a coplanar spacer. Structural elucidation was performed by means of size-exclusion chromatography, spectral titration, and NMR spectroscopy. The association constants for the complementary coordination of the heterogeneous slipped-cofacial tetrads reached extremely high values, in the order of 10(14) M(-1). Close contact of the porphyrin and phthalocyanine planes led to a strong shielding of the cofacial protons, which were split due to the slipped-cofacial heterogeneous environment. In variable-temperature NMR spectroscopy, the split signals remained in the aromatic region, a result suggesting structural robustness. Addition of trifluoroacetic acid dissociated the coordination structure to unify the split signals. The stacked tetrads showed unique electronic structures, such as strong exciton coupling and charge-transfer properties between the porphyrin and phthalocyanine units, which were modulated by the peripheral substituents of the phthalocyanine subunit and by the solvent. Interconversion between the coordination tetrad and the corresponding dyad was observed upon addition of an axial ligand.

Fine-tuning of a ferrocene[porphyrin]ITO redox cascade for efficient sequential electron transfer commenced by an S2 photoexcited special-pair mimic.

A systematic series of ferrocene/porphyrin redox cascade architectures was assembled through a slipped-cofacial porphyrin dimer on ITO electrode in optimizing the anodic photocurrent generation to perform the highest quantum yield compared to reported values on ITO electrodes.