Modular α-Functionalization of Bowl-Shaped Subphthalocyanine Aromatics.

Herein a general strategy for the α-functionalization of subphthalocyanines (SubPcs) via palladium-catalyzed cross-coupling reactions is described. Despite the higher steric demand of α-SubPcs, -symmetric iodinated precursors were found to readily undergo α-arylation, alkynylation, alkenylation, and C-N coupling. This strategy is also applicable to enantiopure and even more sterically congested (-symmetric) tri- and hexa-substituted derivatives.

Too Fast for Spin Flipping: Absence of Chirality-Induced Spin Selectivity in Coherent Electron Transport through Single-Molecule Junctions.

Chirality-induced spin selectivity (CISS), which refers to the ability of chiral molecules to preferentially select spins during electron transfer, has attracted great attention during the past two decades. However, the theoretical and experimental understanding of the CISS effect remains preliminary. In this study, we demonstrate that there is no distinguishable CISS effect in the case of coherent electron transport through single chiral molecular junctions for a set of four molecule studied here.

Spin filtering in self-assembled bowl-shaped aromatics.

Bowl-shaped aromatics can be chiral, so their columnar self-assembly can yield homochiral supramolecular structures. This valuable-but underexploited-property adds a novel twist to the disruptive applications of these materials, rendering them potentially useful in the burgeoning field of molecular spintronics. Herein, we demonstrate that columnar arrays based on chiral subphthalocyanine aromatics can efficiently function as spin filters the chirality-induced spin selectivity (CISS) effect.

Effects of removing boron from subphthalocyanines: a theoretical perspective.

The element hosted within the inner cavity of phthalocyanines (Pcs) dictates the wide functional versatility of these well-known macrocycles. Subphthalocyanines (SubPcs), by contrast, are only known as boron complexes, yet they exhibit a range of emerging properties unattainable with other compounds. The effects of replacing the boron atom in these macrocycles, however, remain unclear.

β-to-β Singly Linked Subphthalocyanine Dimers with Effective π-Conjugation.

In this work, a series of π-conjugated Subphthalocyanine dimers assembled by simple π-bridges were efficiently synthesized through metal-catalyzed reactions. Despite being singly linked, these readily accessible arrays exhibit excellent π-electron communication, significantly perturbing the orbital distribution of conventional SubPcs and inducing notable alterations in their optical properties. The findings presented here demonstrate the potential of SubPcs for constructing curved porphyrin arrays with well-conjugated skeletons and intriguing functionalities.

The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines.

The columnar arrangement of bowl-shaped aromatics is a promising strategy for producing high-performing semiconductors. However, the structural factors that dictate the self-assembly of these molecules remain poorly understood. Herein, we show how chirality and peripheral substitution affect the columnar assembly of subphthalocyanines (SubPcs) in solution.

Columnar liquid crystals based on antiaromatic expanded porphyrins.

Three naphthorosarins, antiaromatic expanded porphyrins bearing different substituents (NRos 1-3), designed to self-assemble into columnar liquid crystalline (LC) structures, were synthesized and characterized using polarized optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as supporting computational calculations. The substituents were found to play a crucial role in modulating the LC behaviour.

Supramolecular Subphthalocyanine Cage as Catalytic Container for the Functionalization of Fullerenes in Water.

Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo-organic Pd(II)-subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C , we have prepared a water-soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C , namely, Diels-Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes co-encapsulation of insoluble C and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions.

Borylated Subphthalocyanines: Versatile Precursors for the Preparation of Functional Bowl-Shaped Aromatics.

The peripheral borylation of porphyrinoids has become a key step to prepare advanced functional materials. This study reports the synthesis, electronic properties, and reactivity of borylated subphthalocyanines. These compounds, which are prepared by Suzuki-Miyaura borylation in excellent yields, are easily purified, display a great stability, and serve as powerful starting materials for the post-functionalization of SubPcs via cross-coupling reactions.

Easily processable spin filters: exploring the chiral induced spin selectivity of bowl-shaped chiral subphthalocyanines.

High spin polarization (SP) in studies of chiral induced spin selectivity (CISS) is only observed when chiral molecules are properly organized. This is generally achieved by using anchoring groups or complex supramolecular polymers. A new class of spin filters based on bowl-shaped aromatics is reported, which form high-quality thin-films by simply spin-coating and displaying high spin filtering properties.

Recent advances in subphthalocyanines and related subporphyrinoids.

Half a century after the synthesis of the first subporphyrinoid, the study of tripyrrole and trisoindole porphyrin analogues constitutes a fervent and rapidly expanding research area. The outstanding structural, electronic and optical features of these cone-shaped aromatic macrocycles render them attractive candidates for a wide variety of applications, ranging from optoelectronics to biomedicine. To tune their properties and exploit their functionalities, the development of novel methodologies for the synthesis and post-functionalization of these contracted porphyrinoids, as well as a deep understanding of their supramolecular organization and their implementation into multicomponent systems of increasing complexity are of paramount importance.

Anthracene-Fused Oligo-BODIPYs: A New Class of π-Extended NIR-Absorbing Materials.

Large π-conjugated systems are key in the area of molecular materials. Herein, we prepare via Au -catalyzed cyclization a series of fully π-conjugated anthracene-fused oligo-BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy.

Preparation, Supramolecular Organization, and On-Surface Reactivity of Enantiopure Subphthalocyanines: From Bulk to 2D-Polymerization.

The development of chiral materials is severely limited by the challenge to achieve enantiopure derivatives with both configurational stability and good optoelectronic properties. Herein we demonstrate that enantiopure subphthalocyanines (SubPcs) fulfill such demanding requirements and bear the prospect of becoming components of chiral technologies. Particularly, we describe the synthesis of enantiopure SubPcs and assess the impact of chirality on aspects as fundamental as the supramolecular organization, the behavior in contact with metallic surfaces, and the on-surface reactivity and polymerization.

Modulating the Electron Transporting Properties of Subphthalocyanines for Inverted Perovskite Solar Cells.

The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of PSCs.

Controlling Electronic Events Through Rational Structural Design in Subphthalocyanine-Corrole Dyads: Synthesis, Characterization, and Photophysical Properties.

Porphyrinoids are considered perfect candidates for their incorporation into electron donor-acceptor (D-A) arrays due to their remarkable optoelectronic properties and low reorganization energies. For the first time, a series of subphthalocyanine (SubPc) and corrole (Cor) were covalently connected through a short-range linkage. SubPc axial substitution strategies were employed, which allowed the synthesis of the target molecules in decent yields.

Subphthalocyaninato Boron(III) Hydride: Synthesis, Structure and Reactivity.

Subphthalocyanine (SubPc) chemistry has been limited so far by their high sensitivity toward strong nucleophiles. In particular, the substitution of the axial chlorine atom by a nucleophilic group in the case of less-reactive SubPcs, such as those bearing electron-withdrawing peripheral substituents, presents some limitations and requires harsh conditions. By taking advantage of the electrophilic character of DIBAL-H, it has been possible to prepare for the first time SubPc-hydride derivatives that exhibit high reactivity as hydroboration reagents of aldehydes.

Annulative π-extension of BODIPYs made easy gold(i)-catalyzed cycloisomerization.

Here we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of π-extended BODIPY derivatives. The catalytic system PPh AuCl/AgSbF enables the synthesis of []-[2,1]naphtho-fused-BODIPYs () under mild conditions, in excellent yields and short reaction times. The reaction is totally regioselective to the 6--dig product and for the α-position of the BODIPY, which is both the kinetically and thermodynamically favored pathway, as supported by the free energy profile calculated by means of Density Functional Theory (DFT).