Ring-Opening Metathesis Polymerization of the Dewar Isomer of 1,2-Azaborinine, a B-N Isostere of Benzene.

The successful polymerization of the Dewar isomer of an azaborinine heterocycle is reported. Controlled ring-opening metathesis polymerization was accomplished with Grubbs and Hoveya-Grubbs second generation catalysts (G2, HG2), as well as a Z-selective Ru catalyst (HGM2001). The structure of the polymers containing 4-membered B-N heterocycles was verified by GPC and multinuclear and 2D NMR. Differences in stereochemistry of polymers derived from G2/HG2 versus the Z-selective catalyst HGM2001 were substantiated by 2D NOESY, FT-IR, and Raman analyses. The incorporation of B-N heterocycles into these polymer structures is promising as a route to functional polymers that contain polar side groups.

Boron-Nitrogen Lewis Pairs in the Assembly of Supramolecular Macrocycles, Molecular Cages, Polymers, and 3D Materials.

Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B-N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self-healing, and responsive thermosets, gels and elastomeric materials.

Tris(pyridyl)borates: an emergent class of versatile and robust polydentate ligands for catalysis and materials applications.

Tridentate ligands that incorporate pyridyl rather than pyrazolyl groups are emerging as an attractive class of "scorpionate"-type ligands with enhanced electron donation, increased stability, and divergent geometry at the metal centre relative to tris(pyrazolyl)borates originally introduced by Trofimenko. Following our initial reports, the tris(pyridyl)borate (Tpyb) ligand architecture has been adopted by several research groups in pursuit of functional metal complexes that offer new opportunities in catalysis and materials science. While earlier work had been focused on symmetric octahedral complexes, ML2, which are advantageous as highly robust building blocks in materials sciences, recently introduced new ligand designs provide access to heteroleptic metal complexes with vacant sites that lend themselves to applications in catalysis. Signficant progress has also been made in the post-complexation functionalization of these ligands via electrophilic and nucleophilic substitution reactions at the boron centres, opening up new routes for integration of Tpyb complexes with diverse functional materials while also raising interesting mechanistic questions.

Synthesis and Structure-Property Relationships in Regioisomeric Alternating Borane-Terthiophene Polymers.

Main-chain boron-containing π-conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene-borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6-tri-tert-butylphenyl, Mes*; 2,4,6-tris(trifluoromethyl)phenyl, FMes) examined. Pd2 dba3 /P(t-Bu)3 -catalyzed Stille polymerization of arylbis(2-thienyl)borane and arylbis(3-thienylborane) with 2,5-bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI-TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5-bis(tri-n-butylstannyl)thiophene as comonomer, and Pd2 dba3 /P(o-tol)3 as the catalyst at 100 °C. Under these conditions, macrocyclic species with n=3-10 repeating units formed preferentially according to MALDI-TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow-green, blue-green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.

Triarylboron-Doped Acenethiophenes as Organic Sonosensitizers for Highly Efficient Sonodynamic Therapy with Low Phototoxicity.

The development of efficient organic sonosensitizers is crucial for sonodynamic therapy (SDT) in the field of cancer treatment. Herein, a new strategy for the development of efficient organic sonosensitizers based on triarylboron-doped acenethiophene scaffolds is presented. The attachment of boron to the linear acenethiophenes lowers the lowest unoccupied molecular orbital (LUMO) energy, resulting in redshifted absorptions and emissions. After encapsulation with the amphiphilic polymer DSPE-mPEG2000 , it is found that the nanostructured BAnTh-NPs and BTeTh-NPs (nanoparticles of BAnTh and BTeTh) shows efficient hydroxyl radical (• OH) generation under ultrasound (US) irradiation in aqueous solution with almost no phototoxicity, which can overcome the shortcomings of O2 -dependent SDT and avoid the potential cutaneous phototoxicity issue. In vitro and in vivo therapeutic results validate that boron-doped acenethiophenes as sonosensitizers enable high SDT efficiency with low phototoxicity and good biocompatibility, indicating that boron-functionalization of acenes is a promising strategy toward organic sonosensitizers for SDT.

Near-Infrared-Absorbing B-N Lewis Pair-Functionalized Anthracenes: Electronic Structure Tuning, Conformational Isomerism, and Applications in Photothermal Cancer Therapy.

B-N-fused dianthracenylpyrazine derivatives are synthesized to generate new low gap chromophores. Photophysical and electrochemical, crystal packing, and theoretical studies have been performed. Two energetically similar conformers are identified by density functional theory calculations, showing that the core unit adopts a curved saddle-like shape (x-isomer) or a zig-zag conformation (z-isomer). In the solid state, the z-isomer is prevalent according to an X-ray crystal structure of a C6F5-substituted derivative (4-Pf), but variable-temperature nuclear magnetic resonance studies suggest a dynamic behavior in solution. B-N fusion results in a large decrease of the HOMO-LUMO gap and dramatically lowers the LUMO energy compared to the all-carbon analogues. 4-Pf in particular shows significant absorbance at greater than 700 nm while being almost transparent throughout the visible region. After encapsulation in the biodegradable polymer DSPE-mPEG2000, 4-Pf nanoparticles (4-Pf-NPs) exhibit good water solubility, high photostability, and an excellent photothermal conversion efficiency of ∼41.8%. 4-Pf-NPs are evaluated both in vitro and in vivo as photothermal therapeutic agents. These results uncover B-N Lewis pair functionalization of PAHs as a promising strategy toward new NIR-absorbing materials for photothermal applications.

Dynamic B/N Lewis Pairs: Insights into the Structural Variations and Photochromism via Light-Induced Fluorescence to Phosphorescence Switching.

Ultralong afterglow emissions due to room-temperature phosphorescence (RTP) are of paramount importance in the advancement of smart sensors, bioimaging and light-emitting devices. We herein present an efficient approach to achieve rarely accessible phosphorescence of heavy atom-free organoboranes via photochemical switching of sterically tunable fluorescent Lewis pairs (LPs). LPs are widely applied in and well-known for their outstanding performance in catalysis and supramolecular soft materials but have not thus far been exploited to develop photo-responsive RTP materials. The intramolecular LP M1BNM not only shows a dynamic response to thermal treatment due to reversible N→B coordination but crystals of M1BNM also undergo rapid photochromic switching. As a result, unusual emission switching from short-lived fluorescence to long-lived phosphorescence (rad-M1BNM, τRTP =232 ms) is observed. The reported discoveries in the field of Lewis pairs chemistry offer important insights into their structural dynamics, while also pointing to new opportunities for photoactive materials with implications for fast responsive detectors.

Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory.

Polycyclic aromatic hydrocarbons (PAHs) are prominent lead structures for organic optoelectronic materials. This work describes the synthesis of three B,S-doped PAHs with heptacene-type scaffolds via nucleophilic aromatic substitution reactions between fluorinated arylborane precursors and 1,2-(Me3SiS)2C6H4/1,8-diazabicyclo[5.4.0]undec-7-ene (72-92% yield). All compounds contain tricoordinate B atoms at their 7,16-positions, kinetically protected by mesityl (Mes) substituents. PAHs 1/2 feature two/four S atoms at their 5,18-/5,9,14,18-positions; PAH 3 is a 6,8,15,17-tetrafluoro derivative of 2. For comparison, we also prepared the skewed naphtho[2,3-c]pentaphene-type isomer 4. The simultaneous presence of electron-accepting B atoms and electron-donating S atoms results in a redox-ambiphilic behavior; the radical cations [1•]+ and [2•]+ were characterized by electron paramagnetic resonance spectroscopy. Several low-lying charge-transfer states exist, some of which (especially S-to-B and Mes-to-B transitions) compete on the excited-state potential-energy surface. Consistent with the calculated state characters and oscillator strengths, this competition results in a spread of fluorescence quantum yields (2-27%). The optoelectronic properties of 1 change drastically upon addition of Ag+ ions: while the color of 1 in CH2Cl2 changes bathochromically from yellow to red (λmax from 463 to 486 nm; -0.13 eV), the emission band shifts hypsochromically from 606 to 545 nm (+0.23 eV), and the fluorescence quantum yield increases from 12 to 43%. According to titration experiments, higher order adducts [Agn1m]n+ are formed. As a suitable system for modeling Ag+ complexation, our calculations predict a dimer structure (n = m = 2) with Ag2S4 core, approximately linear S-Ag-S fragments, and Ag-Ag interaction. The computed optoelectronic properties of [Ag212]2+ agree well with the experimentally observed ones.

A New Platform of B/N-Doped Cyclophanes: Access to a π-Conjugated Block-Type B3 N3 Macrocycle with Strong Dipole Moment and Unique Optoelectronic Properties.

We herein describe a new design principle to achieve B/N-doped cyclophane where an electron-donor block of three triarylamines (Ar3 N) and an acceptor block of three triarylboranes (Ar3 B) are spatially separated on opposite sides of the π-extended ring system. DFT computations revealed the distinct electronic structure of the block-type macrocycle MC-b-B3N3 with a greatly enhanced dipole moment and reduced HOMO-LUMO energy gap in comparison to its analogue with alternating B and N sites, MC-alt-B3N3. The unique arrangement of borane acceptor Ar3 B and amine donor Ar3 N components in MC-b-B3N3 induces exceptionally strong intramolecular charge transfer in the excited state, which is reflected in a largely red-shifted luminescence at 612 nm in solution. The respective linear open-chain oligomer L-b-B3N3 was also synthesized for comparison. Our new approach to donor-acceptor macrocycles offers important fundamental insights and opens up a new avenue to unique optoelectronic materials.

Electrophilic and nucleophilic displacement reactions at the bridgehead borons of tris(pyridyl)borate scorpionate complexes.

Although a wide variety of boron-based "scorpionate" ligands have been implemented, a modular route that offers facile access to different substitution patterns at boron has yet to be developed. Here, we demonstrate new reactivity patterns at the bridgehead positions of a ruthenium tris(pyrid-2-yl)borate complex that allow for facile tuning of steric and electronic properties.

Linear Extension of Anthracene via B←N Lewis Pair Formation: Effects on Optoelectronic Properties and Singlet O2 Sensitization.

The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine-tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and as sensitizers for singlet oxygen generation. We demonstrate that the N-directed electrophilic borylation of 2,6-di(pyrid-2-yl)anthracene offers access to linearly extended acene derivatives Py-BR (R=Et, Ph, C6 F5 ). In comparison to indeno-fused 9,10-diphenylanthracene, the formal "BN for CC" replacement in Py-BR selectively lowers the LUMO, resulting in a much reduced HOMO-LUMO gap. An even more extended conjugated system with seven six-membered rings in a row (Qu-BEt) is obtained by borylation of 2,6-di(quinolin-8-yl)anthracene. Fluorinated Py-BPf shows particularly advantageous properties, including relatively lower-lying HOMO and LUMO levels, strong yellow-green fluorescence, and effective singlet oxygen sensitization, while resisting self-sensitized conversion to its endoperoxide.

A Multiple Excited-State Engineering of Boron-Functionalized Diazapentacene Via a Tuning of the Molecular Orbital Coupling.

Harvesting high-energy excited-state energy is still challenging in organic chromophores. An introduction of boron atoms along the short axis of the diazapentacene backbone induces multiple emission characteristics. Our studies reveal that the weak molecular orbital (MO) coupling of the S3-S1 transition is responsible for the slow internal conversion rates. Such MO coupling-regulated anti-Kasha emission is different from the large band gap-induced anti-Kasha emission character of classical azulene derivatives. Theoretical studies reveal that a strong MO coupling of the S3-S0 transition is responsible for the higher photoluminescence quantum yield of the anti-Kasha emission in a more polar solution (tetrahydrofuran: 11%; cyclohexane: 0%). Such an MO coupling factor is generally overlooked in anti-Kasha emitters reported previously. Furthermore, the multiple emission can be regulated by solvent polarity, solvent temperature, and fluoride anion binding. As a proof of concept of harvesting high-energy emission, the multiple emission character has allowed us to design single-molecule white-light-emitting materials.

Electrochromic Polycationic Organoboronium Macrocycles with Multiple Redox States.

Polycationic macrocycles are attractive as they display unique molecular switching capabilities arising from their redox properties. Although diverse polycationic macrocycles have been developed, those based on cationic boron systems remain very limited. We present herein the development of novel polycationic macrocycles by introducing organoboronium moieties into a conjugated organoboron macrocyclic framework. These macrocycles consist of four bipyridylboronium units that are connected by fluorene and either electron-deficient arylborane or electron-rich arylamine moieties. Electrochemical studies reveal that the macrocycles undergo reversible multi-step redox processes with transfer of up to 10 electrons. Switchable electrochromic behavior is demonstrated via spectroelectrochemical studies and the observed color changes are rationalized by correlation with computed electronic transitions using DFT methods.

Palladium(0) complexes of diferrocenylmercury diphosphines: synthesis, X-ray structure analyses, catalytic isomerization, and C-Cl bond activation.

Palladium(0) phosphine complexes are of great importance as catalysts in numerous bond formation reactions that involve oxidative addition of substrates. Highly active catalysts with labile ligands are of particular interest but can be challenging to isolate and structurally characterize. We investigate here the synthesis and chemical reactivity of Pd0 complexes that contain geometrically adaptable diferrocenylmercury-bridged diphosphine chelate ligands (L) in combination with a labile dibenzylideneacetone (dba) ligand. The diastereomeric diphosphines 1a (pSpR, meso-isomer) and 1b (pSpS-isomer) differ in the orientation of the ferrocene moieties relative to the central Ph2PC5H3-Hg-C5H3PPh2 bridging entity. The structurally distinct trigonal LPd0(dba) complexes 2a (meso) and 2b (pSpS) are obtained upon treatment with Pd(dba)2. A competition reaction reveals that 1b reacts faster than 1a with Pd(dba)2. Unexpectedly, catalytic interconversion of 1a (meso) into 1b (rac) is observed at room temperature in the presence of only catalytic amounts of Pd(dba)2. Both Pd0 complexes, 2a and 2b, readily undergo oxidative addition into the C-Cl bond of CH2Cl2 at moderate temperatures with formation of the square-planar trans-chelate complexes LPdIICl(CH2Cl) (3a, 3b). Kinetic studies reveal a significantly higher reaction rate for the meso-isomer 2a in comparison to (pSpS)-2b.

Optical Characteristics of Hybrid Macrocycles with Dithienogermole and Tricoordinate Boron Units.

The introduction of unconventional elements into π-conjugated systems has been studied to manipulate the electronic states and properties of compounds. Herein, boron- and germanium-containing hybrid macrocycles, as a new class of element-hybrid conjugated systems, have been synthesized. The palladium-catalyzed Stille cross coupling of bis(bromothienyl)borane and bis(trimethylstannylthienyl)- or bis(trimethylstannylphenyl)-substituted dithienogermoles as the boron- and germanium-containing building blocks, respectively, produced a mixture of several macrocyclic compounds. Single-crystal X-ray analysis of the 2:2 coupling product revealed a planar structure with a cavity inside the macrocycle. The optical properties of the macrocyclic products indicated rather small electronic interactions between the building units. However, intramolecular photoenergy transfer from the dithienogermole unit to the boron unit was clearly observed with respect to the fluorescence spectra.

Electron-Deficient Conjugated Materials via p-π* Conjugation with Boron: Extending Monomers to Oligomers, Macrocycles, and Polymers.

The extension of conjugated organoboranes from monomeric species to oligomers, macrocycles, and polymers offers access to a plethora of fascinating new materials. The p-π* conjugation between empty orbitals on boron and the conjugated linkers not only affects the electronic structure and optical properties, but also enables mutual interactions between electron-deficient boron centers. The unique properties of these electron-deficient π-conjugated systems are exploited in highly luminescent materials, organic optoelectronic devices, and sensing applications.

ROMP-Boranes as Moisture-Tolerant and Recyclable Lewis Acid Organocatalysts.

Although widely used in catalysis, the multistep syntheses and high loadings typically employed are limiting broader implementation of highly active tailor-made arylborane Lewis acids and Lewis pairs. Attempts at developing recyclable systems have thus far met with limited success, as general and versatile platforms are yet to be developed. We demonstrate a novel approach that is based on the excellent control and functional group tolerance of ring-opening metathesis polymerization (ROMP). The ROMP of highly Lewis acidic borane-functionalized phenylnorbornenes afforded both a soluble linear copolymer and a cross-linked organogel. The polymers proved highly efficient as recyclable catalysts in the reductive N-alkylation of arylamines under mild conditions and at exceptionally low catalyst loadings. The modular design presented herein can be readily adapted to other finely tuned triarylboranes, enabling wide applications of ROMP-borane polymers as well-defined supported organocatalysts.

Extended conjugated borenium dimers via late stage functionalization of air-stable borepinium ions.

Applications of highly electron-deficient organoborenium ions in conjugated materials remain scarce due to their low stability toward air and moisture. We report here the preparation of benzo[d]dithieno[b,f]borepinium ions as air-stable π-conjugated heterocycles and their conversion into the first dimeric borenium cations, which exhibit very low lying LUMOs and enhanced fluorescence as a result of extended conjugation.

Enhancing the Acceptor Character of Conjugated Organoborane Macrocycles: A Highly Electron-Deficient Hexaboracyclophane.

We introduce a new boron-doped cyclophane, the hexabora[16 ]cyclophane B6-F Mes, in which six tricoordinate borane moieties alternate with short conjugated p-phenylene linkers. Exocyclic 2,4,6-tris(trifluoromethyl)phenyl (F Mes) groups serve not only to further withdraw electron density but at the same time sterically shield the boron atoms, resulting in a macrocycle that is both highly electron-deficient and stable. The optical and electronic properties are compared with those of related linear oligomers and the electronic structure is further evaluated by computational methods. The studies uncover unique properties of B6-F Mes, including a low-lying and extensively delocalized LUMO and a wide HOMO-LUMO gap, which arise from the combination of a cyclic π-system, strong electronic communication between the closely spaced borons, and the attachment of electron-deficient pendent groups. The binding of small anions to the electron-deficient macrocycle and molecular model compounds is investigated and emissive exciplexes are detected in aromatic solvents.

Molecular Acceptors Based on a Triarylborane Core Unit for Organic Solar Cells.

Triarylboranes that exhibit p-π* conjugation serve as versatile building blocks to design n-type organic/polymer semiconductors. A series of new molecular acceptors based on triarylborane is reported here. These molecules are designed with a boron atom that bears a bulky 2,4,6-tri-tert-butylphenyl (Mes*) substituent at the core and strong electron-withdrawing 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) units as the end-capping groups that are linked to the core by bithiophene bridges. Butyl or butoxy groups are introduced to the bithiophene units to tune the optoelectronic properties. These molecules show nearly planar backbones with highly localized steric hindrance at the core, low LUMO/HOMO energy levels, and broad absorption bands spanning the visible region, which are all very desirable characteristics for use as electron acceptors in organic solar cell (OSC) applications. The attachment of butyl groups to the bithiophene bridges brings about a slightly twisted backbone, which in turn promotes good solubility and homogeneous donor/acceptor blend morphology, whereas the introduction of butoxy groups leads to improved planarity, favorable stacking in the film state, and a greatly reduced band gap. OSC devices based on these molecules exhibit encouraging photovoltaic performances with power conversion efficiencies reaching up to 4.07 %. These results further substantiate the strong potential of triarylboranes as the core unit of small molecule acceptors for OSC applications.