Π-extended Ligand Research Articles

π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes.

Cyclometalated platinum complexes play a crucial role in catalysis, bioimaging, and optoelectronics. Phenylpyridines are widespread cyclometalating ligands that generate stable and highly emissive Pt complexes. While it is common practice to modify these ligands to fine-tune their photophysical properties, the incorporation of polycyclic aromatic hydrocarbons into the ligand's structure has been largely overlooked. This report describes the cyclometalation of naphthalenyl- and anthracenylpyridine ligands, which has resulted in ten new luminescent PtII and PtIV complexes. These species are enabled by a dual-binding behavior discovered in our polyaromatic-containing ligands. The introduction of naphthalenyl and anthracenyl groups unlocks dual binding modes, with the Pt center bonding to either of two distant carbon atoms within the ligand. These complexes exhibit both symmetric structures with two 5-membered metallacycles and asymmetric structures with 5- and 6-membered metallacycles. This work presents a strategy for the regioselective synthesis of Pt complexes with bespoke structures and photophysical properties. Our findings offer new opportunities in platinum chemistry and beyond, with potential implications for materials and technologies.

Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D2h -symmetric π-extended ligand (OHPTP), and synthesize the first rhombic 2D c-MOF single crystals (Cu2 (OHPTP)). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu2 (OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm-1 and high charge carrier mobility of ≈10.0 cm2 V-1 s-1 . Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.

Eine halbleitende 2D metallorganische Gerüstverbindung mit einer Bandlücke im nahen IR, rhombischem Gitter und hoher Ladungsträgermobilität

AbstractZweidimensionale konjugierte metallorganische Gerüstverbindungen (2D c‐MOFs) gehören zu einer einzigartigen Gruppe elektronischer Materialien. 2D c‐MOFs mit Bandlücken im sichtbaren oder nahen IR‐Bereich und hohen Ladungsträger‐mobilitäten sind jedoch rar. Die meisten literaturbekannten halbleitenden 2D c‐MOFs sind metallisch, was ihre Verwendung in logischen Bauelementen stark einschränkt. Im Folgenden konzipieren wir einen Phenanthrotriphenylen basierten, D2h‐symmetrischen, π‐konjugierten Liganden (OHPTP) und synthetisieren die ersten rhombischen 2D c‐MOF Einkristalle (Cu2(OHPTP)). Kontinuierliche Rotations‐Elektronendiffraktometrie (cRED) belegt die orthorhombische Kristallstruktur mit versschobene AA‐Schichtung auf atomarer Ebene. Cu2(OHPTP) ist ein p‐Typ Halbleiter mit einer indirekten Bandlücke von ≈0.50 eV, einer hohen elektrischen Leitfähigkeit von 0.10 S cm−1 und einer hohen Ladungsträgermobilität von ≈10.0 cm2 V−1 s−1. Theoretische Berechnungen unterstreichen die dominierende Rolle des Ladungstransports zwischen den Schichten in diesem Semichinon verknüpften 2D c‐MOF.

Tetraquinoxalinoporphyrazine – π-extended NIR-absorbing photosensitizer with improved photostability

A novel ionogenic water-soluble zinc complex with π-extended ligand – tetraquinoxalinoporphyrazine bearing eight benzoate groups – ZnQPz(COONa)8 was synthesized by template condensation of a new building block, dipentyl 4,4'-(6,7-dicyanoquinoxalin-2,3-diyl)dibenzoate followed by alkaline hydrolysis of ester groups. The photophysical properties of the complex were studied and a significant bathochromic shift of the Q-band by 100 nm was observed as compared to conventional phthalocyanine complexes. However, in contrast to other NIR-absorbing π-extended derivatives with similar optical properties, ZnQPz(COONa)8 showed a high degree of photostability – its photobleaching rate in DMSO was about 3 times lower than that of the zinc tetra-15-crown-5-naphthalocyanate Zn[(15C5)4Nc]. The improved photostability together with the ability to generate singlet oxygen (ФΔ = 0.65 in aqueous DMSO) and absorb light in the near infrared region makes quinoxaline-porphyrazine a good candidate for use in photodynamic therapy.

Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers.

One- and two-photon characterizations of a series of hetero- and homoleptic [RuL3-n(bpy)n]2+ (n = 0, 1, 2) complexes carrying bipyridine π-extended ligands (L), have been carried out. These π-extended D−π−A−A−π−D-type ligands (L), where the electron donor units (D) are based on diphenylamine, carbazolyl, or fluorenyl units, have been designed to modulate the conjugation extension and the donating effect. Density functional theory calculations were performed in order to rationalize the observed spectra. Calculations show that the electronic structure of the π-extended ligands has a pronounced effect on the composition of HOMO and LUMO and on the metallic contribution to frontier MOs, resulting in strikingly different nonlinear properties. This work demonstrates that ILCT transitions are the keystone of one- and two-photon absorption bands in the studied systems and reveals how much MLCT and LLCT charge transfers play a decisive role on the two-photon properties of both hetero- and homoleptic ruthenium complexes through cooperative or suppressive effects.

Near-Infrared Emitting Ir(III) Complexes Bearing a Dipyrromethene Ligand for Oxygen Imaging of Deeper Tissues In Vivo.

Phosphorescence lifetime imaging microscopy (PLIM) using a phosphorescent oxygen probe is an innovative technique for elucidating the behavior of oxygen in living tissues. In this study, we designed and synthesized an Ir(III) complex, PPYDM-BBMD, that exhibits long-lived phosphorescence in the near-infrared region and enables in vivo oxygen imaging in deeper tissues. PPYDM-BBMD has a π-extended ligand based on a meso-mesityl dipyrromethene structure and phenylpyridine ligands with cationic dimethylamino groups to promote intracellular uptake. This complex gave a phosphorescence spectrum with a maximum at 773 nm in the wavelength range of the so-called biological window and exhibited an exceptionally long lifetime (18.5 μs in degassed acetonitrile), allowing for excellent oxygen sensitivity even in the near-infrared window. PPYDM-BBMD showed a high intracellular uptake in cultured cells and mainly accumulated in the endoplasmic reticulum. We evaluated the oxygen sensitivity of PPYDM-BBMD phosphorescence in alpha mouse liver 12 (AML12) cells based on the Stern-Volmer analysis, which gave an O2-induced quenching rate constant of 1.42 × 103 mmHg-1 s-1. PPYDM-BBMD was administered in the tail veins of anesthetized mice, and confocal one-photon PLIM images of hepatic tissues were measured at different depths from the liver surfaces. The PLIM images visualized the oxygen gradients in hepatic lobules up to a depth of about 100 μm from the liver surfaces with a cellular-level resolution, allowing for the quantification of oxygen partial pressure based on calibration results using AML12 cells.

Chemiluminescent 1,2-Dioxetane Iridium Complexes for Near-Infrared Oxygen Sensing.

Chemiluminescent iridium-based sensors which demonstrate oxygen dependent responses have been developed. The molecular probes, named IrCL-1, IrCL-2 and IrCL-3 consist of oxygen-sensitive iridium complexes attached to a spiroadamantane 1,2 dioxetane and operate via energy transfer from the chemiexcited benzoate to the corresponding iridium(III) complex. Complexing the iridium(III) center with π-extended ligands results in emission in the biologically relevant, near-infrared (NIR) region. All probes demonstrate varying oxygen tolerance, with IrCL-1 being the most oxygen sensitive. These probes have been further utilized for in vitro ratiometric imaging of oxygen, as well as for intraperitoneal, intramuscular and intratumoral imaging in live mice. To our knowledge, these are the first iridium-based chemiluminescent probes that have been employed for in vitro ratiometric oxygen sensing, and for in vivo tumor imaging.

Rigid π-Extended Boron Difluoride Complex with Mega-Stokes Shift for Bioimaging.

The rational design of a rigid π-extended ligand, suitable for the formation of four-coordinate boron complexes, has led to the synthesis of the fused hexacyclic structure of carbazolo[2,1-c]phenanthridine. The photophysical characterization of the novel fluorophore revealed a significant Stokes shift whose intramolecular charge transfer origin has been corroborated by computational calculations. The usefulness of the reported N,N-difluoroboryl complex as fluorescent probe with large Stokes shift has been demonstrated for cancer cells imaging.

Predictive Strength of Photophysical Measurements for in Vitro Photobiological Activity in a Series of Ru(II) Polypyridyl Complexes Derived from π-Extended Ligands.

This study investigates the correlation between photocytotoxicity and the prolonged excited-state lifetimes exhibited by certain Ru(II) polypyridyl photosensitizers comprised of π-expansive ligands. The eight metal complexes selected for this study differ markedly in their triplet state configurations and lifetimes. Human melanoma SKMEL28 and human leukemia HL60 cells were used as in vitro models to test photocytotoxicity induced by the compounds when activated by either broadband visible or monochromatic red light. The photocytotoxicities of the metal complexes investigated varied over 2 orders of magnitude and were positively correlated with their excited-state lifetimes. The complexes with the longest excited-state lifetimes, contributed by low-lying 3IL states, were the most phototoxic toward cancer cells under all conditions.

Photophysics of a Ruthenium Complex with a π-Extended Dipyridophenazine Ligand for DNA Quadruplex Labeling.

The light-switch mechanism of the complex [Ru(bpy)2(Br-dpqp)](PF6)2 (1, bpy = 2,2'-bipyridine, Br-dpqp = 12-bromo-14-ethoxydipyrido[3,2- a:2',3'- c]quinolino[3,2- h]phenazine), i.e., a light-up probe for the selective labeling of G-quadruplexes, is investigated by time-resolved transient absorption and emission spectroscopy. We show that, in contrast to the prototypical light-switch complex [Ru(bpy)2(dppz)](PF6)2 (2, dppz = dipyrido[3,2- a:2',3'- c]phenazine), a 3ππ* state localized on the π-extended ligand is the state determining the excited-state properties in both protic and aprotic environments. In aprotic environments, emission originates from a bright 3MLCTphen state, which is thermally accessible from the 3ππ* state at ambient temperature. In the presence of water, i.e., in environments resembling in cellulo situations, the thermally accessible 3MLCT state is altered and becomes close in energy to the 3ππ* state, which induces a rapid excited-state deactivation of the 3ππ* state and a comparably weak emission.

Crystal structure of 2,3-bis-(4-methyl-phen-yl)benzo[g]quinoxaline.

The title compound, C26H20N2, was obtained during a search for new π-extended ligands with the potential to generate efficient phosphors with iridium(III) for organic light-emitting devices (OLEDs). The benzoquinoxaline ring system is almost planar (r.m.s. deviation = 0.076 Å). A pseudo-twofold rotation axis runs through the midpoints of the C2-C3 and C9-C10 bonds. The two phenyl rings are twisted relative to the benzoquinoxaline ring system, making dihedral angles of 53.91 (4) and 36.86 (6)°. In the crystal, C-H⋯π (arene) inter-actions link the mol-ecules, but no π-π inter-actions between aromatic rings are observed.

An artificial photosynthetic system for photoaccumulation of two electrons on a fused dipyridophenazine (dppz)-pyridoquinolinone ligand.

Increasing the efficiency of molecular artificial photosynthetic systems is mandatory for the construction of functional devices for solar fuel production. Decoupling the light-induced charge separation steps from the catalytic process is a promising strategy, which can be achieved thanks to the introduction of suitable electron relay units performing charge accumulation. We report here on a novel ruthenium tris-diimine complex able to temporarily store two electrons on a fused dipyridophenazine-pyridoquinolinone π-extended ligand upon visible-light irradiation in the presence of a sacrificial electron donor. Full characterization of this compound and of its singly and doubly reduced derivatives thanks to resonance Raman, EPR and (TD)DFT studies allowed us to localize the two electron-storage sites and to relate charge photoaccumulation with proton-coupled electron transfer processes.

Low-voltage, high-brightness and deep-red light-emitting electrochemical cells (LECs) based on new ruthenium(ii) phenanthroimidazole complexes.

Light-Emitting Electrochemical Cells (LECs) with a simple device structure ITO/Ru complex/Ga:In were prepared by using heteroleptic ruthenium(ii) complexes containing 2-(2-hydroxyphenyl)-1-(4-bromophenyl)-1h-imidazo[4,5-f][1,10]phenanthroline (hpbpip) as the π-extended ligand. After ancillary ligand modification, the [Ru(hpbpip)(dmbpy)2](ClO4)2 complex shows a deep red electroluminescence emission (2250 cd m(-2) at 6 V) centered at 685 nm, 65 nm red-shifted compared to the [Ru(bpy)3](ClO4)2 benchmark red-emitter at a very low turn voltage (2.6 V), demonstrating its potential for low-cost deep-red light sources. Moreover, the PL quantum yield of the [Ru(hpbpip)(bpy)2](ClO4)2 complex was revealed to be higher (0.121) than the benchmark standard [Ru(bpy)3](2+) (0.095).

Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient "chemistry on the complex" approach.

The preparation and characterization of three series of novel ruthenium(ii) complexes are reported, each series differing by the nature of the ancillary ligands (2,2'-bipyridine - bpy, 1,10-phenanthroline - phen or 1,4,5,8-tetraazaphenanthrene - TAP). The third ligand was either the heptacyclic heterocycle dipyrido[3,2-a:2',3'-c]quinolino[3,2-h]phenazine (dpqp) substituted at position 12 by an hydroxyl (oxo), 2,2-dimethoxyethylamine (DMEA) or halogeno (Cl or Br) substituent, or the octacyclic dipyrido[3,2-a:2',3'-c]pyrido[2,3,4-de]quinolino[3,2-h]phenazine (dppqp), prepared by a multi-step "chemistry on the complex" strategy from [RuL2(oxo-dpqp)](PF6)2. The three steps, halogenation, substitution by a dimethoxyethylamino group and cyclization in trifluoroacetic acid, were performed in reasonable to high yields depending on the nature of the ancillary ligands. Isolation and purification processes were facilitated by the ability to switch the solubility of the complex from aqueous to organic solvents, depending on the counter-ion. All new complexes were fully characterized; in particular their absorption properties were compared by UV-vis spectroscopy. Finally, π-stacking properties induced by these extended ligands were studied by 1H NMR studies and quantum chemical calculations.

A new class of color-tunable electroluminescent ruthenium(ii) phenanthroline emitters

A novel class of electroluminescent Ru Π-extended phenanthroline complexes has been demonstrated to possess EL properties. Tunable electroluminescences from 508 to 565 nm have been achieved by adjusting the Π-extended ligand substitution of ruthenium complexes.

Photo- and electroluminescence from deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended ligands

Deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended cyclometalated (C^N) ligands were newly synthesized, and their photo- and electroluminescence properties were investigated. When 2-(benzo[b]furan-2-yl)quinoline and 2-(benzo[b]thiophen-2-yl)quinoline were employed as C^N ligands, deep-red photoluminescence was obtained (Ir-1a and Ir-1b; λPL in CH2Cl2, 647 and 652nm, respectively). In the case of the isoquinoline analogues of Ir-1a and Ir-1b, emission maxima were further red-shifted, ranging from deep-red to near-infrared regions (Ir-2a and Ir-2b; λPL in CH2Cl2, 696 and 690nm, respectively). Especially, Ir-2b showed an excellent photoluminescence quantum yield (ΦPL=0.15), and a polymer light-emitting diode doped with Ir-2b exhibited deep-red–near-infrared electroluminescence with a high external quantum efficiency (λEL=694nm, ηext max=1.41%).

Aryl 5-substitution of a phenyl-pyridine based ligand as a viable way to influence the opto-electronic properties of bis-cyclometalated Ir(iii) heteroleptic complexes

This manuscript reports on the synthesis, the photophysical study and the electroluminescent properties of a series of heteroleptic cyclometalated iridium(III) complexes based on 2,5-diaryl-pyridines as C^N cyclometalating ligands and acetylacetonate as ancillary ligand. The complexes were characterised by elemental analysis, ESI-MS, multinuclear NMR, TGA and electrochemistry. Their optical properties were investigated by UV-Vis and photoluminescence. DFT and TD-DFT calculations provided further insights into the effects of the 5-aryl substitution on the electronic and photophysical properties of the new complexes. The presence of suitable π-extended ligands exerts a beneficial effect on the performances of the corresponding solution-processed light-emitting diodes, leading to a maximum brightness of 10,620 cd m(-2) at a current efficiency of 10.0 cd A(-1).

Photophysical properties of ruthenium(II) polyazaaromatic compounds: a theoretical insight.

Quantum-chemical methods are applied to study the nature of the excited states relevant in the photophysical processes (absorption and emission) of a series of polyazaaromatic-ligand-based ruthenium(II) complexes. The electronic and optical properties of the free polyazaaromatic ligands and their corresponding ruthenium(II) complexes are determined on the basis of correlated Hartree-Fock semiempirical approaches. While the emission of complexes containing small-size ligands, such as 1,10-phenanthroline or 2,2'-bipyridine, arises from a manifold of metal-to-ligand charge-transfer triplet states ((3)MLCTs), an additional ligand-centered triplet state ((3)L) is identified in the triplet manifold of complexes containing a pi-extended ligand such as dipyrido[3,2-a:2',3'-c]phenazine, tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine, and 1,10-phenanthrolino[5,6-b]-1,4,5,8,9,12-hexaazatriphenylene. Recent experimental data are interpreted in light of these theoretical results; namely, the origin for the abnormal solvent- and temperature-dependent emission measured in pi-extended Ru complexes is revisited.

Porphyrinogen tetraanion functioning as a polymetallic assembler: nickel-meso-octaethylporphyrinogen binding four transition metal ions at the periphery

Nickel(II)-meso-octaethylporphyrinogen dianion behaves as a π-extended ligand binding four M(CO)3 [M = Cr, Mo] fragments at the periphery, so that the porphyrinogen can assemble five metal centers around itself.