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The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy) 2 (azab-py)] + , where dtbbpy = 4,4'-di- tert -butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy) 3 ] 2+ (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy) 2 (ppy)] + , where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy) 2 (naft-py)] + (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.51 V decrease in the redox gap of complex A, compared to that of B, leading to electrochemical and photophysical properties that resemble those of C and D. Accordingly, the azaborine complex displays an emission band extending up to the near infrared region of the spectrum (with the maximum at 765 nm in room-temperature acetonitrile solution), arising from a triplet metal-to-ligand charge-transfer ( 3 MLCT) state. As in the case of other mono-cationic cyclometalated ruthenium(II) complexes, A shows modest photoluminescence quantum yields (PLQYs), but higher PLQYs when compared to those of its direct CC analogue D ( e.g. , PLQY = 0.6 vs. 0.1% in a PMMA matrix at 298 K). Density functional theory (DFT) calculations were used to provide complete rationalization of the electronic properties of all the complexes and to identify lower-lying metal-centred triplets ( 3 MC), responsible for the low PLQYs of such an azaborine-based ruthenium(II) complex.

Slightly different reaction conditions afforded two distinct cavity-shaped cis-chelating diphosphanes from the same starting materials, namely diphenyl(2-phosphanylphenyl)phosphane and an α-cyclodextrin-derived dimesylate. Thanks to their metal-confining properties, the two diphosphanes form only mononuclear [CuX(PP)] complexes (X=Cl, Br, or I) with the tricoordinated metal ion located just above the center of the cavity. The two series of Cu I complexes display markedly different luminescence properties that are both influenced by the electronic properties of the ligand and the unique steric environment provided by the cyclodextrin (CD) cavity. The excited state lifetimes of all complexes are significantly longer than those of the cavity-free analogues suggesting peculiar electronic effects that affect radiative deactivation constants. The overall picture stemming from absorption and emission data suggests close-lying charge-transfer (MLCT, XLCT) and triplet ligand-centered (LC) excited states., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The tetrahedral shape-persistent molecule 1 4+ , containing four identical pyridyl pyridinium units connected via a sp 3 hybridized carbon atom, has been investigated in detail by means of steady-state and time resolved spectroscopy. Remarkable photophysical properties are observed, particularly in comparison with protonated and methylated analogues (1H 4 8+ , 1Me 4 8+ ), which exhibit substantially shorter excited state lifetimes and lower emission quantum yields. Theoretical studies have rationalized the behavior of the tetrameric molecules relative to the monomers, with DFT and TD-DFT calculations corroborating steady-state (absorption and emission) and transient absorption spectra. The behavior of the monomeric compounds (each consisting in one of the four identical subunits of the tetramers, i. e., 2 + , 2H 2+ and 2Me 2+ ) considerably differs from that of the tetramers, indicating a strong electronic interaction between the subunits in the tetrameric species, likely promoted by the homoconjugation through the connecting sp 3  C atom. 2 + is characterized by a peculiar S 1 -S 2 excited state inversion, whereas the short-lived emitting S 1 state of 2H 2+ and 2Me 2+ exhibits a partial charge-transfer character, as substantiated by spectro-electrochemical studies. Among the six investigated systems, only 1 4+ is a sizeable luminophore (Φ em =0.15), which is related to the peculiar features of its singlet state., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A new synthetic method has been developed for the preparation of unexpected emissive iridium(III) complexes (A and B), directly obtained from the established [Ir(ppy) 2 (μ-Cl)] 2 dimer, under reaction conditions in which such compounds are usually considered stable. Complex A ([Ir(ppy) 2 (Oppy)], where Hppy = 2-phenylpyridine and HOppy = 2-( o -hydroxyphenyl)pyridine) was obtained from the dimer without the addition of further ancillary ligands in the reaction environment, but in the presence of a basic water environment in 2-ethoxyethanol as solvent at 165 °C. The complex evidences the unexpected insertion of an oxygen atom between the iridium(III) center and the carbon atom of one ppy moiety. Under specific reaction conditions, the mer -[Ir(ppy) 3 ] complex (B) was obtained. The presence of the right amount of water is important to maximize the formation of A relative to B. Both compounds were fully characterized by NMR spectroscopy and mass spectrometry (MS), and the X-ray structure of A was also determined. DFT calculations were used to shed light on the reaction mechanism leading to the unexpected formation of A, suggesting that the Oppy ligand is generated intramolecularly once the [Ir(ppy) 2 (μ-OH)] 2 dimer is formed. The process is probably assisted by a redox reaction involving the second iridium(III) center in the dimer. The electrochemical and photophysical properties of complexes A and B were investigated in comparison with the well-known fac -[Ir(ppy) 3 ] analogue (C). Complex A displays a green emission ( λ max = 605 nm) with a PLQY below 10%. These findings may pave the way for the direct synthesis of neutral luminescent complexes with the general formula [Ir(C^N) λ (OC^N)], even using dimers with non-commercial or highly substituted C^N ligands, without the need for synthesizing the corresponding hydroxyl-substituted ancillary ligand, which may be hardly obtainable.max = 605 nm) with a PLQY below 10%. These findings may pave the way for the direct synthesis of neutral luminescent complexes with the general formula [Ir(C^N) 2 (OC^N)], even using dimers with non-commercial or highly substituted C^N ligands, without the need for synthesizing the corresponding hydroxyl-substituted ancillary ligand, which may be hardly obtainable.

A multi-responsive receptor consisting of two (acridinium-Zn(II) porphyrin) conjugates has been designed. The binding constant between this receptor and a ditopic guest has been modulated (i) upon addition of nucleophiles converting acridinium moieties into the non-aromatic acridane derivatives and (ii) upon oxidation of the porphyrin units. A total of eight states has been probed for this receptor resulting from the cascade of the recognition and responsive events. Moreover, the acridinium/acridane conversion leads to a significant change of the photophysical properties, switching from electron to energy transfer processes. Interestingly, for the bis(acridinium-Zn(II) porphyrin) receptor, charge-transfer luminescence in the near-infrared has been observed.

We report a joint experimental and theoretical work on the steady-state spectroscopy and time-resolved emission of the coumarin C153 dye in methanol. The lowest energy excited state of this molecule is characterized by an intramolecular charge transfer thus leading to remarkable shifts of the time-resolved emission spectra, dictated by the methanol reorganization dynamics. We selected this system as a prototypical test case for the first application of a novel computational protocol aimed at the prediction of transient emission spectral shapes, including both vibronic and solvent effects, without applying any phenomenological broadening. It combines a recently developed quantum-classical approach, the adiabatic molecular dynamics generalized vertical Hessian method (Ad-MD|gVH), with nonequilibrium molecular dynamics simulations. For the steady-state spectra we show that the Ad-MD|gVH approach is able to reproduce quite accurately the spectral shapes and the Stokes shift, while a ∼0.15 eV error is found on the prediction of the solvent shift going from gas phase to methanol. The spectral shape of the time-resolved emission signals is, overall, well reproduced, although the simulated spectra are slightly too broad and asymmetric at low energies with respect to experiments. As far as the spectral shift is concerned, the calculated spectra from 4 ps to 100 ps are in excellent agreement with experiments, correctly predicting the end of the solvent reorganization after about 20 ps. On the other hand, before 4 ps solvent dynamics is predicted to be too fast in the simulations and, in the sub-ps timescale, the uncertainty due to the experimental time resolution (300 fs) makes the comparison less straightforward. Finally, analysis of the reorganization of the first solvation shell surrounding the excited solute, based on atomic radial distribution functions and orientational correlations, indicates a fast solvent response (≈100 fs) characterized by the strengthening of the carbonyl-methanol hydrogen bond interactions, followed by the solvent reorientation, occurring on the ps timescale, to maximize local dipolar interactions.

A novel 1,2-azaborine ( i.e. , 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene, 1a ) has been synthesized and used for the first time as a B-N alternative to common cyclometalating ligands to obtain neutral phosphorescent iridium(III) complexes ( i.e. , 2a , 3 , and 4 ) of general formula [Ir(C ∧ N) 2 (N ∧ NB)], where C ∧ N indicates three different cyclometalating ligands (Hppy = 2-phenylpyridine; Hdfppy = 2-(2,4-difluoro-phenyl)pyridine; Hpqu = 2-methyl-3-phenylquinoxaline). Moreover, the azaborine-based complex 2a was compared to the isoelectronic C═C iridium(III) complex 2b , obtained using the corresponding 2-(naphthalen-2-yl)pyridine ligand 1b . Due to the dual cyclometalation mode of such C═C ligand, the isomeric complex 2c was also obtained. All new compounds have been fully characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and the X-ray structure of 2a was determined. The electronic properties of both ligands and complexes were investigated by electrochemical, density functional theory (DFT), and photophysical methods showing that, compared to the naphthalene analogues, the azaborine ligand induces a larger band gap in the corresponding complexes, resulting in increased redox gap (basically because of the highest occupied molecular orbital (HOMO) stabilization) and blue-shifted emission bands ( e.g. , λ max = 523 vs 577 nm for 2a vs 2b , in acetonitrile solution at 298 K). On the other hand, the 3 LC nature of the emitting state is the same in all complexes and remains centered on the pyridyl-borazaronaphthalene or its C═C pyridyl-naphthalene analogue. As a consequence, the quantum yields of such azaborine-based complexes are comparable to those of the more classical C═C counterparts ( e.g. , photoluminescence quantum yield (PLQY) = 16 vs 22% for 2a vs 2b , in acetonitrile solution at 298 K) but with enhanced excited-state energy. This proves that such type of azaborine ligands can be effectively used for the development of novel classes of photoactive transition-metal complexes for light-emitting devices or photocatalytic applications.

A β-cyclodextrin-based diphosphane with metal-confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of diphenyl-(2-phosphanylphenyl)phosphane in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)] + complexes in which a metal-bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)