Antiprotozoal Pt(II) Complexes as Luminophores Bearing Monodentate P/As/Sb-Based Donors: An X-ray Diffractometric, Photoluminescence, and 121Sb-Mössbauer Spectroscopic Study with TD-DFT-Guided Interpretation and Predictive Extrapolation toward Bi.

In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due to the high tridentate-ligand-centered character of the excited states, the P-related radiative rate is rather low while showing a significant boost upon replacement of the P donor by heavier As- and Sb-based units. The syntheses of the three complexes containing PPh3, AsPh3, and SbPh3 were completed by unambiguous characterization of the clean products using exact mass spectrometry, X-ray diffractometry, bidimensional NMR, and 121Sb-Mössbauer spectroscopy (for [PtL(SbPh3)]) as well as steady state and time-resolved photoluminescence spectroscopies. Hence, it was shown that the hybridization defects of the Vth main-group atoms can be overcome by complexation with the Pt center. Notably, the enhancement of the radiative rate constants mediated by heavier coligands was achieved without significantly influencing the character of the excited states. A rationalization of the results was achieved by TD-DFT. Even though the Bi-based homologue was not accessible due to phenylation side reactions, the experimental data allowed a reasonable extrapolation of the structural features whereas the hybridization defects and the excited state properties related to the Bi-species and its phosphorescence rate can be predicted by theory. The three complexes showed an interesting antiprotozoal activity, which was unexpectedly notorious for the P-containing complex. This work could pave the road toward new efficient materials for optoelectronics and novel antiparasitic drugs.

Dual Emissive Zn(II) Naphthalocyanines: Synthesis, Structural and Photophysical Characterization with Theory-Supported Insights towards Soluble Coordination Compounds with Visible and Near-Infrared Emission.

Metal phthalocyaninates and their higher homologues are recognized as deep-red luminophores emitting from their lowest excited singlet state. Herein, we report on the design, synthesis, and in-depth characterization of a new class of dual-emissive (visible and NIR) metal naphthalocyaninates. A 4-N,N-dimethylaminophen-4-yl-substituted naphthalocyaninato zinc(II) complex (Zn-NMe2Nc) and the derived water-soluble coordination compound (Zn-NMe3Nc) exhibit a near-infrared fluorescence from the lowest ligand-centered state, along with a unique push-pull-supported luminescence in the visible region of the electromagnetic spectrum. An unprecedentedly broad structural (2D-NMR spectroscopy and mass spectrometry) as well as photophysical characterization (steady-state state and time-resolved photoluminescence spectroscopy) is presented. The unique dual emission was assigned to two independent sets of singlet states related to the intrinsic Q-band of the macrocycle and to the push-pull substituents in the molecular periphery, respectively, as predicted by TD-DFT calculations. In general, the elusive chemical aspects of these macrocyclic compounds are addressed, involving both reaction conditions, thorough purification, and in-depth characterization. Besides the fundamental aspects that are investigated herein, the photoacoustic properties were exemplarily examined using phantom gels to assess their tomographic imaging capabilities. Finally, the robust luminescence in the visible range arising from the push-pull character of the peripheral moieties demonstrated a notable independence from aggregation and was exemplarily implemented for optical imaging (FLIM) through time-resolved multiphoton micro(spectro)scopy.

Room-Temperature Phosphorescence from Pd(II) and Pt(II) Complexes as Supramolecular Luminophores: The Role of Self-Assembly, Metal-Metal Interactions, Spin-Orbit Coupling, and Ligand-Field Splitting.

The synthesis as well as the structural and photophysical characterization of two isoleptic bis-cyclometalated Pt(II) and Pd(II) complexes, namely [PtL] and [PdL], bearing a tailored dianionic tetradentate ligand (L2-) are reported. The isostructural character and intermolecular interactions of [PtL] and [PdL] were assessed by NMR spectroscopy and X-ray diffraction analysis. Both complexes show fully ligand-controlled aggregation, demonstrating that a judicious molecular design can tune the photophysical properties. In fact, by introduction of fluorine atoms on defined positions and methoxy groups on complementary sites, metal-metal interactions can be forced by a head-to-tail stacking. Hence, [PtL] shows luminescence from metal-perturbed ligand-centered or from metal-metal-to-ligand charge-transfer triplet states in diluted solutions, in frozen glasses and in crystals, with high photoluminescence quantum yields and long lifetimes in the microsecond range. At room temperature (RT) in concentrated fluid solutions, the palladium analogue [PdL] surprisingly emits luminescence from aggregated species involving supramolecular interactions. Time-resolved photoluminescence and transient absorption spectroscopies demonstrated that ultrafast intersystem crossing occurs for both metals, which outruns any competitive relaxation pathway from the photoexcited singlet state. Furthermore, we demonstrate that the radiationless deactivation can be suppressed in frozen glassy matrices at 77 K and by intermolecular interactions in fluid solutions at RT. In both cases and as indicated by density functional theory calculations, the lowest emissive state acts as an energy trap from which the thermal population of dissociative states with formal occupation of an antibonding Pd-centered 4dx2-y2 orbital is suppressed. This occurs as the energy gap between the emissive and the dark states surpasses kT.

Triplet Emitting C

In a series of Pt(II) complexes [Pt(dba)(L)] containing the very rigid, dianionic, bis-cyclometalating, tridentate C^N^C2− heterocyclic ligand dba2− (H2dba = dibenzo[c,h]acridine), the coligand (ancillary ligand) L = dmso, PPh3, CNtBu and Me2Imd (N,N'-dimethylimidazolydene) was varied in order to improve its luminescence properties. Beginning with the previously reported dmso complex, we synthesized the PPh3, CNtBu and Me2Imd derivatives and characterized them by elemental analysis, 1H (and 31P) NMR spectroscopy and MS. Cyclic voltammetry showed partially reversible reduction waves ranging between −1.89 and −2.10 V and increasing along the series Me2Imd < dmso ≈ PPh3 < CNtBu. With irreversible oxidation waves ranging between 0.55 (L = Me2Imd) and 1.00 V (dmso), the electrochemical gaps range between 2.65 and 2.91 eV while increasing along the series Me2Imd < CNtBu < PPh3 < dmso. All four complexes show in part vibrationally structured long-wavelength absorption bands peaking at around 530 nm. TD-DFT calculated spectra agree quite well with the experimental spectra, with only a slight redshift. The photoluminescence spectra of all four compounds are very similar. In fluid solution at 298 K, they show broad, only partially structured bands, with maxima at around 590 nm, while in frozen glassy matrices at 77 K, slightly blue-shifted (~580 nm) bands with clear vibronic progressions were found. The photoluminescence quantum yields ΦL ranged between 0.04 and 0.24, at 298 K, and between 0.80 and 0.90 at 77 K. The lifetimes τ at 298 K ranged between 60 and 14040 ns in Ar-purged solutions and increased from 17 to 43 µs at 77 K. The TD-DFT calculated emission spectra are in excellent agreement with the experimental findings. In terms of high ΦL and long τ, the dmso and PPh3 complexes outperform the CNtBu and Me2Imd derivatives. This is remarkable in view of the higher ligand strength of Me2Imd, compared with all other coligands, as concluded from the electrochemical data.

Isoelectronic Pt(II) complexes of cyclometalating C

A series of cyclometalated Pt(II) complexes [Pt(C^N^N)X] (X = Cl, CCPh, CCC6F5) was synthesised from the protoligands HC^N^N containing either phenyl (ph), naphthyl (na) or (benzo)thiophenyl (b(th)) C aryl functions and either pyridyl (py) or (benzo)thiazolyl ((b)tz) peripheral N units, alongside the central 4-phenyl-pyridyl (ppy) or tBu2-phenyl-pyridyl (tbppy) N group. Depending on the combination of the peripheral N or C aryl building blocks, these square planar complexes reveal very different electrochemical, UV-vis absorption and emission behaviour. The reversible reductions shift anodically along the series th/py < ph/tz ≈ th/tz < ph/btz while the irreversible oxidations shift cathodically along the series Cl ≈ CCC6F5 < CCPh. Similar trends were observed for the long-wavelength UV-vis absorption and photoluminescence properties. The emission maxima range from 605 to 675 nm at 298 K in CH2Cl2 solution and from 555 to 655 nm at 77 K in glassy frozen CH2Cl2/MeOH matrices. Large differences in amplitude-weighted average lifetimes τav (up to 0.9 µs at 298 K, up to 12 µs at 77 K) and photoluminescence quantum yields ΦL (up to 0.15 at 298 K and up to 0.82 at 77 K) were found. TD-DFT calculations showed that the decomposition of the triplet excited states into LC (π-π*, centred in the individual parts of the C^N^N ligand) and LLCT (π-π*, between the individual parts of the C^N^N ligand + X-π* from coligand to C^N^N) contributions for the ligand-centred states as well as MLCT (dPt-to-π*C^N^N) and LMCT (pCl or πCCR-to-dPt) character for the charge-transfer states involving the metal is beneficial to assess the participation of the individual heteroaryl groups of the C^N^N ligands. In view of the modular synthesis of these ligands, this will allow the realisation of tailor-made Pt(II) triplet emitters in future work.

Ligand-controlled and nanoconfinement-boosted luminescence employing Pt(ii) and Pd(ii) complexes: from color-tunable aggregation-enhanced dual emitters towards self-referenced oxygen reporters.

In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(ii) and Pt(ii) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields (Φ L) and long excited state lifetimes (τ) at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal-metal-to-ligand charge-transfer (3MMLCT) excimers acting as red-shifted energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(ii) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting. Encapsulation of these complexes in 100 nm-sized aminated polystyrene nanoparticles enables concentration-controlled aggregation-enhanced dual emission. This phenomenon facilitates the tunability of the absorption and emission colors while providing a rigidified environment supporting an enhanced Φ L up to about 80% and extended τ exceeding 100 µs. Additionally, these nanoarrays constitute rare examples for self-referenced oxygen reporters, since the phosphorescence of the aggregates is insensitive to external influences, whereas the monomeric species drop in luminescence lifetime and intensity with increasing triplet molecular dioxygen concentrations (diffusion-controlled quenching).

On-Surface Reactive Planarization of Pt(II) Complexes.

A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces with the aim to produce highly planar self-assembled monolayers. Low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. A subsequent metal-catalyzed separation of the nonplanar moiety at the bridging unit via the scission of a C-N bond is observed, leaving behind a largely planar core complex. The activation barrier of this bond scission process is found to depend strongly on the chemical nature of both bridging group and coordination plane, and to increase from Cu(111) through Ag(111) to Au(111).