Ultrafast charge transfer dynamics in supramolecular Pt(II) donor-bridge-acceptor assemblies: the effect of vibronic coupling

Thanks to major advances in laser technologies, recent investigations of the ultrafast coupling of nuclear and electronic degrees of freedom (vibronic coupling) have revealed that such coupling plays a crucial role in a wide range of photoinduced reactions in condensed phase supramolecular systems. This paper investigates several new donor–bridge–acceptor charge-transfer molecular assemblies built on a trans-Pt(II) acetylide core. We also investigate how targeted vibrational excitation with low-energy IR light post electronic excitation can perturb vibronic coupling and affect the efficiency of electron transfer (ET) in solution phase. We compare and contrast properties of a range of donor–bridge–acceptor Pt(II) trans-acetylide assemblies, where IR excitation of bridge vibrations during UV-initiated charge separation in some cases alters the yields of light-induced product states. We show that branching to multiple product states from a transition state with appropriate energetics is the most rigid condition for the type of vibronic control we demonstrate in our study

Pyridazine-bridged cationic diiridium complexes as potential dual-mode bioimaging probes

A novel diiridium complex [(N^C^N)2Ir(bis-N^C)Ir(N^C^N)2Cl]PF6 (N^C^N = 2-[3-tert-butyl-5-(pyridin-2-yl)phenyl]pyridine; bis-N^C = 3,6-bis(4-tert-butylphenyl)pyridazine) was designed, synthesised and characterised. The key feature of the complex is the bridging pyridazine ligand which brings two cyclometallated Ir(III) metal centres close together so that Cl also acts as a bridging ligand leading to a cationic complex. The ionic nature of the complex offers a possibility of improving solubility in water. The complex displays broad emission in the red region (λem = 520–720 nm, τ = 1.89 μs, Φem = 62% in degassed acetonitrile). Cellular assays by multiphoton (λex = 800 nm) and confocal (λex = 405 nm) microscopy demonstrate that the complex enters cells and localises to the mitochondria, demonstrating cell permeability. Further, an appreciable yield of singlet oxygen generation (ΦΔ = 0.45, direct method, by 1O2 NIR emission in air equilibrated acetonitrile) suggests a possible future use in photodynamic therapy. However, the complex has relatively high dark toxicity (LD50 = 4.46 μM), which will likely hinder its clinical application. Despite this toxicity, the broad emission spectrum of the complex and high emission yield observed suggest a possible future use of this class of compound in emission bioimaging. The presence of two heavy atoms also increases the scattering of electrons, supporting potential future applications as a dual fluorescence and electron microscopy probe

I=3/2 KπK \pi Scattering in the Nonrelativisitic Quark Potential Model

We study $I=3/2$ elastic $K\pi$ scattering to Born order using nonrelativistic quark wavefunctions in a constituent-exchange model. This channel is ideal for the study of nonresonant meson-meson scattering amplitudes since s-channel resonances do not contribute significantly. Standard quark model parameters yield good agreement with the measured S- and P-wave phase shifts and with PCAC calculations of the scattering length. The P-wave phase shift is especially interesting because it is nonzero solely due to $SU(3)_f$ symmetry breaking effects, and is found to be in good agreement with experiment given conventional values for the strange and nonstrange constituent quark masses.Comment: 12 pages + 2 postscript figures, Revtex, MIT-CTP-210

Transition metal complexes as photosensitisers in one- and two-photon photodynamic therapy

Photodynamic therapy (PDT) exploits light-activated compounds for therapeutic use. It relies on a photosensitiser (PS) that is inactive in the absence of light. When irradiated, the PS absorbs light and is promoted to a higher energy, “excited” state (PS ∗ ), which is either toxic to cells in itself or triggers formation of other species which are toxic to cells, and hence particular wavelengths of light can be used to induce light-dependent cell killing. In PDT occurring via the so-called type I and type II mechanisms, the PS ∗ engages in energy transfer to dioxygen present in cells and tissues. This process generates highly reactive singlet oxygen ( 1 O 2 ) and/or other reactive oxygen species (ROS), which in turn cause damage in the immediate vicinity of the irradiation and ultimately can lead to cell death. Whilst the main focus of research for the last 50 years has been on organic molecules or porphyrins as sensitisers, there is now emerging interest in extending the use to transition metal (TM) complexes, which can display intense absorptions in the visible region, and many also possess high two-photon absorption cross-sections, enabling two-photon excitation with NIR light. As with any other type of photosensitiser, the issues to consider whilst designing a TM complex as a photosensitiser include cell permeability, efficient absorption of NIR light for deeper penetration, preferential affinity to cancer cells over healthy cells, targeted intracellular localisation and lack of side effects. This review summarises recent developments involving photosensitisers containing Ru(II), Os(II), Pt, Ir(III), and Re(I) ions, and the approaches used to address the above requirements. Several remarkable recent advances made in this area, including the first clinical trial of a metal complex as a photosensitiser, indicate the bright future of this class of compounds in PDT

J/\Psi \to \phi \pi \pi (K \bar{K}) decays, chiral dynamcis and OZI violation

We have studied the invariant mass distributions of the \pi\pi and K \bar{K} systems for invariant masses up to 1.2 GeV from the J/\Psi \to \phi \pi\pi(K\bar{K}) decays. The approach exploits the connection between these processes and the \pi\pi and K\bar{K} strange and non-strange scalar form factors by considering the \phi meson as a spectator. The calculated scalar form factors are then matched with the ones from next-to-leading order chiral perturbation theory, including the calculation of the the K\bar{K} scalar form factors. Final state interactions in the J/\Psi \to \phi \pi\pi (K\bar{K}) processes are taken into account as rescattering effects in the system of the two pseudoscalar mesons. A very good agreement with the experimental data from DM2 and MARK-III is achieved. Furthermore, making use of SU(3) symmetry, the S-wave contribution to the \pi^+\pi^- event distribution in the J/\Psi \to \omega \pi^+\pi^- reaction is also given and the data up to energies of about 0.7 GeV are reproduced. These decays of the J/\Psi to a vector and a pair of pseudoscalars turn out to be very sensitive to OZI violating physics which we parametrize in terms of a direct OZI violation parameter and the chiral perturbation theory low energy constants L_4^r and L_6^r. These constants all come out very different from zero, lending further credit to the statement that the OZI rule is not operative in the scalar 0^{++} channel.Comment: revtex, 21 pages, 10 figures, extended discussion of the model in section 2 and some minor corrections, version accepted for publication in Nucl. Phys.

Ultrafast photoinduced charge transport in Pt(II) donor-acceptor assembly bearing naphthalimide electron acceptor and phenothiazine electron donor

Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor–chromophore–donor, (NDI–phen)Pt(II)(–C[triple bond, length as m-dash]C–Ph–CH2–PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(–C[triple bond, length as m-dash]C–Ph–)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a 3MLCT/LL′CT, with {Pt(II)–acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI−–phen–[Pt–(C[triple bond, length as m-dash]C)2]+–PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of [similar]15 ps during which the hole migrates from the [Pt–(C[triple bond, length as m-dash]C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C[triple bond, length as m-dash]C–Ph–CH2–PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C[triple bond, length as m-dash]C–Ph–C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed

Photonics design theory enhancing light extraction efficiency in quantum dot light emitting diodes

The external quantum efficiency (EQE) of quantum dot light emitting diodes (QLEDs) needs improvement for more power-efficient devices. One of the main limitations is the low light extraction efficiency (LEE). Generally, only 20% of the light that is generated inside the emissive layer makes its way out of the device into air, with the rest being lost to waveguide and substrate modes and surface plasmon polaritons. Different photonics structures have been previously tested to help extract the light that is trapped inside the device. Here we report a photonics design which is a combination of nanopillars and grating structures for improving the LEE of QLEDs. The effect of changing the nanopillar height, radius and material has been studied. It was found that ZnO nanopillars of 500 nm pitch, 200 nm height and 400 nm width alongside 150 nm width and pitch grating structure can increase the LEE at 460 nm by 50% and at 640 nm by 20%. It was also found that different materials can help extract light at different wavelengths. TiO2 nanopillars increased the extraction efficiency at ∼590 nm region which was not observed by the other materials. As around 19% of the world's electricity consumption is due to lighting applications, increasing the LEE can significantly reduce the power consumption

Oxygen mapping of melanoma spheroids using small molecule platinum probe and phosphorescence lifetime imaging microscopy

Solid tumours display varied oxygen levels and this characteristic can be exploited to develop new diagnostic tools to determine and exploit these variations. Oxygen is an efficient quencher of emission of many phosphorescent compounds, thus oxygen concentration could in many cases be derived directly from relative emission intensity and lifetime. In this study, we extend our previous work on phosphorescent, low molecular weight platinum(II) complex as an oxygen sensing probe to study the variation in oxygen concentration in a viable multicellular 3D human tumour model. The data shows one of the first examples of non-invasive, real-time oxygen mapping across a melanoma tumour spheroid using one-photon phosphorescence lifetime imaging microscopy (PLIM) and a small molecule oxygen sensitive probe. These measurements were quantitative and enabled real time oxygen mapping with high spatial resolution. This combination presents as a valuable tool for optical detection of both physiological and pathological oxygen levels in a live tissue mass and we suggest has the potential for broader clinical application

Photodynamic killing of cancer cells by a Platinum(II) complex with cyclometallating ligand

Photodynamic therapy that uses photosensitizers which only become toxic upon light-irradiation provides a strong alternative to conventional cancer treatment due to its ability to selectively target tumour material without affecting healthy tissue. Transition metal complexes are highly promising PDT agents due to intense visible light absorption, yet the majority are toxic even without light. This study introduces a small, photostable, charge-neutral platinum-based compound, Pt(II) 2,6-dipyrido-4-methyl-benzenechloride, complex 1, as a photosensitizer, which works under visible light. Activation of the new photosensitizer at low concentrations (0.1–1 μM) by comparatively low dose of 405 nm light (3.6 J cm−2) causes significant cell death of cervical, colorectal and bladder cancer cell lines, and, importantly, a cisplatin resistant cell line EJ-R. The photo-index of the complex is 8. We demonstrate that complex 1 induces irreversible DNA single strand breaks following irradiation, and that oxygen is essential for the photoinduced action. Neither light, nor compound alone led to cell death. The key advantages of the new drug include a remarkably fast accumulation time (diffusion-controlled, minutes), and photostability. This study demonstrates a highly promising new agent for photodynamic therapy, and attracts attention to photostable metal complexes as viable alternatives to conventional chemotherapeutics, such as cisplatin

Long-lived metal complexes open up microsecond lifetime imaging microscopy under multiphoton excitation: from FLIM to PLIM and beyond

Lifetime imaging microscopy with sub-micron resolution provides essential understanding of living systems by allowing both the visualisation of their structure, and the sensing of bio-relevant analytes in vivo using external probes. Chemistry is pivotal for the development of the next generation of bio-tools, where contrast, sensitivity, and molecular specificity facilitate observation of processes fundamental to life. A fundamental limitation at present is the nanosecond lifetime of conventional fluorescent probes which typically confines the sensitivity to sub-nanosecond changes, whilst nanosecond background autofluorescence compromises the contrast. High-resolution visualization with complete background rejection and simultaneous mapping of bio-relevant analytes including oxygen – with sensitivity orders of magnitude higher than that currently attainable – can be achieved using time-resolved emission imaging microscopy (TREM) in conjunction with probes with microsecond (or longer) lifetimes. Yet the microsecond timescale has so far been incompatible with available multiphoton excitation/detection technologies. Here we realize for the first time microsecond-imaging with multiphoton excitation whilst maintaining the essential sub-micron spatial resolution. The new method is background-free and expands available imaging and sensing timescales 1000-fold. Exploiting the first engineered water-soluble member of a family of remarkably emissive platinum-based, microsecond-lived probes amongst others, we demonstrate (i) the first instance of background-free multiphoton-excited microsecond depth imaging of live cells and histological tissues, (ii) over an order-of-magnitude variation in the probe lifetime in vivo in response to the local microenvironment. The concept of two-photon TREM can be seen as “FLIM + PLIM” as it can be used on any timescale, from ultrafast fluorescence of organic molecules to slower emission of transition metal complexes or lanthanides/actinides, and combinations thereof. It brings together transition metal complexes as versatile emissive probes with the new multiphoton-excitation/microsecond-detection approach to create a transformative framework for multiphoton imaging and sensing across biological, medicinal and material sciences