Jonathan Rochford

Shining Light on the Dark Side of Imaging: Excited State Absorption Enhancement of a Bis-styryl BODIPY Photoacoustic Contrast Agent

A first approach toward understanding the targeted design of molecular photoacoustic contrast agents (MPACs) is presented. Optical and photoacoustic Z-scan spectroscopy was used to identify how nonlinear (excited-state) absorption contributes to enhancing the photoacoustic emission of the curcuminBF2 and bis-styryl (MeOPh)2BODIPY dyes relative to Cy3.

Engineering of Ruthenium(II) Photosensitizers with Non-Innocent Oxyquinolate and Carboxyamidoquinolate Ligands for Dye-Sensitized Solar Cells

An alternative approach to replacing the isothiocyantate ligands of the N3 photosensitizer with light-harvesting bidentate ligands is investigated for application in dye-sensitized solar cells (DSSCs). An in-depth theoretical analysis has been applied to investigate the optical and redox properties of four non-innocent ligand platforms, which is then corroborated with experiment. Taking advantage of the 5- and 7-positions of 8-oxyquinolate, or the carboxyaryl ring system of the N-arylcarboxy-8-amidoquinolate ligand, fluorinated aryl substituents are demonstrated as an effective means of tuning complex redox potentials and light-harvesting properties. The non-innocent character, resulting from mixing of both the central metal-dπ and ligand-π manifolds, generates hybrid metal-ligand frontier orbitals. These play a major role by contributing to the redox properties and visible electronic transitions, and promoting an improved power conversion efficiency in a Ru DSSC device featuring non-innocent ligands.

Rigid triarylamine donor–π–acceptor porphyrin dyes and their application in dye-sensitized solar cells

Three donor–π–acceptor porphyrin dyes bearing a variety of rigid triarylamine donor groups were synthesized for application as photosensitizers in TiO2 based dye-sensitized solar cells (DSSCs). Compared with the “naked” porphyrin ZnP, i.e. having no triarylamine moiety, broadened and red-shifted spectral features were exhibited by the triaylamine porphyrin sensitizers ISB-ZnP, CZ-ZnP, and IDB-ZnP where ISB = 5-phenyliminostilbene, CZ = 5-phenylcarbazole, and IDB = 5-phenyliminodibenzyl. Percentage power conversion efficiencies (η) and incident photon-to-current conversion efficiencies (%IPCE) in DSSC devices show the trend ISB-ZnP < ZnP < CZ-ZnP < IDB-ZnP. Inferior performance of the ISB-ZnP dye is attributed to its weaker adsorption to the TiO2 film, which is roughly half that of ZnP. In contrast, introduction of the CZ and IDB electron donors is demonstrated to promote a better performance than the “naked” ZnP porphyrin. The best performance was observed for the IDB-ZnP device reaching a power conversion efficiency of η = 3.62% under AM 1.5 irradiation conditions with a corresponding %IPCE maximizing at 48% for both Soret band (450 nm) and Q band (570 nm) photoexcitation.

Probing the Noninnocent π-Bonding Influence of N-Carboxyamidoquinolate Ligands on the Light Harvesting and Redox Properties of Ruthenium Polypyridyl Complexes

Electronic and photophysical characterization is presented for a series of bis-heteroleptic [Ru(bpy)2(R-CAQN)](+) complexes where CAQN is a bidentate N-(carboxyaryl)amidoquinolate ligand and the aryl substituent R = p-tolyl, p-fluorobenzene, p-trifluoromethylbenzene, 3,5-bis(trifluoromethyl)benzene, or 4-methoxy-2,3,5,6-tetrafluorobenzene. Characterized by a strong noninnocent Ru(dπ)-CAQN(π) bonding interaction, density functional theory (DFT) analysis is used to estimate the contribution of both atomic Ru(dπ) and ligand CAQN(π) manifolds to the frontier molecular orbitals of these complexes. UV-vis absorption and emission studies are presented where the noninnocent Ru(dπ)-CAQN(π) bonding scheme plays a major role in defining complex electronic and photophysical properties. Oxidation potentials are tuned over a range of 0.92 V with respect to the [Ru(bpy)3](2+) reference system, hereafter referred to as 1(2+), by varying the degree of R-CAQN fluorination while maintaining consistently strong and panchromatic visible absorption properties. Electron paramagnetic resonance (EPR) spectroscopy is employed to experimentally map delocalization of the unpaired electron/electron-hole within the delocalized Ru(dπ)-CAQN(π) singly occupied valence molecular orbital of the one-electron oxidized complexes. EPR data is complemented experimentally by UV-vis-NIR spectroelectrochemistry, and computationally by molecular orbital Mulliken contributions and spin-density analysis. It is ultimately demonstrated that the CAQN ligand framework provides a simple yet broad synthetic platform in the design of redox-active transition metal chromophores with a range of electronic and spectroscopic characteristics hinting at the diversity and potential of these complexes toward photochemical and catalytic applications.

Molecular Photoacoustic Contrast Agents: Design Principles & Applications

Photoacoustic imaging (PAI) is a rapidly growing field which offers high spatial resolution and high contrast for deep‐tissue imaging in vivo. PAI is nonionizing and noninvasive and combines the optical resolution of fluorescence imaging with the spatial resolution of ultrasound imaging. In particular, the development of exogenous PA contrast agents has gained significant momentum of late with a vastly expanding complexity of dye materials under investigation ranging from small molecules to macromolecular proteins, polymeric and inorganic nanoparticles. The goal of this review is to survey the current state of the art in molecular photoacoustic contrast agents (MPACs) for applications in biomedical imaging. The fundamental design principles of MPACs are presented and a review of prior reports spanning from early‐to‐current literature is put forth.

Photophysical and Photoacoustic Properties of π-Extended Curcumin Dyes. Effects of the Terminal Dimethylamino Electron-donor and the Bridging Aryl Ring

The synthesis, photophysical and photoacoustic characterization for a series of nine π‐extended quadrupolar curcumin dyes is presented. A systematic evaluation of the π‐bridging unit including the p‐phenyl, naphth‐4‐yl, thien‐2‐yl and hybrid 4‐naphthathien‐2‐yl groups is presented. Furthermore, evaluation of the strongly donating donor‐π‐acceptor‐π‐donor quadrupolar dimethylamino terminated derivatives is also included. Select dyes exhibit excited state absorption at increased laser fluence which translates to the production of a nonlinear enhanced photoacoustic response. In particular, the bis‐4‐dimethylaminonaphtha‐2‐thien‐5‐yl curcuminBF2 contrast agent DMA‐5 exhibits an excellent molar photoacoustics (PA) emission at both low (9.4 × 103 V M−1) and high (1.47 × 105 V M−1) laser fluence which is confirmed by its strong contrast by photoacoustic tomography (PAT). In summary, the strong absorbance and enhanced photoacoustic properties of naphthyl and thienyl curcuminoids here presented provides great promise for future photoacoustic imaging applications as demonstrated by preliminary PAT studies.

Principles of Electrocatalysis

Abstract The challenges associated with sustainable fuels production have seen a major growth in the need for, and application of, electrocatalysis in chemical transformations. Electrochemical analysis allows for a detailed and quantitative thermodynamic and kinetic analysis of critical reaction mechanisms that govern the most pressing energy concerns. This chapter will address the current state of the art in homogeneous molecular electrocatalysts for CO2 reduction. Before discussion of any applications of electrochemical catalysis, the fundamentals of cyclic voltammetry are summarized followed by an introduction to the topics of proton-coupled electron transfer and turnover frequency-voltammetry analysis (including foot-of-the-wave analysis), which are necessary to gain a true appreciation of any CO2 reduction electrocatalyst. Armed with this knowledge, interpretation and appreciation of scientific advancements in this field will be straightforward.

Solar Energy Conversion

Solar energy is an abundant and renewable source of power that could alleviate world energy demand. New materials technologies are rising to the challenge of replacing a silicon-dominated market with the promise of cheaper and more versatile photovoltaics. In this chapter, one of the most highly studied alternatives, the dye-sensitized solar cell (DSSC), is discussed from a historical perspective as well as recent advances in DSSC technologies. In addition, the emerging technology of perovskite solar cells, which bear some similarity to DSSCs, is also introduced.

Principles of Photochemical Activation Toward Artificial Photosynthesis and Organic Transformations

Abstract The basic principles of photocatalysis are introduced from the perspective of a homogeneous system using a molecular photosensitizer. Model photophysical and redox properties of a molecular photosensitizer are discussed. Generic reaction schemes are presented for established photocatalytic protocols via photooxidative and photoreductive mechanisms with sacrificial electron donating or accepting agents. Inspired by natural photosynthesis, prototypical examples of photocatalytic CO2 reduction and photocatalytic H2O oxidation are also included. Finally, an introduction to the growing field of photocatalytic organic transformations is provided.

Linear and Nonlinear Absorption Enhanced Photoacoustic Response of BODIPY and Curcuminoid Photoacoustic-phores

We report the development of efficient photoacoustic-phores based on BODIPY and curcuminiod fluorophores. Enhancement of PA response is attributed to strong linear absorption and excited state at incident wavelength, and long lived excited states.