The process of photosynthesis is initiated by the capture of sunlight by a network of light-absorbing molecules (chromophores), which are also responsible for the subsequent funneling of the excitation energy to the reaction centers. Through evolution, genetic drift, and speciation, photosynthetic organisms have discovered many solutions for light harvesting. In this review, we describe the underlying photophysical principles by which this energy is absorbed, as well as the mechanisms of electronic excitation energy transfer (EET). First, optical properties of the individual pigment chromophores present in light-harvesting antenna complexes are introduced, and then we examine the collective behavior of pigment-pigment and pigment-protein interactions. The description of energy transfer, in particular multichromophoric antenna structures, is shown to vary depending on the spatial and energetic landscape, which dictates the relative coupling strength between constituent pigment molecules. In the latter half of the article, we focus on the light-harvesting complexes of purple bacteria as a model to illustrate the present understanding of the synergetic effects leading to EET optimization of light-harvesting antenna systems while exploring the structure and function of the integral chromophores. We end this review with a brief overview of the energy-transfer dynamics and pathways in the light-harvesting antennas of various photosynthetic organisms.

Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = (i)Pr, 1-(i)Pr; R = Cy, 1-Cy), with C(3v) and C(2v) solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1-(i)Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1-(i)Pr revealed the (2)A1 excited states corresponded to singly occupied 5d(z(2)) orbitals. The strongly reducing metalloradical character of 1, 1-(i)Pr, and 1-Cy in their (2)A1 excited states afforded photochemical halogen atom abstraction reactions from sp(3) and sp(2) C-X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions.

Two complete mixed-ligand series of luminescent Ce(III) complexes with the general formulas [(Me3Si)2NC(N(i)Pr)2]xCe(III)[N(SiMe3)2]3-x (x = 0, 1-N; x = 1, 2-N, x = 2, 3-N; x = 3, 4) and [(Me3Si)2NC(N(i)Pr)2]xCe(III)(OAr)3-x (x = 0, 1-OAr; x = 1, 2-OAr, x = 2, 3-OAr; x = 3, 4) were developed, featuring photoluminescence quantum yields up to 0.81(2) and lifetimes to 117(1) ns. Although the 4f → 5d absorptive transitions for these complexes were all found at ca. 420 nm, their emission bands exhibited large Stokes shifts with maxima occurring at 553 nm for 1-N, 518 nm for 2-N, 508 nm for 3-N, and 459 nm for 4, featuring yellow, lime-green, green, and blue light, respectively. Combined time-dependent density functional theory (TD-DFT) calculations and spectroscopic studies suggested that the long-lived (2)D excited states of these complexes corresponded to singly occupied 5dz(2) orbitals. The observed difference in the Stokes shifts was attributed to the relaxation of excited states through vibrational processes facilitated by the ligands. The photochemistry of the sterically congested complex 4 was demonstrated by C-C bond forming reaction between 4-fluoroiodobenzene and benzene through an outer sphere electron transfer pathway, which expands the capabilities of cerium photosensitizers beyond our previous results that demonstrated inner sphere halogen atom abstraction reactivity by 1-N.

The hexachlorocerate(III) anion, [CeCl], was found to be a potent photoreductant in acetonitrile solution with an estimated excited-state reduction potential of -3.45 V versus CpFe. Despite a short lifetime of 22.1(1) ns, the anion exhibited a photoluminescence quantum yield of 0.61(4) and fast quenching kinetics toward organohalogens allowing for its application in the photocatalytic reduction of aryl chloride substrates.

Metal carbonyl complexes offer both rich chemistry and complex vibrational spectroscopy due to strong coupling among the carbonyl stretches. Using two-dimensional infrared (2DIR) spectroscopy, it is possible to resolve the underlying transitions between vibrational energy levels, determine the orientations and relative magnitude of the corresponding transition dipole moments, measure the coupling between modes due to the anharmonicity of the potential, and probe energy redistribution among the modes as well as energy relaxation to other degrees of freedom. Measurements on metal carbonyl complexes have played, and continue to play, a crucial role in facilitating the development of 2DIR spectroscopy. These compounds have provided powerful demonstrations of the unique ability of 2DIR spectroscopy to resolve vibrational structure and dynamics in multimode systems. In addition, invaluable new information has been obtained on metal-to-ligand charge transfer processes, solvent-solute interactions and fluxionality. Since transition metal complexes play important roles in catalysis and as dye sensitizers for semiconductor nanoparticle photocatalysis, detailed probes of equilibrium and phototriggered dynamics should aid our understanding of these key catalytic systems. The richness and level of detail provided by the 2DIR spectra of metal carbonyl complexes turn them into extremely useful model systems for testing the accuracy of ab initio quantum chemical calculations. Accurate modeling of the 2DIR spectra of solvated metal carbonyl complexes requires the development of new theoretical and computational tools beyond those employed in the standard analysis of one-dimensional IR spectra, and represents an ongoing challenge to currently available computational methodologies. These challenges are further compounded by the increasing interest in triggered 2DIR experiments that involve nonequilibrium vibrational dynamics on multiple electronic potential surfaces. In this Account, we review the various metal carbonyl complexes studied via 2DIR spectroscopy and outline the theoretical approaches used in order to model the spectra. The capabilities of 2DIR spectroscopy and its interplay with modern ab initio calculations are demonstrated in the context of the metal carbonyl complex Mn(2)(CO)(10) recently studied in our lab. Continued progress in experimental implementation and theoretical analysis will enable transient 2D spectroscopy to provide structurally sensitive details of complex, highly interacting nonequilibrium processes that are central to diverse chemical transformations.