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Title: Altering Molecular Photophysics by Merging Organic and Inorganic Chromophores

  1. Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
Resource Type:
Journal Article: Published Article
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 48; Journal Issue: 3; Related Information: CHORUS Timestamp: 2017-11-27 09:30:57; Journal ID: ISSN 0001-4842
American Chemical Society
Country of Publication:
United States

Citation Formats

Castellano, Felix N. Altering Molecular Photophysics by Merging Organic and Inorganic Chromophores. United States: N. p., 2015. Web. doi:10.1021/ar500385e.
Castellano, Felix N. Altering Molecular Photophysics by Merging Organic and Inorganic Chromophores. United States. doi:10.1021/ar500385e.
Castellano, Felix N. 2015. "Altering Molecular Photophysics by Merging Organic and Inorganic Chromophores". United States. doi:10.1021/ar500385e.
title = {Altering Molecular Photophysics by Merging Organic and Inorganic Chromophores},
author = {Castellano, Felix N.},
abstractNote = {},
doi = {10.1021/ar500385e},
journal = {Accounts of Chemical Research},
number = 3,
volume = 48,
place = {United States},
year = 2015,
month = 2

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/ar500385e

Citation Metrics:
Cited by: 32works
Citation information provided by
Web of Science

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  • To date, the breadth of scientific research that has been devoted to investigating the photochemical and photophysical behavior of the lanthanide elements has generally fallen into one of two camps: solution studies of luminescent lanthanide metal-ligand complexes or investigations of solid-state nanoparticles, composed primarily of, or doped with, lanthan ide lumiphores. In the latter case, most research of lanthanide nanocolloids has precluded any investigations regarding the use of organic ligands to overcome the difficulties associated with f-f excitation of lanthanides. Instead, most work on condensed-phase lanthanide luminescence has centered on strategies such as d-f charge separation in divalent lanthanides andmore » the sensitization of lanthanide excited states using quantum dots. Current work now aims at bridging the camps of condensed-phase lanthanide photophysics and the solution chemistry of ligand-lanthanide molecular complexes. Some recent efforts have partly focused on the fundamental characterization of NaGd 1-x Ln x F 4 nanoparticles featuring surface display of the sensitizer ligand 3,4,3-LI(1,2-HOPO), showing these structures to be capable of converting absorbed UV light into luminescence from Eu 3+ and Tb 3+ ions. Our results suggest such a use of the ligand sensitization as a tool of choice to overcome the constraints of UV solar spectrum/semiconductor band-gap mismatch and low absorption cross sections in solid-state lanthanide systems.« less
  • Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) dependmore » strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.« less
  • The search for molecules possessing large second-order optical nonlinearities (i.e., having large {beta} values) is currently an area of intense activity. Once identified, such molecules can be incorporated into macroscopic assemblies to form materials exhibiting very large nonlinear optical (NLO) responses. There are several theoretical approaches for calculating molecular nonlinear optical responses. The ZINDO (INDO/S, intermediate neglect of differential overlap/spectroscopy) electronic structure formalism has been successfully parameterized for a wide range of main-group and transition-metal elements and is therefore potentially ideal for computing the quadratic NLO characteristics of molecules inaccessible to other approximate or semiempirical models. The authors communicate themore » first application of ZINDO to calculating the quadratic hyperpolarizabilities of main-group inorganic chromophores.« less
  • The photophysics and photochemistry of tris(2,2{prime}-bipyridyl)ruthenium(II) (Ru(bpy){sub 3}{sup 2+}) adsorbed into the layered solid zirconium phosphate sulfophenylphosphonate are described. The decay kinetics of the metal complex are shown to depart from first-order behavior. Albery's model of dispersed kinetics, which assumes a continuous distribution of rate constants, is used to explain the decay kinetics. The oxidative quencher methylviologen (MV{sup 2+}) is shown to react with Ru(bpy){sub 3}{sup 2+} in ZrPS via a combined dynamic and quasi static (sphere of action) quenching mechanism.
  • The synthesis, crystal structure and physical properties of the new series {alpha}{sub 1} and {alpha}{sub 2} of radical salts made with bis (ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) and Keggin polyoxoanions are reported. The structure of the {alpha}{sub 1}-ET{sub 8}[XW{sub 12}O{sub 40}] (X=Co{sup II}, Cu{sup II}, 2(H{sup +}) and Fe{sup III}) series consists of alternating layers of the organic donor and the Keggin polyoxometalates. The organic layers contain three crystallographically independent molecules that form two different parallel stacks alternating in the [101] direction. The structure of the {alpha}{sub 2}-ET{sub 8}[XW{sub 12}O{sub 40}] (X=Co{sup II}, Cu{sup II}, 2(H{sup +}), Fe{sup III} andmore » B{sup III}) series is similar to that of the {alpha}{sub 1} phase but the organic layers contain only two crystallographically independent molecules. In both {alpha} phases the Keggin polyanions form closed packed pseudohexagonal layers. Both crystal structures suggest the presence of two types of differently charged stacks: a dimerized one with almost neutral ET molecules, and an eclipsed one formed by almost ionized ET molecules. This inhomogeneous charge distribution is confirmed by Raman spectroscopy. Conductivity measurements show that all compounds are semiconductors, in agreement with the band structure EHT calculations. Magnetic measurements indicate the presence of antiferromagnetic interactions in the organic sublattice with the presence of a strong Curie tail and confirm the electronic distribution in the two kinds of stacks. ESR spectra of the salts with dimagnetic anions complete these results and for the radical salts with paramagnetic anions indicate that both sublattices coexist but do not interact significantly.« less