Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

Kohler, Lars; Hayes, Dugan; Hong, Junghwa; Carter, Tyler J.; Shelby, Megan L.; Fransted, Kelly A.; Chen, Lin X.; Mulfort, Karen L.

doi:10.1039/c6dt00324a

Cited by 53 publications

(95 citation statements)

References 69 publications

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“…[47] A4 15 nm pump beam was used for the pump-probe measurements on NiPcOBu 8 ,w hich was dissolved in anhydrous toluene at ac oncentration of 19 mm. [47] A4 15 nm pump beam was used for the pump-probe measurements on NiPcOBu 8 ,w hich was dissolved in anhydrous toluene at ac oncentration of 19 mm.…”

Section: Ultrafast Optical Transient Absorption Spectroscopymentioning

confidence: 99%

“…[47] The beamline operates on the Si(111) double crystal monochromator with resolution of DE/E = 10 À4 .T he 400 nm laser pump pulses (3 kHz repetition rate with 13 ps pulse duration at FWHM) were generated from the second harmonic of the output from aT i:Sapphire laser system (Coherent Lasers, Micra-5O scillator and Legend Elite Duo regenerative amplifier). [47] The beamline operates on the Si(111) double crystal monochromator with resolution of DE/E = 10 À4 .T he 400 nm laser pump pulses (3 kHz repetition rate with 13 ps pulse duration at FWHM) were generated from the second harmonic of the output from aT i:Sapphire laser system (Coherent Lasers, Micra-5O scillator and Legend Elite Duo regenerative amplifier).…”

Section: X-ray Transient Absorption Spectroscopymentioning

confidence: 99%

“…The details of the instrument used for ultrafast optical TA measurements has been described previously. [47] A4 15 nm pump beam was used for the pump-probe measurements on NiPcOBu 8 ,w hich was dissolved in anhydrous toluene at ac oncentration of 19 mm. All experiments were performed at room temperature with constant stirring of the sample solution in as ealed 2mmq uartz cuvette.…”

Section: Ultrafast Optical Transient Absorption Spectroscopymentioning

confidence: 99%

“…The XTAm easurements were performed at beamline 11-ID-D of the Advanced Photon Source at Argonne National Laboratory,a s described preciously. [47] The beamline operates on the Si(111) double crystal monochromator with resolution of DE/E = 10 À4 .T he 400 nm laser pump pulses (3 kHz repetition rate with 13 ps pulse duration at FWHM) were generated from the second harmonic of the output from aT i:Sapphire laser system (Coherent Lasers, Micra-5O scillator and Legend Elite Duo regenerative amplifier). The laser spot size was focused to as pot size of 1mma tt he sample and the X-ray spot size was 0.2 mm(v) 0.5 mm(h).…”

Section: X-ray Transient Absorption Spectroscopymentioning

confidence: 99%

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The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

et al. 2018

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The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu ) with a 500 ps lifetime was investigated by X-ray transient absorption (XTA) spectroscopy. Previous optical, vibrational, and computational studies have suggested that this photoexcited state has a ligand-to-metal charge transfer (LMCT) nature. By using XTA, which provides unambiguous information on the local electronic and nuclear configuration around the Ni center, the nature of the excited state of NiPcOBu was reassessed. Using X-ray probe pulses from a synchrotron source, the ground- and excited-state X-ray absorption spectra of NiPcOBu were measured. Based on the results, we identified that the excited state exhibits spectral features that are characteristic of a Ni (3dz2 ,3dx2-y2 ) state rather than a LMCT state with a transiently reduced Ni center. This state resembles the (d,d) state of nickel(II) tetramesitylphorphyrin. The XTA features are rationalized based on the inherent cavity sizes of the macrocycles. These results may provide useful guidance for the design of photocatalysts in the future.

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Section: Ultrafast Optical Transient Absorption Spectroscopymentioning

confidence: 99%

Section: X-ray Transient Absorption Spectroscopymentioning

confidence: 99%

Section: Ultrafast Optical Transient Absorption Spectroscopymentioning

confidence: 99%

Section: X-ray Transient Absorption Spectroscopymentioning

confidence: 99%

See 2 more Smart Citations

The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

et al. 2018

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“…We conclude by noting that it is not possible to isolate the heteroleptic complexes with simple ligands of the type illustrated here, but by using ligands with sterically demanding substituents the heteroleptic complexes may be isolated as the major or only products. This is illustrated with bulky substituents in the HETPHEN approach to the design of copper(I) dyes for DSCs (167,168,169,170,171,172) In the course of these studies we developed scanning electrochemical microscopic (SECM) methods to directly interrogate copper(I) DSCs under irradiation and in the dark (173,174). This allowed us access to a powerful method for the high throughput evaluation of combinations of anchoring ligand, ancillary ligand (see later) and electrolyte.…”

Section: Figure 29mentioning

confidence: 99%

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Constable

2018

Advances in Inorganic Chemistry

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This article describes the development of concepts in metallosupramolecular chemistry. In particular, the transfer of the concepts from solution phase to metallosupramolecular chemistry at solid-fluid interfaces is discussed. The concept of metal-binding domains is quantified and used for the design of ligands for specific supramolecular applications. The use of weak interactions for the investigation of surface supramolecular chemistry is presented followed by the "surfaces as ligands, surfaces as complexes" approach for the design of functional devices. This conceptual development is placed in the concept the author's own laboratory.This account is about a journey from "traditional" coordination chemistry, through solution phase supramolecular chemistry to the use of the paradigms and methodologies of self-organization and self-assembly in the construction of ordered and hierarchical structures at solid-fluid interfaces. At the end phase of this journey, interactions with atomically well-defined and low-dimensional surfaces as well-as complex nanostructured surfaces will be considered. FROM COORDINATION CHEMISTRY TO METALLOSUPRAMOLECULAR CHEMISTRY Coordination chemistry as molecular recognition"What goes around comes around" -this journey begins with the design of 2,2'bipyridine ligands for application in what came to be known as dye-sensitized solar cells and ends in the development of new methodologies for the design of these and related systems. Rutile (TiO 2 ) is a semiconductor with a band gap of » 3.0 eV and exhibits no photocurrent upon irradiation with light l > 450 nm. In contrast, the complex [Ru(bpy) 2 (1)] exhibits a typical {Ru II (bpy) 3 } absorption close to 450 nm.The complex [Ru(bpy) 2 (1)] binds to the surface of single crystal rutile and acts as a photosensitizer, allowing the photoinjection of electrons directly into the conduction band upon irradiation with visible light l > 450 nm (Figure 1) (3). The photocurrents were modest and it was only when Grätzel used this strategy for the modification of nanostructured TiO 2 surfaces, allowing very high dye-loading, that the method became viable (4,5,6).

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Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

et al. 2021

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High-energy X-rays cattering and pair distribution function analysis (HEXS/PDF) is apowerfulmethod to reveal the structure of materials lackingl ong-range order,b ut is underutilized for molecular complexes in solution. We demonstrate the application of HEXS/PDF with 0.26 resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes.H EXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal•••metal distances separated by over 12 .T he metal•••metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state.T his work presents the first example of observing sub-ngstrçm conformational differences by direct comparison of solution phase and solid-state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

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Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

Cited by 53 publications

References 69 publications

The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

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Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

Cited by 53 publications

References 69 publications

The Nature of the Long‐Lived Excited State in a NiII Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

The Nature of the Long‐Lived Excited State in a NiII Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

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Product

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The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy

The Nature of the Long‐Lived Excited State in a Ni^II Phthalocyanine Complex Investigated by X‐Ray Transient Absorption Spectroscopy