Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins

Pattengale, Brian; Liu, Qiuhua; Hu, Wenhui; Yang, Shaohua; He, Peilei; Tender, Sir Lawrence; Wang, Yingqi; Zhang, Xiaoyi; Zhou, Zaichun; Zhang, Jian; Huang, Jier

doi:10.1021/acs.jpcc.9b05413

Cited by 10 publications

(12 citation statements)

References 40 publications

(84 reference statements)

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“…Comparatively longer decay time is observed in case of Cu-TCBD ( 3 ) porphyrin. Similar, transient dynamics were observed in different Ni-porphyrins, which showed that the excited state lifetime could be varied in the range of 0.7–560 ps. − …”

Section: Resultssupporting

confidence: 60%

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

et al. 2021

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A series of β-TCBD (1,1,4,4-tetracyano-buta-1,3diene)-appended porphyrins, M-TCBD (M = 2H, Co(II), Ni(II), Cu(II), and Zn(II)), was synthesized from 2,3-diphenylethynyl-12nitro-meso-tetraphenylporphyrin, H 2 -PE 2 , and characterized by various spectroscopic techniques and electrochemical studies. The reaction proceeds via [2 + 2] cycloaddition and retroelectrocyclization reactions of tetracyanoethylene (TCNE) with H 2 -PE 2 . The observed unusual reduction potentials in the cyclic voltammograms of the synthesized porphyrins in the range of −0.06 to −0.10 V are the consequence of the TCBD moiety present at the β-position of the porphyrin macrocycle. Notably, these porphyrins exhibited three porphyrin ring-centered reductions due to extended π-conjugation. The higher nonlinear optical response exhibited by the M-TCBD series as compared to the precursor (H 2 -PE 2 ) was attributed to the existence of intramolecular charge transfer and enhanced polarization in the M-TCBD series. The single-beam femtosecond Z-scan measurements were performed to elucidate the third-order nonlinear optical properties, and the temporal response of these porphyrin molecules was investigated using optical pump−probe spectroscopy to study the excited state absorption dynamics. Zscan measurements revealed that Co-TCBD exhibited a higher nonlinear optical response as compared to free base porphyrins. The two-photon absorption coefficient (β) and the imaginary part of third-order nonlinear optical susceptibility (χ (3) ) were obtained from the open aperture experiment, whereas the close aperture experiment delivered the magnitude and the sign of the nonlinear refractive index (n 2 ) and the real part of χ (3) . Furthermore, the femtosecond transient absorption spectroscopy revealed a faster relaxation dynamics of various absorption processes in a picosecond timescale. The excellent optical limiting threshold (1.90−2.33 × 10 15 W/m 2 ) of the synthesized porphyrins makes them good materials for laser protection and high-power laser operation.

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Section: Resultssupporting

confidence: 60%

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

et al. 2021

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“…In molecular systems, such timeresolved EXAFS investigations are possible. 44 Interestingly, there is a report of using electron paramagnetic resonance (EPR) with a guest molecule reporter to investigate temperature-induced structural changes in MOFs. 123 This opens the possibility of time-resolved EPR as a potential strategy in certain cases, such as with a guest molecule reporter in a MOF that does not give background signal in order to infer photoinduced structural changes.…”

Section: Overview and Time-resolved Techniques Appliedmentioning

confidence: 99%

“…Despite this, one clear signature that can be relied upon is an edge shift corresponding to a change in binding energy or oxidation state of the probed atom. Further information can be gathered above the transition edge where interference patterns between the probed atom and its neighbors can be analyzed using Fourier-transform techniques to provide excited state local structure information . In practice, the X-ray absorption spectrum is collected at discrete energies with and without laser excitation, and a difference spectrum is generated by subtracting laser on–laser off spectra …”

Section: Overview Of Time-resolved Techniquesmentioning

confidence: 99%

“…For instance, inferred structure changes were observed in the XANES region of ZIF-67, however, collecting extensive EXAFS data to quantify the changes at various delay times would be insurmountably challenging due to signal-to-noise partly due to needing to measure the sample as a powder suspended in a solvent jet. In molecular systems, such time-resolved EXAFS investigations are possible …”

Section: Structural Dynamicsmentioning

confidence: 99%

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Interrogating Light-initiated Dynamics in Metal–Organic Frameworks with Time-resolved Spectroscopy

et al. 2021

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Time-resolved spectroscopy is an essential part of both fundamental and applied chemical research. Such techniques access light-initiated dynamics on time scales ranging from femtosecond to microsecond. Many techniques falling under this description have been applied to gain significant insight into metal–organic frameworks (MOFs), a diverse class of porous coordination polymers. MOFs are highly tunable, both compositionally and structurally, and unique challenges are encountered in applying time-resolved spectroscopy to interrogate their light-initiated properties. These properties involve various excited state mechanisms such as crystallographically defined energy transfer, charge transfer, and localization within the framework, photoconductivity, and structural dynamics. The field of time-resolved MOF spectroscopic studies is quite nascent; each original report cited in this review was published within the past decade. As such, this review is a timely and comprehensive summary of the most significant contributions in this emerging field, with focuses on the overarching spectroscopic concepts applied and on identifying key challenges and future outlooks moving forward.

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“…Thus, AXMP can efficiently capture sub-ns XTA sample dynamics, which are often of particular interest. [14][15][16][17][18][19][20][21][22][23] This is accomplished using a carefully selected pump laser repetition rate, which makes the acquired time delays increase by δt in each subsequent pump-probe cycle. For example, in Fig.…”

Section: Introductionmentioning

confidence: 99%

Asynchronous x-ray multiprobe data acquisition for x-ray transient absorption spectroscopy

Kinigstein

Otolski

Jennings

et al. 2023

Review of Scientific Instruments

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Laser pump X-ray Transient Absorption (XTA) spectroscopy offers unique insights into photochemical and photophysical phenomena. X-ray Multiprobe data acquisition (XMP DAQ) is a technique that acquires XTA spectra at thousands of pump-probe time delays in a single measurement, producing highly self-consistent XTA spectral dynamics. In this work, we report two new XTA data acquisition techniques that leverage the high performance of XMP DAQ in combination with High Repetition Rate (HRR) laser excitation: HRR-XMP and Asynchronous X-ray Multiprobe (AXMP). HRR-XMP uses a laser repetition rate up to 200 times higher than previous implementations of XMP DAQ and proportionally increases the data collection efficiency at each time delay. This allows HRR-XMP to acquire more high-quality XTA data in less time. AXMP uses a frequency mismatch between the laser and x-ray pulses to acquire XTA data at a flexibly defined set of pump-probe time delays with a spacing down to a few picoseconds. AXMP introduces a novel pump-probe synchronization concept that acquires data in clusters of time delays. The temporally inhomogeneous distribution of acquired data improves the attainable signal statistics at early times, making the AXMP synchronization concept useful for measuring sub-nanosecond dynamics with photon-starved techniques like XTA. In this paper, we demonstrate HRR-XMP and AXMP by measuring the laser-induced spectral dynamics of dilute aqueous solutions of Fe(CN)64− and [FeII(bpy)3]2+ (bpy: 2,2′-bipyridine), respectively.

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Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins

Cited by 10 publications

References 40 publications

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

Interrogating Light-initiated Dynamics in Metal–Organic Frameworks with Time-resolved Spectroscopy

Asynchronous x-ray multiprobe data acquisition for x-ray transient absorption spectroscopy

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