Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Photoswitching dynamics of a guanidine anion receptor

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d5cp00233h· OSTI ID:2573695
 [1];  [1];  [1];  [2];  [2];  [1];  [1];  [1]
  1. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
+ Show Author Affiliations
Photoswitchable molecules involving large-scale structural changes such as E/Z photoisomerization offer remarkable opportunities for light-stimulated catch-and-release chemical separations. While the feasibility of this photochemically driven mechanism has been demonstrated in pioneering studies, the electronic excited-state relaxation processes and concomitant structural changes of such a functional photoswitcher remain largely unexplored. Here, we investigate an exceptional photoswitchable molecule, 2-pyridyl-diiminoguanidinium (2PyDIG), which exhibits strong and selective anion binding, along with an extraordinary capability for light-induced release of a guest ion. Through time-resolved fluorescence measurements and multireference and time-dependent density functional theory calculations, we reveal the dynamics underlying electronic excited state relaxation and photoisomerization central to photoswitching. A very rapid and dominant decay component was found that is consistent with radiationless de-excitation from S1 to S0 through conical intersections. This process competes effectively with the slower photoisomerization process taking place in 94 ps. We further identified the underlying causes through theoretical calculations and potential routes towards improved photoisomerization efficiencies.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
2573695
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 25 Vol. 27; ISSN 1463-9076; ISSN 1463-9084
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (59)

Enlightening Materials with Photoswitches journal January 2020
Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly journal November 2017
A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion‐Binding Switching journal April 2022
Light‐Modulated Self‐Blockage of a Urea Binding Site in a Stiff‐Stilbene Based Anion Receptor journal November 2019
A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides: A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides journal June 2016
Helicity-Encoded Molecular Strands: Efficient Access by the Hydrazone Route and Structural Features journal May 2003
Photoresponsive receptors for binding and releasing anions: PHOTORESPONSIVE RECEPTORS FOR BINDING AND RELEASING ANIONS journal June 2012
Software update: the ORCA program system, version 4.0: Software update journal July 2017
The ORCA program system: The ORCA program system journal June 2011
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Photochemistry: A Modern Theoretical Perspective book January 2018
Bacteriochlorophyll organization and energy transfer kinetics in chlorosomes from Chloroflexus aurantiacus depend on the light regime during growth journal February 1996
A discussion of the problem of determining multiple lifetimes from picosecond absorption recovery data as encountered in two carbocyanine dyes journal August 1983
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Primary processes and structure of the Photosystem II reaction center: II. Low-temperature picosecond fluorescence kinetics of a D1-D2-cyt-b-559 reaction center complex isolated by short Triton exposure journal July 1993
Picosecond fluorescence kinetics of the D1-D2-cyt-b-559 photosystem II reaction center complex. Energy transfer and primary charge separation processes journal November 1991
Excitation Energy Transfer Dynamics and Excited-State Structure in Chlorosomes of Chlorobium phaeobacteroides journal February 2003
Photocontrolled extraction ability of azobenzene-bridged azacrown ether journal January 1979
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Decomposition of Intermolecular Interaction Energies within the Local Pair Natural Orbital Coupled Cluster Framework journal September 2016
Upper Excited State Photophysics of Malachite Green in Solution and Films journal May 2020
Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies journal April 2018
Photocontrol of Anion Binding Affinity to a Bis-urea Receptor Derived from Stiff-Stilbene journal January 2017
Tetra-(meta-butylcarbamoyl)azobenzene: A Rationally Designed Photoswitch with Binding Affinity for Oxoanions in a Long-Lived Z-State journal February 2017
Reorientation and isomerization of trans-stilbene in alkane solutions journal April 1988
Temperature dependence of photoisomerization. VI. Viscosity effect journal January 1968
Absorption Spectra and Tautomerism of Cyanuric Acid, Melamine and Some Related Compounds journal April 1947
Flipping the Switch on Chloride Concentrations with a Light-Active Foldamer journal September 2010
Multi-State Regulation of the Dihydrogen Phosphate Binding Affinity to a Light- and Heat-Responsive Bis-Urea Receptor journal November 2014
Acylhydrazones as Widely Tunable Photoswitches journal November 2015
Allosteric Control of Photofoldamers for Selecting between Anion Regulation and Double-to-Single Helix Switching journal November 2018
Energy Transfer Dynamics in Light-Harvesting Assemblies Templated by the Tobacco Mosaic Virus Coat Protein journal June 2008
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Ring Opening in the Dehydrocholesterol−Previtamin D System Studied by Ultrafast Spectroscopy journal January 1996
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model journal March 1998
Femtosecond Dynamics of Pyridine in the Condensed Phase:  Valence Isomerization by Conical Intersections journal September 1999
Amide- and Urea-Functionalized Dithienylethene: Synthesis, Photochromism, and Binding with Halide Anions journal October 2011
Photoswitching hydrazones based on benzoylpyridine journal January 2019
Molecular photoswitches in aqueous environments journal January 2021
Azopyridine: a smart photo- and chemo-responsive substituent for polymers and supramolecular assemblies journal January 2020
Photoresponsive macrocycles for selective binding and release of sulfate journal January 2021
Unravelling photoisomerization dynamics in a metastable-state photoacid journal January 2024
Photoisomerization mechanism of iminoguanidinium receptors from spectroscopic methods and quantum chemical calculations journal January 2024
Ultrafast ring-opening reactions: a comparison of α-terpinene, α-phellandrene, and 7-dehydrocholesterol with 1,3-cyclohexadiene journal January 2013
Spin—Orbit Coupling and the Radiationless Processes in Nitrogen Heterocyclics journal June 1963
A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution journal August 2006
Ultrafast electrocyclic ring opening of 7-dehydrocholesterol in solution: The influence of solvent on excited state dynamics journal March 2011
Observation of fluorescence of pyridine in the vapor phase journal June 1977
Vapor‐phase fluorescence emissions of pyridine and its methyl derivatives: Excitation‐energy dependence of nonradiative electronic relaxation journal July 1979
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Guanidine and guanidinium cation in the excited state—theoretical investigation journal August 2014
A domain-based local pair natural orbital implementation of the equation of motion coupled cluster method for electron attached states journal April 2019
Ultrafast excited state dynamics of provitamin D3 and analogs in solution and in lipid bilayers journal March 2021
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Ultrafast Photochemistry in Liquids journal April 2013
Subpicosecond Spectroscopy journal October 1986
Using Pyridinium Styryl Dyes as the Standards of Time-Resolved Instrument Response journal May 2016
Photochromism of Phenylazopyridines and Its Application to the Fluorescence Modulation of Zinc–Porphyrins journal August 2004
Electron-transfer dyads suitable for novel self-assembled light-harvesting antenna/electron-transfer devices journal January 2001

Similar Records

A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion-Binding Switching
Journal Article · Tue Mar 22 20:00:00 EDT 2022 · Chemistry - A European Journal · OSTI ID:1862148
Laser control of reactions of photoswitching functional molecules
Journal Article · Fri Jul 21 00:00:00 EDT 2006 · Journal of Chemical Physics · OSTI ID:20864274

Related Subjects