Systematic Modulation of Hydrogen Bond Donors in Aminoazobenzene Derivatives Provides Further Evidence for the Concerted Inversion Photoisomerization Pathway

Bandara, H. M. Dhammika; Basa, Prem N.; Yan, Jingjing; Camire, Casey E.; MacDonald, John C.; Jackson, Randy K.; Burdette, Shawn C.

doi:10.1002/ejoc.201300525

Cited by 9 publications

(11 citation statements)

References 52 publications

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“…Flash chromatography on silica (CH 2 Cl 2 /CH 3 OH, 25/1) gave AzoAE o P (448 mg, 35.1%) as a dark red solid. Analytical data matched previously reported values …”

Section: Experimental Sectionsupporting

confidence: 86%

“…Although the wavelengths vary, all the five compounds emit with a λ max value between 566 and 610 nm (Table ). Similar to AzoAM o P and AzoAE o P, , none of the new AzoAX x P derivatives exhibit significant evidence for photoisomerization upon irradiation. While quantitative measurements of minimally emissive complexes are imprecise, qualitatively, AzoAE o P and AzoAE p P exhibit brighter emission in comparison to AzoAM m P and AzoAM p P. AzoAM o P appears to emit more weakly than the other four derivatives.…”

Section: Resultsmentioning

confidence: 85%

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Emissive Azobenzenes Delivered on a Silver Coordination Polymer

et al. 2018

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Azobenzene has become a ubiquitous component of functional molecules and polymeric materials because of the light-induced trans→cis isomerization of the diazene group. In contrast, there are very few applications utilizing azobenzene luminescence since excitation energy typically dissipates via non-radiative pathways. Inspired by our earlier studies with 2,2′-bis[N,N′-(2pyridyl)methyl]diaminoazobenzene (AzoAMoP) and related compounds, we investigated a series of five aminoazobenzene derivatives and their corresponding silver complexes. Four of the aminoazobenzene ligands, which exhibit no emission under ambient conditions, form silver coordination polymers that are luminescent at room temperature. AzoAEpP (2,2′-bis[N,N′-(4pyridyl)ethyl]diaminoazobenzene) assembles into a three-dimensional coordination polymer 2 (AgAAEpP) that undergoes a reversible loss of emission upon the addition of metal coordinating analytes like pyridine. The switching behavior is consistent with the disassembly-reassembly of the coordination polymer driven by displacement of the aminoazobenzene ligands by coordinating analytes.

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“…Flash chromatography on silica (CH 2 Cl 2 /CH 3 OH, 25/1) gave AzoAE o P (448 mg, 35.1%) as a dark red solid. Analytical data matched previously reported values …”

Section: Experimental Sectionsupporting

confidence: 86%

Section: Resultsmentioning

confidence: 85%

Emissive Azobenzenes Delivered on a Silver Coordination Polymer

et al. 2018

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“…It is well‐known that intramolecular H‐bonding interactions involving the nitrogen atom of the N=N group may strongly influence the switching equilibrium of the azobenzene moiety. For example, in molecules 19 a – b , the intramolecular H‐bonds involving the amine group a H‐bond donor and the azo group and the pyridine nitrogen as the acceptor suppress the E → Z photoisomerization and strongly accelerates the thermal recovery process (Figure ) . The isomerization of azobenzene occurs via a concerted inversion mechanism where both aryl rings must adopt a collinear arrangement prior to inversion.…”

Section: Configurational Selection Following H‐bonding Complexes Formmentioning

confidence: 99%

Configurational Selection in Azobenzene‐Based Supramolecular Systems Through Dual‐Stimuli Processes

Tecilla

Bonifazi

2020

ChemistryOpen

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Azobenzene is one of the most studied light-controlled molecular switches and it has been incorporated in a large variety of supramolecular systems to control their structural and functional properties. Given the peculiar isomeric distribution at the photoexcited state (PSS), azobenzene derivatives have been used as photoactive framework to build metastable supramolecular systems that are out of the thermodynamic equilibrium. This could be achieved exploiting the peculiar E/Z photoisomerization process that can lead to isomeric ratios that are unreachable in thermal equilibrium conditions. The challenge in the field is to find molecular architectures that, under given external circumstances, lead to a given isomeric ratio in a reversible and predictable manner, ensuring an ultimate control of the configurational distribution and system composition. By reviewing early and recent works in the field, this review aims at describing photoswitchable systems that, containing an azobenzene dye, display a controlled configurational equilibrium by means of a molecular recognition event. Specifically, examples include programmed photoactive molecular architectures binding cations, anions and H-bonded neutral guests. In these systems the non-covalent molecular recognition adds onto the thermal and light stimuli, equipping the supramolecular architecture with an additional external trigger to select the desired configuration composition.[a] Prof. P. Tecilla

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“…Intramolecular hydrogen bonding interactions involving the nitrogen atom of the NN group may strongly influence the switching equilibrium of the azobenzene moiety. For example, intramolecular hydrogen bonds were reported to suppress the trans → cis photoisomerization and strongly accelerates the thermal recovery process. , Furthermore, in the case of azobenzenes with amino groups in para positions and four methoxy groups in ortho positions, the corresponding azonium form is greatly stabilized . These far-red and near-IR absorbing azonium ions show in contrast to typical azonium ions robust cis – trans photoisomerization in aqueous solutions at neutral pH …”

Section: Introductionmentioning

confidence: 99%

Design of Azobenzene beyond Simple On–Off Behavior

et al. 2021

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Azobenzenes are without a doubt the most widely used light-induced switching units, and there is a plethora of application examples ranging from supramolecular chemistry to material science and biological chemistry. Here, we present a smart azobenzene, in which the photoswitching capability of the azobenzene moiety can be reversibly switched on and off using a second unit (redox switch). This second switching unit is based on the variation of the strength of a chalcogen bond between the azo group and a Te–Ph unit in ortho position to the azo group. This allows the selective switching of only one azobenzene unit in the presence of other azobenzene switches. The entire double-switch is a very simple, small system that can also be easily synthesized. As a result, this double-switch can be used as a smarter replacement for the established azobenzene system in the future. For example, in contrast to the latter this double-switch could be employed to store state information analogous to a flip-flop in digital electronic systems.

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Systematic Modulation of Hydrogen Bond Donors in Aminoazobenzene Derivatives Provides Further Evidence for the Concerted Inversion Photoisomerization Pathway

Cited by 9 publications

References 52 publications

Emissive Azobenzenes Delivered on a Silver Coordination Polymer

Emissive Azobenzenes Delivered on a Silver Coordination Polymer

Configurational Selection in Azobenzene‐Based Supramolecular Systems Through Dual‐Stimuli Processes

Design of Azobenzene beyond Simple On–Off Behavior

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