Exciplex Formation and Aggregation Induced Emission in Di‐(<i>N</i>‐benzyl)cyclen and Its Complexes – Selective Fluorescence with Lead(II), and as the Cadmium(II) Complex, with the Chloride Ion

Correia, Bruna; Brown, Thomas R.; Reibenspies, Joseph H.; Lee, Heeseung; Hancock, Robert D.

doi:10.1002/ejic.201800573

Cited by 9 publications

(5 citation statements)

References 54 publications

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“…In the case of fluorophore-substituted cyclens, fluorescent complexes where excimers formed were reported. − We also reported tetra-armed cyclens ( L a – L c ) with fluorophore as side arms and their silver(I) complexes. However, in the silver(I) complexes of cyclens L a – L c , the excimer formation was not observed even if fluorophores have existed in the side arms. , It is considered that the formation of excimer has been difficult due to the steric hindrance when the complex formed the silver(I) complex.…”

Section: Introductionmentioning

confidence: 91%

Argentivorous Molecules with Chromophores in Side Arms: Silver Ion-Induced Turn On and Turn Off of Fluorescence

Taniguchi

Kikukawa

et al. 2021

Inorg. Chem.

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The synthesis of argentivorous molecules (L1 and L2 ) having two chromophores (4-(anthracen-9-yl)benzyl or 4-(pyren-1-yl)benzyl groups) and two benzyl groups and the fluorescence properties of their silver complexes in a solution and the solid state are reported. A crystallographic approach for the Ag+ complexes with L1 and L2 revealed that the observed fluorescence changes stem from the excimer formation and extinction of fluorescent. Furthermore, binding stabilities of L1 and L2 toward Ag+ ions were estimated by the Ag+-induced UV–vis and PL spectral changes.

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Section: Introductionmentioning

confidence: 91%

Argentivorous Molecules with Chromophores in Side Arms: Silver Ion-Induced Turn On and Turn Off of Fluorescence

Taniguchi

Kikukawa

et al. 2021

Inorg. Chem.

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“… Coordination about the metal ion in [Cu( 2 )(OCHNMe 2 ) 2 ](PF 6 ) 2 · 2(OCHNMe 2 ) [ 57 ]. Atoms are drawn as 50% probability ellipsoids.…”

Section: Figurementioning

confidence: 99%

“…The cyclam ligand 2 has been complexed to a number of metal ions previously [ 49 , 50 , 51 , 52 , 53 , 54 , 55 ], but the characterization of its complexes has been limited. The cyclen analogue 1 has a long history [ 56 ] but only a few published complexes, most of which are large second- and third-row transition metal ions [ 54 , 57 , 58 , 59 , 60 ]. Therefore, we aimed to synthesize and characterize the complexes of these two analogous tetraazamacrocycle ligands for comparison.…”

Section: Introductionmentioning

confidence: 99%

A Bridge too Far? Comparison of Transition Metal Complexes of Dibenzyltetraazamacrocycles with and without Ethylene Cross-Bridges: X-ray Crystal Structures, Kinetic Stability, and Electronic Properties

et al. 2023

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Tetraazamacrocycles, cyclic molecules with four nitrogen atoms, have long been known to produce highly stable transition metal complexes. Cross-bridging such molecules with two-carbon chains has been shown to enhance the stability of these complexes even further. This provides enough stability to use the resulting compounds in applications as diverse and demanding as aqueous, green oxidation catalysis all the way to drug molecules injected into humans. Although the stability of these compounds is believed to result from the increased rigidity and topological complexity imparted by the cross-bridge, there is insufficient experimental data to exclude other causes. In this study, standard organic and inorganic synthetic methods were used to produce unbridged dibenzyl tetraazamacrocycle complexes of Co, Ni, Cu, and Zn that are analogues of known cross-bridged tetraazamacrocycles and their transition metal complexes to allow direct comparison of molecules that are identical except for the cross-bridge. The syntheses of the known tetraazamacrocycles and the new transition metal complexes were successful with high yields and purity. Initial chemical characterization of the complexes was conducted by UV-Visible spectroscopy, while cyclic voltammetry showed more marked differences in electronic properties from bridged versions. Direct comparison studies of the unbridged and bridged compounds’ kinetic stabilities, as demonstrated by decomposition using high acid concentration and elevated temperature, showed that the cyclen-based complex stability did not benefit from cross-bridging. This is likely due to poor complementarity with the Cu2+ ion while cyclam-based complexes benefited greatly. We conclude that ligand–metal complementarity must be maintained in order for the topological and rigidity constraints imparted by the cross-bridge to contribute significantly to complex robustness.

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“…Cyclen is a 12-membered cyclic polyamine which forms stable complexes with transition-metal ions as well as main group metal ions. − To enhance the coordination ability and applicability, substituted cyclens in which functional groups or macrocycles were adopted in the cyclen amine part were reported, and their complexes were determined. − For example, Hancock et al have reported lead(II), copper(II), silver(I), and cadmium(II) complexes of di( N -benzyl)cyclen. Using cadmium(II) complex, the selective fluorescence sensor for the chloride anion was investigated . Rosenthal et al have prepared nickel(II) complexes of ancillary amide group substituted cyclen and revealed their applicability for electrocatalysts in the reduction of CO 2 to CO .…”

Section: Introductionmentioning

confidence: 99%

“…Using cadmium(II) complex, the selective fluorescence sensor for the chloride anion was investigated. 10 Rosenthal et al have prepared nickel(II) complexes of ancillary amide group substituted cyclen and revealed their applicability for electrocatalysts in the reduction of CO 2 to CO. 11 Delgado et al have synthesized m-xylyl-bis-cyclen for the first time and determined their copper(II) and zinc(II) complexes. 14 We have reported that silver(I) complexes with cyclen having two, three, and four aromatic side arms behave like insectivorous plants (e.g., Venus flytrap).…”

Section: ■ Introductionmentioning

confidence: 99%

Mole-Ratio-Dependent Reversible Transformation between 2:2 and Cyclic 3:6 Silver(I) Complexes with an Argentivorous Molecule

Abe

Takahashi

et al. 2021

Inorg. Chem.

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A tetra-armed cyclen (L) with two substituted 3,5-difluorobenzyl and two substituted pyridine-4-yl methyl groups at the 1,4- and 7,10-positions of the cyclen ring as side arms was synthesized. When L was reacted with 1 equiv of the silver(I), dimetallo[3.3]paracyclophane-like 2:2 cyclic dimer, [Ag2(L)2](PF6)2, was obtained. The reaction of L with 2 equiv of silver(I) gave a 3:6 cyclic trimer, [Ag6(L)3(CH3CN)3](OTf)6·3CH3CN. Furthermore, reversible complexation between the 2:2 cyclic dimer and 3:6 cyclic trimer was confirmed by 1H NMR and the CSI mass in the addition of silver(I) or the [2.2.2]cryptand.

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Exciplex Formation and Aggregation Induced Emission in Di‐(N‐benzyl)cyclen and Its Complexes – Selective Fluorescence with Lead(II), and as the Cadmium(II) Complex, with the Chloride Ion

Cited by 9 publications

References 54 publications

Argentivorous Molecules with Chromophores in Side Arms: Silver Ion-Induced Turn On and Turn Off of Fluorescence

Argentivorous Molecules with Chromophores in Side Arms: Silver Ion-Induced Turn On and Turn Off of Fluorescence

A Bridge too Far? Comparison of Transition Metal Complexes of Dibenzyltetraazamacrocycles with and without Ethylene Cross-Bridges: X-ray Crystal Structures, Kinetic Stability, and Electronic Properties

Mole-Ratio-Dependent Reversible Transformation between 2:2 and Cyclic 3:6 Silver(I) Complexes with an Argentivorous Molecule

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