A series of new emissive mononuclear copper(I) bipyridyl complexes bearing the methoxycarbonyl groups

Chen, Jing‐Lin; Fu, Xing-Feng; Wang, Jin-Yun; Guo, Zong-Hao; Xiao, Yi-Liang; He, Lin; Wen, He‐Rui

doi:10.1016/j.inoche.2015.01.026

Cited by 12 publications

(8 citation statements)

References 23 publications

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“…This phenomenon is usually explained not only by the aforementioned flattening distortions but also by the formation of pentacoordinated exciplexes containing solvent molecules, which deactivate via nonemissive pathways. 32,41,44,51,52 Cooling the solution to lower temperatures resulted in an increase of the emission intensity, which confirms the above statement. Moreover, complexes 1P−3P, 1N, and 3N exhibit a luminescence with structureless MLCT emission bands in frozen 1,2-DCE solution at T = 77 K (Figure S20 and Table S4).…”

Section: Design and Synthesis Of Cu(i) Complexessupporting

confidence: 83%

“…9,39 The molecular structure of 3N is also similar to the ones already reported in literature. 40,41 Additionally, the identity, purity, and phase composition of all polycrystalline powder samples were confirmed by powder Xray diffraction analysis with subsequent comparison of the measured and calculated PXRD patterns for 1P, 3P, 3N, and NN (Figures S17, S18).…”

Section: Design and Synthesis Of Cu(i) Complexessupporting

confidence: 76%

“…The behavior of coordination compounds 1N and 3N is consistent with the already published data for phosphine-diimine Cu(I) complexes. 41,53 In fact, the emission bands show a bathochromic shift at T = 77 K, whereas the excited-state lifetimes seem to increase. The tendency of photophysical parameters to change with decreasing temperature is usually associated with a TADF character of luminescence.…”

Section: Design and Synthesis Of Cu(i) Complexesmentioning

confidence: 99%

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So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes

et al. 2022

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The manipulation of the photophysical properties of molecular emitters can be realized by composing the close environment of the metal center with the “heavier pnictogen atom” effect. Replacing a nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change of the photophysical parameters. Herein, we report on the synthesis of four pairs of novel phosphinine-based and isostructural diimine-based Cu(I) complexes, which feature peculiar photophysical properties, and show how these parameters depend on the “heavier pnictogen atom” effect. The obtained Cu(I) complexes show triplet luminescence with MLCT character, which was investigated by means of spectroscopic and computational methods. It has been found that the photophysical properties of the coordination compounds show a dependency on the rigidity of the ancillary phosphine ligand in an unexpected manner. Replacing the nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change in emission energy and especially in the lifetime of the excited state. The results obtained demonstrate an efficient approach to the design of emissive molecular materials, which allows the construction of luminescent complexes with controlled photophysical properties.

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Section: Design and Synthesis Of Cu(i) Complexessupporting

confidence: 83%

Section: Design and Synthesis Of Cu(i) Complexessupporting

confidence: 76%

Section: Design and Synthesis Of Cu(i) Complexesmentioning

confidence: 99%

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So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes

et al. 2022

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“…In particular, copper(I) complexes have tunable emission properties that can be modulated throughout the visible spectrum depending on the ligand coordinated to the copper(I) center [6,7]. Furthermore, multinuclear Cu(I) complexes [8,9] present photophysical properties different from those of mononuclear complexes [10,11].…”

Section: Introductionmentioning

confidence: 99%

New emissive mononuclear copper (I) complex: Structural and photophysical characterization focusing on solvatochromism, rigidochromism and oxygen sensing in mesoporous solid matrix

Ravaro

Mafud

et al. 2018

Dyes and Pigments

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We report the structural and photophysical property analyses of a new emissive copper (I) complex CuI(PPh3)(L) (1, L = 4,4'-dimethoxy-2,2'-bipyridine) which demonstrates solvatochromism. When recrystallized from acetonitrile, the originally orange color of 1 becomes yellow and demonstrates a blue-shifted, broad emission spectrum. This process is reversed when the yellow solid is redissolved in dichloromethane and recrystallized. The lattice parameters and angles found were a = 17.769 Å, β = 114.05 o and a = 11.555 Å, angle β = 92.70 o for the orange and yellow forms of 1, respectively, and there are notable structure differences for CuI(PPh3)(L) in these two solids. When loaded into a mesoporous silica, the emission blue shift becomes greater, indicating a strong rigidochromic effect at room temperature. The emission from such copper complex loaded mesoporous silica matrix is quenched by oxygen and this quenching has been quantified.

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“…In that case, the unsymmetric substitution of the bipyridine skeleton was achieved by partial decarboxylation of the tetracarboxylic acid precursor. Some examples are known of simple bipyridine ligands unsymmetrically substituted with a carboxylate group at a single 6 position, , although the corresponding 1,10-phenanthroline analogue is more common. − …”

Section: Introductionmentioning

confidence: 99%

Crystal Engineering of 6-Carboxy-4-aryl-2,2′-bipyridine Complexes: Potent Chelators with Intrinsic Intermolecular Affinity

Dalton

Hawes

Gunnlaugsson

2017

Crystal Growth & Design

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Herein we report the coordination chemistry and structural properties of two multifunctional terdentate 2,2′-bipyridine derivatives 4- and 3-(4-nitrophenyl)-2,2′-bipyridine-6-carboxylate, L1/L2, respectively. We report eight new coordination complexes with CdII, CoII, and CoIII, and study their behavior in the crystalline phase with the view of establishing L1 and L2 as robust and functional chelators for use in extended metallosupramolecular systems. The divalent complexes [Cd(L1)2]·H2O 1, [Cd(L2)2] 2, [Co(L1)2] 5, and [Co(L2)2] 7 are mononuclear complexes with distorted octahedral coordination geometries dictated by the two meridionally coordinated L1/L2 ligands. Also reported are two trivalent byproducts [Co(L1)2]NO3 6 and [Co(L2)2]NO3 8 which were formed in trace quantities during the initial screening of complexes 5 and 7, respectively. The extended structures of these complexes are dominated by substantial intermolecular interactions, including anion···π hole interactions. Modification of the reaction conditions from 1 and 2 gives two closely related trinuclear cluster species [Cd3(L1)3(NO3)2(DMF)4]NO3 3 and [Cd3(L2)3(NO3)2(DMF)4]NO3·DMF 4, in which three cadmium ions, with pentagonal bipyramidal coordination geometries, form disc-shaped assemblies with L1/L2, which undergo further weak interactions between neighboring complexes in the crystalline state. With these outcomes L1 and L2 are established as exciting new building blocks for metallosupramolecular assemblies involving d-block metal ions.

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A series of new emissive mononuclear copper(I) bipyridyl complexes bearing the methoxycarbonyl groups

Cited by 12 publications

References 23 publications

So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes

So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes

New emissive mononuclear copper (I) complex: Structural and photophysical characterization focusing on solvatochromism, rigidochromism and oxygen sensing in mesoporous solid matrix

Crystal Engineering of 6-Carboxy-4-aryl-2,2′-bipyridine Complexes: Potent Chelators with Intrinsic Intermolecular Affinity

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