Near-IR absorbing donor–acceptor charge-transfer gallium complex, an example from non-transition metal chemistry

Maleeva, A. V.; Ershova, Irina V.; Trofimova, O. Yu.; Arsenyeva, Kseniya V.; Yakushev, I. A.; Пискунов, А. В.

doi:10.1016/j.mencom.2022.01.027

Cited by 17 publications

(4 citation statements)

References 49 publications

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“…It should be noted that the decrease in the molar extinction coefficient in low-polar solvents for Co II derivative 3 is not observed, despite the formation of a five-coordinate environment of the metal atom. This configuration of the complex can provide charge transfer between the donor and the acceptor [ 114 ]. However, it is significantly inferior to structures with a square-planar geometry.…”

Section: Resultsmentioning

confidence: 99%

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes

et al. 2022

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A series of new charge transfer (CT) chromophores of “α-diimine-MII-catecholate” type (where M is 3d-row transition metals—Cu, Ni, Co) were derived from 4,4′-di-tert-butyl-2,2′-bipyridyl and 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric [CuII(3,6-Cat)(bipytBu)]∙THF (1) and NiII(3,6-Cat)(bipytBu) (2) chromophores, while dimeric complex [CoII(3,6-Cat)(bipytBu)]2∙toluene (3) units two substantially distorted heteroleptic D-MII-A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores 1–3 undergo an effective photoinduced intramolecular charge transfer (λ = 500–715 nm, extinction coefficient up to 104 M−1·cm−1) with a concomitant generation of a less polar excited species, the energy of which is a finely sensitive towards solvent polarity, ensuring a pronounced negative solvatochromic effect. Special attention was paid to energetic characteristics for CT and interacting HOMO/LUMO orbitals that were explored by a synergy of UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT study. The current work sheds light on the dependence of CT peculiarities on the nature of metal centers from various groups of the periodic law. Moreover, the “α-diimine-MII-catecholate” CT chromophores on the base of “late” transition elements with differences in d-level’s electronic structure were compared for the first time.

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Section: Resultsmentioning

confidence: 99%

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes

et al. 2022

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“…Recently, the possibility of intramolecular charge transfer between the donor and acceptor ligands has been demonstrated in gallium(III) [12] and zinc(II) [13] complexes with a distorted tetragonal‐pyramidal coordination polyhedron. The octahedral structure of gallium(III) coordination compounds designed with the same ligand systems does not provide conditions for the occurrence of such charge transfer [12a,14] . At the same time, the realization of charge transfer with absorption in the UV region for distorted octahedral germanium(IV) complexes based on 2,3‐dihydroxynaphthalene ligand and bipyridyl or phenanthroline was recently demonstrated by the authors [15] …”

Section: Introductionmentioning

confidence: 99%

“…At present, the number of papers describing LL'CT complexes based on non-transition elements is not so numerous. Recently, the possibility of intramolecular charge transfer between the donor and acceptor ligands has been demonstrated in gallium(III) [12] and zinc(II) [13] complexes with a distorted tetragonal-pyramidal coordination polyhedron. The octahedral structure of gallium(III) coordination compounds designed with the same ligand systems does not provide conditions for the occurrence of such charge transfer.…”

Section: Introductionmentioning

confidence: 99%

Donor‐Acceptor Tin(IV) Complexes with α‐Diimine and Catecholate Ligands

Klimashevskaya,

Arsenyeva,

Maleeva

et al. 2023

Eur J Inorg Chem

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A series of new octahedral bis‐3,6‐di‐tert‐butylcatecholates based on tin(IV) containing metal‐coordinated N‐donor ligands (substituted iminopyridines and diazabutadienes) has been synthesized and structurally characterized. The compounds, both solid and in solution, are intensely colored. They absorb in the visible region of the spectrum. Charge transfer between the catecholate donor and the diimine acceptor is responsible for the absorption. This observation is in good agreement with the DFT calculations and with the electrochemical studies carried out by CV.

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“…The development of sibling LL CT chromophores based on main-group metals seems exceedingly attractive since it would allow one to cheapen the potential production process. Recently, we have synthesized several LL CT gallium complexes, bearing the quinone-type redox-active ligands as donor and 2,2 -bipyridyl as acceptor [34][35][36]. Furthermore, in the complexes with two differently charged o-quinone ligands, the absorption maximum shifts to the near IR region [35].…”

Section: Introductionmentioning

confidence: 99%

[4,6-Di-tert-butyl-N-(2,6-Dimethylphenyl)-o-Amidophenolato][4,6-Di-tert-butyl-N-(2,6-Dimethylphenyl)-o-Iminobenzosemiquinolato](2,2′-Bipyridyl)Indium(III)

Ershova

Cherkasov

Piskunov

2023

Molbank

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A six-coordinated indium(III) complex (APMe)(imSQMe)In(bipy) (1), bearing two types of redox-active ligands—mono- (imSQMe) and dianion (APMe) of 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzoquinone and 2,2’-bipyridyl—was synthesized and characterized in detail. The intense, well-resolved ESR spectrum of 1 in dichloromethane solution clearly indicates the spin density delocalization between both AP and imSQ ligands. The UV-vis spectrum of 1 possesses an absorption band in the NIR region. The molecular structure of compound 1 was established by single-crystal X-ray diffraction analysis.

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Near-IR absorbing donor–acceptor charge-transfer gallium complex, an example from non-transition metal chemistry

Cited by 17 publications

References 49 publications

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes

Donor‐Acceptor Tin(IV) Complexes with α‐Diimine and Catecholate Ligands

[4,6-Di-tert-butyl-N-(2,6-Dimethylphenyl)-o-Amidophenolato][4,6-Di-tert-butyl-N-(2,6-Dimethylphenyl)-o-Iminobenzosemiquinolato](2,2′-Bipyridyl)Indium(III)

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