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Tuning the architectures and luminescence properties of Cu(I) compounds of phenyl and carboranyl pyrazoles: the impact of 2D versus 3D aromatic moieties in the ligand backbone

Tuning the architectures and luminescence properties of Cu(I) compounds of phenyl and carboranyl pyrazoles: the impact of 2D versus 3D aromatic moieties in the ligand backbone
Tuning the architectures and luminescence properties of Cu(I) compounds of phenyl and carboranyl pyrazoles: the impact of 2D versus 3D aromatic moieties in the ligand backbone
Incorporation of one or two o-carborane moieties at the backbone of the pyrazole ring was achieved by lithiation and nucleophilic addition onto the corresponding 3,5-dimethyl-1-(2-toluene-p-sulfonyloxyethyl)pyrazole. Two monosubstituted carboranyl pyrazoles (L2 and L3) and one disubstituted carboranyl pyrazole (L4) were synthesized and fully characterized. All new compounds, and the corresponding monosubstituted phenylderivative (L1) behave as N-type ligands upon coordination with CuI to afford different polynuclear Cu(I) compounds 1–4. Compounds 1–4 were fully characterized and their molecular structures were determined by X-ray diffraction. It is noteworthy that whereas the pyrazolylphenyl ligand L1, without o-carborane, provides a 1D coordination polymer (1), ligands containing carborane, L2–L3, affords 0D coordination compounds 2 and 3, and disubstituted carboranyl pyrazole ligand L4 gives rise to a 3D coordination polymer. The photoluminescence behaviour of compounds 1–4 has been investigated in the solid state and by TDDFT calculations for molecular compounds 2 and 3. Complex 2 exhibits blue emission with a maximum at 483 nm and a high fluorescence quantum yield of 66.5%. According to TDDFT calculations the emission occurs from LUMO to HOMO−1 and HOMO−2 and deexcitation could be described as cluster-centred excited state of d–s transition in origin. This result contradicts previous studies of scarce tri-coordinated rhombohedral Cu(I) clusters, where it was assumed the origin of their emissions is (X + M)LCT in nature by analogy with tetra-coordinated rhombohedral Cu(I) clusters. Complex 3 exhibits very weak emission (ΦF of 5%) in the green region with a maximum at 517 nm, which according to TDDFT is through a 3CC state. Calculations also show that, upon excitation, 3 suffers a notable distortion resulting in the total cleavage of the Cu4I4 framework. This cleavage could be the cause of the relatively large Stokes shift observed for 3. To the best of our knowledge, this is the first time that such behaviour is observed for this type of octahedral compounds. Additionally, the 1D polymer 1 exhibits weak fluorescence emission in the orange range with a maximum at 609 nm and a remarkable Stokes shift, whereas the 3D polymer 4 exhibits a similar emission to compound 2, with a moderate quantum yield (ΦF of 13.7%).
2050-7526
7643-7657
Soldevila-Sanmartín, Joan
73e426a4-90a6-443b-b858-06cb21c0529c
Ruiz, Eliseo
1994cd8f-3b20-4d3f-8a60-06c2765be53d
Choquesillo-Lazarte, Duane
b96b9413-2131-44ce-880c-243a1c00e234
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Núñez, Rosario
502e95d3-a1dc-4abd-9c4b-45f231d8614e
Pons, Josefina
a339c58c-7ad1-429a-8f82-1c5523a453ed
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Soldevila-Sanmartín, Joan
73e426a4-90a6-443b-b858-06cb21c0529c
Ruiz, Eliseo
1994cd8f-3b20-4d3f-8a60-06c2765be53d
Choquesillo-Lazarte, Duane
b96b9413-2131-44ce-880c-243a1c00e234
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Núñez, Rosario
502e95d3-a1dc-4abd-9c4b-45f231d8614e
Pons, Josefina
a339c58c-7ad1-429a-8f82-1c5523a453ed
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652

Soldevila-Sanmartín, Joan, Ruiz, Eliseo, Choquesillo-Lazarte, Duane, Light, Mark, Viñas, Clara, Teixidor, Francesc, Núñez, Rosario, Pons, Josefina and Planas, José Giner (2021) Tuning the architectures and luminescence properties of Cu(I) compounds of phenyl and carboranyl pyrazoles: the impact of 2D versus 3D aromatic moieties in the ligand backbone. Journal of Materials Chemistry C, 9, 7643-7657. (doi:10.1039/D1TC01395E).

Record type: Article

Abstract

Incorporation of one or two o-carborane moieties at the backbone of the pyrazole ring was achieved by lithiation and nucleophilic addition onto the corresponding 3,5-dimethyl-1-(2-toluene-p-sulfonyloxyethyl)pyrazole. Two monosubstituted carboranyl pyrazoles (L2 and L3) and one disubstituted carboranyl pyrazole (L4) were synthesized and fully characterized. All new compounds, and the corresponding monosubstituted phenylderivative (L1) behave as N-type ligands upon coordination with CuI to afford different polynuclear Cu(I) compounds 1–4. Compounds 1–4 were fully characterized and their molecular structures were determined by X-ray diffraction. It is noteworthy that whereas the pyrazolylphenyl ligand L1, without o-carborane, provides a 1D coordination polymer (1), ligands containing carborane, L2–L3, affords 0D coordination compounds 2 and 3, and disubstituted carboranyl pyrazole ligand L4 gives rise to a 3D coordination polymer. The photoluminescence behaviour of compounds 1–4 has been investigated in the solid state and by TDDFT calculations for molecular compounds 2 and 3. Complex 2 exhibits blue emission with a maximum at 483 nm and a high fluorescence quantum yield of 66.5%. According to TDDFT calculations the emission occurs from LUMO to HOMO−1 and HOMO−2 and deexcitation could be described as cluster-centred excited state of d–s transition in origin. This result contradicts previous studies of scarce tri-coordinated rhombohedral Cu(I) clusters, where it was assumed the origin of their emissions is (X + M)LCT in nature by analogy with tetra-coordinated rhombohedral Cu(I) clusters. Complex 3 exhibits very weak emission (ΦF of 5%) in the green region with a maximum at 517 nm, which according to TDDFT is through a 3CC state. Calculations also show that, upon excitation, 3 suffers a notable distortion resulting in the total cleavage of the Cu4I4 framework. This cleavage could be the cause of the relatively large Stokes shift observed for 3. To the best of our knowledge, this is the first time that such behaviour is observed for this type of octahedral compounds. Additionally, the 1D polymer 1 exhibits weak fluorescence emission in the orange range with a maximum at 609 nm and a remarkable Stokes shift, whereas the 3D polymer 4 exhibits a similar emission to compound 2, with a moderate quantum yield (ΦF of 13.7%).

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Accepted/In Press date: 27 May 2021
e-pub ahead of print date: 28 May 2021

Identifiers

Local EPrints ID: 449969
URI: http://eprints.soton.ac.uk/id/eprint/449969
ISSN: 2050-7526
PURE UUID: 5cbe1e1b-99be-4363-983b-f6a3762ce30c
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 30 Jun 2021 16:32
Last modified: 01 Jul 2021 01:36

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Contributors

Author: Joan Soldevila-Sanmartín
Author: Eliseo Ruiz
Author: Duane Choquesillo-Lazarte
Author: Mark Light ORCID iD
Author: Clara Viñas
Author: Francesc Teixidor
Author: Rosario Núñez
Author: Josefina Pons
Author: José Giner Planas

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