Dual Emission with Efficient Phosphorescence Promoted by Intermolecular Halogen Interactions in Luminescent Tetranuclear Zinc(II) Clusters

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2024 Aug 9

PMID 39119626

Authors

Fumiya Kobayashi

Yuta Takatsu

Daisuke Saito

Masaki Yoshida

Masako Kato

Makoto Tadokoro

Affiliations

Soon will be listed here.

Abstract

The development of Zn-based phosphorescent materials, associated with a ligand-centered (LC) transition, is extremely limited. Herein, we demonstrated dual emissions including fluorescence and phosphorescence in luminescent tetranuclear Zn(II) clusters [ZnL(μ-OMe)X] ( = methyl-5-iode-3-methoxysalicylate; X = I, Br, Cl), incorporating iodine-substituted ligands. Single-crystal X-ray structural analyses and variable-temperature emission spectra studies revealed the presence of iodine substitutions, and intermolecular halogen interactions produced the internal/external heavy-atom effects and yielded strong green phosphorescence with a long emission lifetime (λ = 510-522 nm, Φ = 0.28-0.47, τ = 0.78-0.95 ms, at 77 K). This work provided a new example that the introduction of halogen interactions is an advantageous approach for inducing phosphorescence in fluorescent metal complexes.

References

Yan Z, Lin X, Sun S, Ma X, Tian H . Activating Room-Temperature Phosphorescence of Organic Luminophores via External Heavy-Atom Effect and Rigidity of Ionic Polymer Matrix*. Angew Chem Int Ed Engl. 2021; 60(36):19735-19739. DOI: 10.1002/anie.202108025. View

Kobayashi F, Ohtani R, Teraoka S, Yoshida M, Kato M, Zhang Y . Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters. Chemistry. 2019; 25(23):5875-5879. DOI: 10.1002/chem.201900343. View

Lee J, Chen H, Batagoda T, Coburn C, Djurovich P, Thompson M . Deep blue phosphorescent organic light-emitting diodes with very high brightness and efficiency. Nat Mater. 2015; 15(1):92-8. DOI: 10.1038/nmat4446. View

Dai W, Niu X, Wu X, Ren Y, Zhang Y, Li G . Halogen Bonding: A New Platform for Achieving Multi-Stimuli-Responsive Persistent Phosphorescence. Angew Chem Int Ed Engl. 2022; 61(13):e202200236. DOI: 10.1002/anie.202200236. View

Kukhta N, Bryce M . Dual emission in purely organic materials for optoelectronic applications. Mater Horiz. 2021; 8(1):33-55. DOI: 10.1039/d0mh01316a. View

Wei J, Ou W, Luo J, Kuang D . Zero-Dimensional Zn-Based Halides with Ultra-Long Room-Temperature Phosphorescence for Time-Resolved Anti-Counterfeiting. Angew Chem Int Ed Engl. 2022; 61(33):e202207985. DOI: 10.1002/anie.202207985. View

Wada Y, Maruchi T, Ishii R, Sunada Y . Visible Light Responsive Dinuclear Zinc Complex Consisting of Proximally Arranged Two d -Zinc Centers. Angew Chem Int Ed Engl. 2023; 62(50):e202310571. DOI: 10.1002/anie.202310571. View

Behera S, Park S, Gierschner J . Dual Emission: Classes, Mechanisms, and Conditions. Angew Chem Int Ed Engl. 2020; 60(42):22624-22638. DOI: 10.1002/anie.202009789. View

Wenger O . Photoactive Complexes with Earth-Abundant Metals. J Am Chem Soc. 2018; 140(42):13522-13533. DOI: 10.1021/jacs.8b08822. View

10.

Ma Y, Qi Z, Xiao G, Fang X, Yan D . Metal-Halide Coordination Polymers with Excitation Wavelength- and Time-Dependent Ultralong Room-Temperature Phosphorescence. Inorg Chem. 2022; 61(41):16477-16483. DOI: 10.1021/acs.inorgchem.2c02750. View

11.

Hsu C, Lin C, Chung M, Chi Y, Lee G, Chou P . Systematic investigation of the metal-structure-photophysics relationship of emissive d10-complexes of group 11 elements: the prospect of application in organic light emitting devices. J Am Chem Soc. 2011; 133(31):12085-99. DOI: 10.1021/ja2026568. View

12.

Li H, Li H, Wang W, Tao Y, Wang S, Yang Q . Stimuli-Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence. Angew Chem Int Ed Engl. 2020; 59(12):4756-4762. DOI: 10.1002/anie.201915164. View

13.

Bolton O, Lee K, Kim H, Lin K, Kim J . Activating efficient phosphorescence from purely organic materials by crystal design. Nat Chem. 2011; 3(3):205-10. DOI: 10.1038/nchem.984. View

14.

Lozada I, Braun J, Williams J, Herbert D . Yellow-Emitting, Pseudo-Octahedral Zinc Complexes of Benzannulated N^N^O Pincer-Type Ligands. Inorg Chem. 2022; 61(44):17568-17578. DOI: 10.1021/acs.inorgchem.2c02585. View

15.

Cariati E, Forni A, Lucenti E, Marinotto D, Previtali A, Righetto S . Extrinsic Heavy Metal Atom Effect on the Solid-State Room Temperature Phosphorescence of Cyclic Triimidazole. Chem Asian J. 2019; 14(6):853-858. DOI: 10.1002/asia.201801604. View

16.

Yin Zhang K, Yu Q, Wei H, Liu S, Zhao Q, Huang W . Long-Lived Emissive Probes for Time-Resolved Photoluminescence Bioimaging and Biosensing. Chem Rev. 2018; 118(4):1770-1839. DOI: 10.1021/acs.chemrev.7b00425. View

17.

Zhao Y, Yang X, Lu X, Yang C, Fan N, Yang Z . {Zn} Cluster Based Metal-Organic Framework with Enhanced Room-Temperature Phosphorescence and Optoelectronic Performances. Inorg Chem. 2019; 58(9):6215-6221. DOI: 10.1021/acs.inorgchem.9b00450. View

18.

Lo K . Luminescent Rhenium(I) and Iridium(III) Polypyridine Complexes as Biological Probes, Imaging Reagents, and Photocytotoxic Agents. Acc Chem Res. 2015; 48(12):2985-95. DOI: 10.1021/acs.accounts.5b00211. View

19.

Peng Q, Ma H, Shuai Z . Theory of Long-Lived Room-Temperature Phosphorescence in Organic Aggregates. Acc Chem Res. 2020; 54(4):940-949. DOI: 10.1021/acs.accounts.0c00556. View

20.

Sun X, Zhang B, Li X, Trindle C, Zhang G . External Heavy-Atom Effect via Orbital Interactions Revealed by Single-Crystal X-ray Diffraction. J Phys Chem A. 2016; 120(29):5791-7. DOI: 10.1021/acs.jpca.6b03867. View