A smart post-synthetic route towards [Fe2Co2] molecular capsules with electron transfer and bidirectional switching behaviors

Lingyi Meng; Yi Fei Deng; Shihao Liu; Zhiping Zheng; Yuan Zhu Zhang

doi:10.1007/s11426-021-1043-9

A smart post-synthetic route towards [Fe₂Co₂] molecular capsules with electron transfer and bidirectional switching behaviors

Lingyi Meng, Yi Fei Deng, Shihao Liu, Zhiping Zheng, Yuan Zhu Zhang

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Aldehyde groups were intentionally equipped on the cyanide-bridged [Fe₂Co₂] square molecules: {[(Tp*)Fe(CN)₃Co(bpy^CHO)₂]₂-[PF₆]₂}·4MeOH (1, Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; bpy^CHO = 4-formyl-4′-methyl-2,2′-bipyridine), thus providing chemical-active windows for post-modification towards desired functions. In this contribution, by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative (bpy^CHO) and alkyl diamines (H₂N-(CH₂)_nNH₂), two discrete [Fe₂Co₂] compounds {[(Tp∗)Fe(CN)3Co(bpyC=N(CH2)nN=Cbpy)]2[PF6]2}⋅6DMF(2,n=5;3,n=7) were prepared, where the cyanide-bridged [Fe₂Co₂] square cores were encapsulated by the flexible alkyl chains. Variable-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo (T_1/2 = 233 K (2) and 237 K (3)) and photo-induced electron transfer event accompanying spin transition between the diamagnetic [Fe^II_LS2Co^III_LS2] state and the paramagnetic [Fe^III_LS2Co^II_HS2] state (LS, low spin; HS, high spin). In addition, the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K. [Figure not available: see fulltext.].

Original language	English (US)
Pages (from-to)	1340-1348
Number of pages	9
Journal	Science China Chemistry
Volume	64
Issue number	8
DOIs	https://doi.org/10.1007/s11426-021-1043-9
State	Published - Aug 2021
Externally published	Yes

Keywords

bidirectional switch
capsule
cyanide
electron transfer
post-modification
supramolecule

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1007/s11426-021-1043-9

Cite this

@article{3fdb279990b64267aaa0d1b85509ee17,

title = "A smart post-synthetic route towards [Fe2Co2] molecular capsules with electron transfer and bidirectional switching behaviors",

abstract = "Aldehyde groups were intentionally equipped on the cyanide-bridged [Fe2Co2] square molecules: {[(Tp*)Fe(CN)3Co(bpyCHO)2]2-[PF6]2}·4MeOH (1, Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; bpyCHO = 4-formyl-4′-methyl-2,2′-bipyridine), thus providing chemical-active windows for post-modification towards desired functions. In this contribution, by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative (bpyCHO) and alkyl diamines (H2N-(CH2)nNH2), two discrete [Fe2Co2] compounds {[(Tp∗)Fe(CN)3Co(bpyC=N(CH2)nN=Cbpy)]2[PF6]2}⋅6DMF(2,n=5;3,n=7) were prepared, where the cyanide-bridged [Fe2Co2] square cores were encapsulated by the flexible alkyl chains. Variable-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo (T1/2 = 233 K (2) and 237 K (3)) and photo-induced electron transfer event accompanying spin transition between the diamagnetic [FeIILS2CoIIILS2] state and the paramagnetic [FeIIILS2CoIIHS2] state (LS, low spin; HS, high spin). In addition, the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K. [Figure not available: see fulltext.].",

keywords = "bidirectional switch, capsule, cyanide, electron transfer, post-modification, supramolecule",

author = "Lingyi Meng and Deng, {Yi Fei} and Shihao Liu and Zhiping Zheng and Zhang, {Yuan Zhu}",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (21671095, 21901108), and start-up fund from SUSTech. We thank Dr. Bin Chen from Soochow University for UV-Vis-NIR measurements. Publisher Copyright: {\textcopyright} 2021, Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature.",

year = "2021",

month = aug,

doi = "10.1007/s11426-021-1043-9",

language = "English (US)",

volume = "64",

pages = "1340--1348",

journal = "Science China Chemistry",

issn = "1674-7291",

publisher = "Science China Press",

number = "8",

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TY - JOUR

T1 - A smart post-synthetic route towards [Fe2Co2] molecular capsules with electron transfer and bidirectional switching behaviors

AU - Meng, Lingyi

AU - Deng, Yi Fei

AU - Liu, Shihao

AU - Zheng, Zhiping

AU - Zhang, Yuan Zhu

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (21671095, 21901108), and start-up fund from SUSTech. We thank Dr. Bin Chen from Soochow University for UV-Vis-NIR measurements. Publisher Copyright: © 2021, Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature.

PY - 2021/8

Y1 - 2021/8

N2 - Aldehyde groups were intentionally equipped on the cyanide-bridged [Fe2Co2] square molecules: {[(Tp*)Fe(CN)3Co(bpyCHO)2]2-[PF6]2}·4MeOH (1, Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; bpyCHO = 4-formyl-4′-methyl-2,2′-bipyridine), thus providing chemical-active windows for post-modification towards desired functions. In this contribution, by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative (bpyCHO) and alkyl diamines (H2N-(CH2)nNH2), two discrete [Fe2Co2] compounds {[(Tp∗)Fe(CN)3Co(bpyC=N(CH2)nN=Cbpy)]2[PF6]2}⋅6DMF(2,n=5;3,n=7) were prepared, where the cyanide-bridged [Fe2Co2] square cores were encapsulated by the flexible alkyl chains. Variable-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo (T1/2 = 233 K (2) and 237 K (3)) and photo-induced electron transfer event accompanying spin transition between the diamagnetic [FeIILS2CoIIILS2] state and the paramagnetic [FeIIILS2CoIIHS2] state (LS, low spin; HS, high spin). In addition, the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K. [Figure not available: see fulltext.].

AB - Aldehyde groups were intentionally equipped on the cyanide-bridged [Fe2Co2] square molecules: {[(Tp*)Fe(CN)3Co(bpyCHO)2]2-[PF6]2}·4MeOH (1, Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; bpyCHO = 4-formyl-4′-methyl-2,2′-bipyridine), thus providing chemical-active windows for post-modification towards desired functions. In this contribution, by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative (bpyCHO) and alkyl diamines (H2N-(CH2)nNH2), two discrete [Fe2Co2] compounds {[(Tp∗)Fe(CN)3Co(bpyC=N(CH2)nN=Cbpy)]2[PF6]2}⋅6DMF(2,n=5;3,n=7) were prepared, where the cyanide-bridged [Fe2Co2] square cores were encapsulated by the flexible alkyl chains. Variable-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo (T1/2 = 233 K (2) and 237 K (3)) and photo-induced electron transfer event accompanying spin transition between the diamagnetic [FeIILS2CoIIILS2] state and the paramagnetic [FeIIILS2CoIIHS2] state (LS, low spin; HS, high spin). In addition, the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K. [Figure not available: see fulltext.].

KW - bidirectional switch

KW - capsule

KW - cyanide

KW - electron transfer

KW - post-modification

KW - supramolecule

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DO - 10.1007/s11426-021-1043-9

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AN - SCOPUS:85111157671

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