Crystal polymorphism and crystalline-state photochromism of a rhodium dithionite complex with n-methoxypropyl moieties

Yuu Kajiwara; Hidetaka Nakai

doi:10.1039/d1ce01613j

Crystal polymorphism and crystalline-state photochromism of a rhodium dithionite complex with n-methoxypropyl moieties

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Abstract

A rhodium dinuclear complex having n-methoxypropyltetramethylcyclopentadienyl (Cp^MPro = η⁵-C₅Me₄nC₃H₆OCH₃) and photoresponsive dithionite (μ-O₂SSO₂) ligands, [(Cp^MProRh)₂(μ-CH₂)₂(μ-O₂SSO₂)] (1^MPro), was found to form two polymorphic crystals (a previously reported block-like α-crystal and a newly obtained plate-like β-crystal). The crystalline-state photochromism of 1^MPro in the β-crystal, which involves photoisomerization from the μ-O₂SSO₂ complex (1^MPro) to the corresponding μ-O₂SOSO complex (2^MPro) and a thermal back-reaction from 2^MPro to 1^MPro, was successfully studied by performing time-dependent X-ray diffraction experiments. The results obtained from the β-crystal were compared with the previous results obtained from the α-crystal: the thermal back-reaction in the β-crystal is eight times longer than that in the α-crystal.

Original language	English
Pages (from-to)	1437-1441
Number of pages	5
Journal	CrystEngComm
Volume	24
Issue number	7
DOIs	https://doi.org/10.1039/d1ce01613j
Publication status	Published - Feb 21 2022
Externally published	Yes

All Science Journal Classification (ASJC) codes

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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title = "Crystal polymorphism and crystalline-state photochromism of a rhodium dithionite complex with n-methoxypropyl moieties",

abstract = "A rhodium dinuclear complex having n-methoxypropyltetramethylcyclopentadienyl (CpMPro = η5-C5Me4nC3H6OCH3) and photoresponsive dithionite (μ-O2SSO2) ligands, [(CpMProRh)2(μ-CH2)2(μ-O2SSO2)] (1MPro), was found to form two polymorphic crystals (a previously reported block-like α-crystal and a newly obtained plate-like β-crystal). The crystalline-state photochromism of 1MPro in the β-crystal, which involves photoisomerization from the μ-O2SSO2 complex (1MPro) to the corresponding μ-O2SOSO complex (2MPro) and a thermal back-reaction from 2MPro to 1MPro, was successfully studied by performing time-dependent X-ray diffraction experiments. The results obtained from the β-crystal were compared with the previous results obtained from the α-crystal: the thermal back-reaction in the β-crystal is eight times longer than that in the α-crystal.",

author = "Yuu Kajiwara and Hidetaka Nakai",

note = "Funding Information: This work was supported by JSPS KAKENHI Grant Number JP21K05103. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry",

year = "2022",

month = feb,

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doi = "10.1039/d1ce01613j",

language = "English",

volume = "24",

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journal = "CrystEngComm",

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T1 - Crystal polymorphism and crystalline-state photochromism of a rhodium dithionite complex with n-methoxypropyl moieties

AU - Kajiwara, Yuu

AU - Nakai, Hidetaka

N1 - Funding Information: This work was supported by JSPS KAKENHI Grant Number JP21K05103. Publisher Copyright: © The Royal Society of Chemistry

PY - 2022/2/21

Y1 - 2022/2/21

N2 - A rhodium dinuclear complex having n-methoxypropyltetramethylcyclopentadienyl (CpMPro = η5-C5Me4nC3H6OCH3) and photoresponsive dithionite (μ-O2SSO2) ligands, [(CpMProRh)2(μ-CH2)2(μ-O2SSO2)] (1MPro), was found to form two polymorphic crystals (a previously reported block-like α-crystal and a newly obtained plate-like β-crystal). The crystalline-state photochromism of 1MPro in the β-crystal, which involves photoisomerization from the μ-O2SSO2 complex (1MPro) to the corresponding μ-O2SOSO complex (2MPro) and a thermal back-reaction from 2MPro to 1MPro, was successfully studied by performing time-dependent X-ray diffraction experiments. The results obtained from the β-crystal were compared with the previous results obtained from the α-crystal: the thermal back-reaction in the β-crystal is eight times longer than that in the α-crystal.

AB - A rhodium dinuclear complex having n-methoxypropyltetramethylcyclopentadienyl (CpMPro = η5-C5Me4nC3H6OCH3) and photoresponsive dithionite (μ-O2SSO2) ligands, [(CpMProRh)2(μ-CH2)2(μ-O2SSO2)] (1MPro), was found to form two polymorphic crystals (a previously reported block-like α-crystal and a newly obtained plate-like β-crystal). The crystalline-state photochromism of 1MPro in the β-crystal, which involves photoisomerization from the μ-O2SSO2 complex (1MPro) to the corresponding μ-O2SOSO complex (2MPro) and a thermal back-reaction from 2MPro to 1MPro, was successfully studied by performing time-dependent X-ray diffraction experiments. The results obtained from the β-crystal were compared with the previous results obtained from the α-crystal: the thermal back-reaction in the β-crystal is eight times longer than that in the α-crystal.

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Crystal polymorphism and crystalline-state photochromism of a rhodium dithionite complex with n-methoxypropyl moieties

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