The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Paul Raithby; Lauren Hatcher

doi:10.1039/c7ce01366c

The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Paul Raithby, Lauren Hatcher

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

21 Citations (SciVal)

Abstract

Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.

Original language	English
Pages (from-to)	6297-6304
Number of pages	9
Journal	CrystEngComm
Volume	19
Issue number	42
DOIs	https://doi.org/10.1039/c7ce01366c
Publication status	Published - 11 Sept 2017

Keywords

Photocrystallography
linkage isomers
palladium
hydrogen bnding

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10.1039/c7ce01366cLicence: CC BY-NC

Cite this

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title = "The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers",

abstract = "Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.",

keywords = "Photocrystallography, linkage isomers, palladium, hydrogen bnding",

author = "Paul Raithby and Lauren Hatcher",

year = "2017",

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doi = "10.1039/c7ce01366c",

language = "English",

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T1 - The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

AU - Raithby, Paul

AU - Hatcher, Lauren

PY - 2017/9/11

Y1 - 2017/9/11

N2 - Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.

AB - Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.

KW - Photocrystallography

KW - linkage isomers

KW - palladium

KW - hydrogen bnding

UR - http://doi.org/10.1039/C7CE01366C

U2 - 10.1039/c7ce01366c

DO - 10.1039/c7ce01366c

M3 - Article

SN - 1466-8033

VL - 19

SP - 6297

EP - 6304

JO - CrystEngComm

JF - CrystEngComm

IS - 42

ER -

The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Abstract

Keywords

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RCaH Impact Acceleration Fellowships and Workshops

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

MC2- Nuclear Magnetic Resonance (NMR)

MC2- X-ray diffraction (XRD)

Cite this

The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

RCaH Impact Acceleration Fellowships and Workshops

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Equipment

MC2- Nuclear Magnetic Resonance (NMR)

MC2- X-ray diffraction (XRD)

Cite this