Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium
Abstract Bond rotation is an important phenomenon governing the fate of reactions. In particular, heterogeneously substituted ethane derivatives provide distinct structural conformations around the bond, empowering them as ideal systems for studying the rotation along carbon-containing single bonds....
Saved in:
| Main Authors: | , , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-02-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57279-7 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849768365389774848 |
|---|---|
| author | Seonggon Lee Hosung Ki Donghwan Im Jungmin Kim Yunbeom Lee Jain Gu Alekos Segalina Jun Heo Yongjun Cha Kyung Won Lee Doyeong Kim Jeongho Kim Rory Ma Jae Hyuk Lee Hyotcherl Ihee |
| author_facet | Seonggon Lee Hosung Ki Donghwan Im Jungmin Kim Yunbeom Lee Jain Gu Alekos Segalina Jun Heo Yongjun Cha Kyung Won Lee Doyeong Kim Jeongho Kim Rory Ma Jae Hyuk Lee Hyotcherl Ihee |
| author_sort | Seonggon Lee |
| collection | DOAJ |
| description | Abstract Bond rotation is an important phenomenon governing the fate of reactions. In particular, heterogeneously substituted ethane derivatives provide distinct structural conformations around the bond, empowering them as ideal systems for studying the rotation along carbon-containing single bonds. However, structural dynamics of ultrafast single-bond rotation, especially along C–C• bonds, have remained elusive as tracking the detailed changes in structural parameters during the rotational isomerization is challenging with conventional spectroscopic tools. Here, we employ femtosecond time-resolved X-ray liquidography to visualize the rotational isomerization between anti and gauche conformers of tetrafluoroiodoethyl radical (C2F4I•) and 1,2-tetrafluorodiiodoethane (C2F4I2), simultaneously. The TRXL data captures perturbations in conformer ratios and structures of each reacting species, revealing that the rotational isomerization of C2F4I• and C2F4I2 follows anti-to-gauche and gauche-to-anti paths with time constants of 1.2 ps and 26 ps, respectively. These findings also align with the computational predictions. This work offers an atomic-level insight into the kinetics and structural dynamics of single-bond rotation. |
| format | Article |
| id | doaj-art-bd660e0b8e0448f5a024b5c7c0ba562d |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-bd660e0b8e0448f5a024b5c7c0ba562d2025-08-20T03:03:50ZengNature PortfolioNature Communications2041-17232025-02-0116111210.1038/s41467-025-57279-7Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibriumSeonggon Lee0Hosung Ki1Donghwan Im2Jungmin Kim3Yunbeom Lee4Jain Gu5Alekos Segalina6Jun Heo7Yongjun Cha8Kyung Won Lee9Doyeong Kim10Jeongho Kim11Rory Ma12Jae Hyuk Lee13Hyotcherl Ihee14Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Center for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Department of Chemistry, Inha University, 100 Inha-ro, Michuhol-guPohang Accelerator LaboratoryPohang Accelerator LaboratoryCenter for Advanced Reaction Dynamics, Institute for Basic Science (IBS)Abstract Bond rotation is an important phenomenon governing the fate of reactions. In particular, heterogeneously substituted ethane derivatives provide distinct structural conformations around the bond, empowering them as ideal systems for studying the rotation along carbon-containing single bonds. However, structural dynamics of ultrafast single-bond rotation, especially along C–C• bonds, have remained elusive as tracking the detailed changes in structural parameters during the rotational isomerization is challenging with conventional spectroscopic tools. Here, we employ femtosecond time-resolved X-ray liquidography to visualize the rotational isomerization between anti and gauche conformers of tetrafluoroiodoethyl radical (C2F4I•) and 1,2-tetrafluorodiiodoethane (C2F4I2), simultaneously. The TRXL data captures perturbations in conformer ratios and structures of each reacting species, revealing that the rotational isomerization of C2F4I• and C2F4I2 follows anti-to-gauche and gauche-to-anti paths with time constants of 1.2 ps and 26 ps, respectively. These findings also align with the computational predictions. This work offers an atomic-level insight into the kinetics and structural dynamics of single-bond rotation.https://doi.org/10.1038/s41467-025-57279-7 |
| spellingShingle | Seonggon Lee Hosung Ki Donghwan Im Jungmin Kim Yunbeom Lee Jain Gu Alekos Segalina Jun Heo Yongjun Cha Kyung Won Lee Doyeong Kim Jeongho Kim Rory Ma Jae Hyuk Lee Hyotcherl Ihee Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium Nature Communications |
| title | Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium |
| title_full | Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium |
| title_fullStr | Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium |
| title_full_unstemmed | Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium |
| title_short | Ultrafast structural dynamics of carbon–carbon single-bond rotation in transient radical species at non-equilibrium |
| title_sort | ultrafast structural dynamics of carbon carbon single bond rotation in transient radical species at non equilibrium |
| url | https://doi.org/10.1038/s41467-025-57279-7 |
| work_keys_str_mv | AT seonggonlee ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT hosungki ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT donghwanim ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT jungminkim ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT yunbeomlee ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT jaingu ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT alekossegalina ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT junheo ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT yongjuncha ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT kyungwonlee ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT doyeongkim ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT jeonghokim ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT roryma ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT jaehyuklee ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium AT hyotcherlihee ultrafaststructuraldynamicsofcarboncarbonsinglebondrotationintransientradicalspeciesatnonequilibrium |